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WO2015076399A1 - Glycoluriles ayant un groupe fonctionnel et leur utilisation - Google Patents

Glycoluriles ayant un groupe fonctionnel et leur utilisation Download PDF

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Publication number
WO2015076399A1
WO2015076399A1 PCT/JP2014/081009 JP2014081009W WO2015076399A1 WO 2015076399 A1 WO2015076399 A1 WO 2015076399A1 JP 2014081009 W JP2014081009 W JP 2014081009W WO 2015076399 A1 WO2015076399 A1 WO 2015076399A1
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Prior art keywords
group
glycoluril
resin composition
component
formula
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PCT/JP2014/081009
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English (en)
Japanese (ja)
Inventor
岳 熊野
琢磨 武田
昌三 三浦
隆志 柏原
昇 溝部
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Shikoku Chemicals Corp
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Shikoku Chemicals Corp
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Priority claimed from JP2014218061A external-priority patent/JP2015121775A/ja
Application filed by Shikoku Chemicals Corp filed Critical Shikoku Chemicals Corp
Priority to KR1020167016467A priority Critical patent/KR102305379B1/ko
Priority to US15/038,506 priority patent/US10000622B2/en
Priority to EP14864012.1A priority patent/EP3075735B1/fr
Priority to CN201480064419.1A priority patent/CN105745213A/zh
Priority to EP18167788.1A priority patent/EP3369735A1/fr
Publication of WO2015076399A1 publication Critical patent/WO2015076399A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to glycolurils having a functional group and use thereof.
  • the present invention has at least one carboxyalkyl group, glycidyl group, or allyl group in the molecule as a functional group, and glycolurils useful as components of various resin compositions depending on the functional group, Furthermore, it is related with various useful resin compositions containing them as utilization of such glycolurils.
  • Glycolurils are heterocyclic compounds having four urea nitrogens in the ring structure, and are used for various applications and production of new functional compounds by utilizing the reactivity of the urea nitrogens. Yes.
  • a functional group rich in reactivity for example, a compound having a plurality of allyl groups in the molecule, for example, triallyl isocyanurate, is well known as a crosslinking agent for synthetic resins and synthetic rubbers. Tetraallyl glycolurils having four allyl groups in the molecule that function as a crosslinking agent for resins and synthetic rubbers are also known.
  • a compound in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group is useful as an intermediate for the synthesis of an oxygen-containing compound, and a glycoluril having one epoxy group in the molecule.
  • a glycoluril having one epoxy group in the molecule are useful as reactive diluents in epoxy resins, for example, and glycolurils having two or more epoxy groups in the molecule are expected to be useful as crosslinking agents for epoxy resins, for example.
  • tetraallyl glycolurils are already known, but glycolurils having one allyl group in the molecule are useful as such, for example, as synthetic intermediates, and Although allyl glycolurils having 2 or 3 allyl groups in the molecule are expected to be useful as crosslinking agents for synthetic resins and synthetic rubbers, they have not been known so far.
  • the basic invention according to the present invention relates to novel glycolurils having a carboxyalkyl group, a glycidyl group or an allyl group as a functional group. Further, the present invention includes some already known glycolurils. The present invention relates to various useful resin compositions using glycolurils having a carboxyalkyl group, a glycidyl group or an allyl group as a functional group.
  • the present invention comprises the above basic invention and the first, second and third inventions which are resin compositions using glycolurils each having a carboxyalkyl group, a glycidyl group and an allyl group as functional groups.
  • first, second and third inventions are resin compositions using glycolurils each having a carboxyalkyl group, a glycidyl group and an allyl group as functional groups.
  • the first invention according to the present invention relates to the following two inventions.
  • Polyester resin composition for powder coatings comprising a polyester resin obtained by polycondensation reaction of the above tetrakis (carboxyalkyl) glycolurils and glycols.
  • polyester resin powder coating As the powder coating, epoxy resin, acrylic resin, and polyester resin are mainly used. Among them, polyester resin powder coating has a balanced coating performance. It is.
  • polyester resin In order to obtain a powder coating having excellent weather resistance, it is necessary to improve the weather resistance of the polyester resin as a main component. Usually, co-use of isophthalic acid as a carboxylic acid component and neopentyl glycol as a glycol component is required. A polyester resin having a high polymerization rate is used.
  • polyesters with more of these components are less susceptible to photodegradation. It is known that the weather resistance is good.
  • Isocyanate-based curing agents with hydroxyl groups at the main ends used in polyester resin powder coatings have a structure that shows no activity below a certain temperature by blocking highly reactive isocyanate groups with blocking agents. However, the block agent is dissociated at the time of baking, so that the baking furnace is contaminated.
  • the triglycidyl isocyanurate-based curing agent does not contain a blocking agent, it is not preferable to use it because of its mutagenicity.
  • hydroxyalkylamide curing agents have attracted attention as curing agents that can replace triglycidyl isocyanurate curing agents.
  • a powder coating using a hydroxyalkylamide-based curing agent can be baked at a low temperature, does not generate volatiles during baking, and can be a clean coating with no environmental burden.
  • powder coatings using a hydroxyalkylamide-based curing agent have the disadvantage that the smoothness of the coating film and the adhesion to the object to be coated, particularly the adhesion after water and moisture resistance, are poor.
  • Patent Document 2 a powder coating mainly composed of a resin obtained by depolymerizing a polyester resin composed of isophthalic acid and neopentyl glycol with isophthalic acid or the like has been proposed (see Patent Document 2).
  • this powder coating is excellent in weather resistance, low-temperature curability, coating film smoothness, and adhesion to a material, but the coating film smoothness is still not sufficient.
  • the second invention according to the present invention is a novel glycidyl glycoluril in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group and use thereof, particularly an epoxy containing the same.
  • the present invention relates to a resin composition.
  • the second invention according to the present invention relates to the following four inventions.
  • Novel glycidyl glycolurils and resin compositions containing the same Glycolurils having a glycidyl group as a functional group have not been known so far, but are expected to be useful due to the reactivity of the glycidyl group. Is done.
  • Epoxy resin composition for sealing an optical semiconductor element In recent years, as a thermosetting resin composition used for sealing an optical semiconductor element such as a light emitting element or a light receiving sensor, transparency of the cured body is required. Therefore, in general, an epoxy resin composition obtained by using an epoxy resin such as a bisphenol A type epoxy resin and a curing agent such as an acid anhydride is widely used.
  • thermosetting resin compositions have higher heat resistance or light resistance than before. There is a demand for a transparent sealing material having a property.
  • thermosetting resin composition as a technique for improving heat resistance or light resistance, a technique for increasing the glass transition temperature (Tg) of the cured product using a polyfunctional epoxy resin or an alicyclic epoxy is used.
  • Tg glass transition temperature
  • thermosetting resin composition using triglycidyl isocyanurate is used.
  • the cured body of the thermosetting resin composition using triglycidyl isocyanurate is hard and brittle, there arises a problem that cracks occur in the cured body due to thermal contraction when the optical semiconductor element is sealed with resin.
  • triglycidyl isocyanurate has high crystallinity, a liquid thermosetting resin composition using the triglycidyl isocyanurate has problems such as an increase in viscosity due to crystallization. There was a problem that time could not be obtained.
  • thermosetting resin composition containing phenolic compound Thermosetting resin composition represented by the epoxy resin composition is excellent in workability and has excellent electrical properties, heat resistance and adhesiveness. Due to moisture resistance (water resistance), etc., it is widely used in the fields of electric / electronic parts, structural materials, adhesives, paints, and the like.
  • the resin used as a material has been improved in purity, moisture resistance, adhesiveness, dielectric properties, and low resistance for high filler filling. There is a need for further improvements in various properties such as viscosity increase and increased reactivity to shorten the molding cycle.
  • Bromine compounds have been used in conventional printed wiring boards to make them flame retardant. However, since there is a possibility of generating harmful substances during combustion, it is expected that this bromine compound will not be usable in the near future. Is done.
  • solder that does not contain lead is also being put into practical use as a solder generally used for connecting electronic components to a printed wiring board. Since this lead-free solder has a use temperature of about 20 to 30 ° C. higher than that of conventional eutectic solder, the material is required to have higher heat resistance than ever before.
  • a low dielectric constant layer is formed on the surface of a recent silicon chip for high-speed computation or the like, and the formation of this low dielectric constant layer makes the silicon chip very brittle.
  • Conventional printed wiring boards have a large difference in thermal expansion coefficient from silicon chips, and in order to ensure connection reliability when silicon chips are mounted, the thermal expansion coefficient of printed wiring boards is comparable to the thermal expansion coefficient of silicon chips. It is demanded to reduce it to a minimum.
  • a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method of increasing the crosslinking density, increasing the glass transition temperature (Tg), and reducing the thermal expansion coefficient (Patent Document 6). And 7).
  • Tg glass transition temperature
  • Patent Document 6 Patent Document 6
  • Patent Document 7 Patent Document 7
  • thermosetting resin composition for build-up using an aromatic diamine having an imide group and an epoxy resin is proposed.
  • a low molecular weight polyimide compound is used as a curing agent for an epoxy resin, most of them are not different from the characteristics of the epoxy resin in many cases.
  • a printed wiring board used in an electrical product has a solder resist film formed as a permanent protective film on a substrate having a circuit of a conductor layer. Yes.
  • This solder resist film prevents solder from adhering to unnecessary parts in the soldering process for bonding (mounting) electrical / electronic components to printed wiring boards, avoiding short circuits and conductors. It is what protects the layer.
  • the solder resist film is required to have properties such as adhesion to the substrate and the conductor layer, chemical resistance, and insulation.
  • a resin composition from which a solder resist film satisfying these characteristics can be obtained a resin composition that can be developed with an alkaline aqueous solution is known (see Patent Document 9).
  • the solder resist film obtained by curing this composition has insufficient flexibility and has a problem that cracks occur during cutting and thermal shock tests. Note that the cracks in the solder resist film not only serve to protect the insulation, but also cause circuit disconnection.
  • the third invention relates to the following six inventions.
  • Novel allylglycolurils Reactive compounds having a plurality of allyl groups in the molecule, such as triallyl isocyanurate, are well known as crosslinking agents for synthetic resins and synthetic rubbers. Further, tetraallylglycolurils having four allyl groups in a molecule that functions as a crosslinking agent for synthetic resins and synthetic rubbers are also known (see Patent Document 13).
  • glycolurils having one allyl group in the molecule are useful as such as, for example, synthetic intermediates, and glycolurils having two or three allyl groups in the molecule are also useful. Although it is expected to be useful as a crosslinking agent for synthetic resins and synthetic rubbers, it has not been known so far.
  • Olefin-based resin composition Olefin-based resins have excellent electrical insulation and solvent resistance, and include radiation crosslinking, electron beam crosslinking, peroxide crosslinking, sulfur crosslinking, and silane crosslinking with silane compounds. By appropriately adopting various crosslinking means, it is possible to control various physical properties of the olefin resin, and it is widely used in various fields including electric and electronic materials.
  • glycolurils are heterocyclic compounds having four urea nitrogens in the ring structure, and use intermediates of various applications and functional compounds by utilizing the reactivity of urea nitrogens. Is used.
  • glycolurils having an allyl group rich in reactivity in the molecule are expected to be useful as a crosslinking agent for olefinic resins due to the active allyl group.
  • thermosetting resins have been used for a long time.
  • epoxy resins have been widely used because of their versatility and high adhesion to various substrates.
  • peripheral materials such as luminance light emitting diodes and power semiconductors, they are insufficient from the viewpoint of long-term heat resistance and light resistance.
  • glass has been known for a long time, but there is a problem that workability and adhesion to a substrate are poor.
  • thermosetting resins using a hydrosilylation reaction that is an addition reaction of a carbon-carbon double bond and a hydrosilyl group have been proposed (see, for example, Patent Documents 14, 15, and 16). Has excellent heat resistance, light resistance and adhesion.
  • thermosetting resin that suppresses warping and provides excellent adhesion by reducing thermal stress while maintaining excellent heat resistance, light resistance, and transparency has been eagerly desired.
  • Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril In order to encapsulate a semiconductor device with a resin, a transfer mold using a mold, potting with a liquid encapsulating resin, Screen printing and the like are performed. In recent years, with the miniaturization of semiconductor elements, there has been a demand for downsizing and thinning of electronic devices, and it has become necessary to resin seal a thin package having a thickness of 500 ⁇ m or less and a stack of silicon dies.
  • an epoxy of polysiloxane obtained by addition reaction of diallyl monoglycidyl isocyanurate to an Si—H group-containing polysiloxane.
  • Patent Document 19 Group-opening polymer-containing composition
  • Patent Document 20 the above-described isocyanurate ring-containing polysiloxane and Si—H group-containing polysiloxane polymer-containing composition
  • Patent Document 21 triallyl isocyanurate and Si— Addition-curable composition with H group-containing polysiloxane
  • Patent Document 21 polysiloxane containing isocyanurate ring and Si—H group, alkenyl group-containing cured product, and addition-curable composition
  • the isocyanurate ring-containing polymer composition contains a siloxane bond in the main component, it is flexible but poorly compatible with the crosslinking agent. Further, since the position of the alkenyl group is uncertain, it is difficult to cure by addition reaction, and the characteristics (rapid curing reaction) of hydrosilylation (addition reaction) cannot be utilized. In addition, the isocyanuric acid-containing polymer composition has a problem that it has a high crosslinking density, is rigid and lacks flexibility.
  • Electron beam curable resin composition Since LED elements are power-saving and have a long life, they have been widely used in recent years as light sources to replace incandescent bulbs and the like. In general, when an LED element is used as a light source, a plurality of LED elements are installed on a metal substrate, and a reflector is disposed around the LED element, thereby reflecting light and improving illuminance.
  • Silicone resin composition Conventionally, it has been proposed to use an epoxy resin as a resin in a composition for sealing an optical semiconductor (for example, see Patent Document 26).
  • an epoxy resin as a resin in a composition for sealing an optical semiconductor (for example, see Patent Document 26).
  • the sealing body obtained from the composition containing an epoxy resin has a problem such as yellowing due to heat generated from the white LED element.
  • Siloxane compositions have been proposed (see Patent Documents 27 and 28). Furthermore, it has been proposed to mix and heat a condensation catalyst to diorganopolysiloxane having two silanol groups and silane having three or more alkoxy groups (see Patent Documents 29 and 30).
  • silicone resin gas permeability is higher than epoxy resin and air easily passes through, so the silver plating of the optical semiconductor package is easily discolored over time due to hydrogen sulfide in the air. There was a problem that decreased.
  • silicone resin it is generally performed to harden the resin in order to improve the sulfidation resistance.
  • shrinkage due to curing, peeling from the LED package, and wire breakage. .
  • An object of the present invention is to provide a novel glycoluril having a functional group and various resin compositions containing the same as a basic invention. Furthermore, the present invention has an object to provide the following first, second, and third inventions in particular in view of the above-described state of the art.
  • the 1st invention by this invention, (1) Novel tetrakis (carboxyalkyl) glycolurils and their use, in particular, epoxy resin compositions using tetrakis (carboxyalkyl) glycolurils, (2) It aims at providing the polyester resin composition for powder coatings which gives the powder coating material which was excellent in the weather resistance of the coating film, smoothness, and low-temperature curability.
  • the 2nd invention by this invention is: (1) Novel glycidyl glycolurils and their use, in particular, various resin compositions containing the same, (2) An object is to provide an epoxy resin composition for sealing an optical semiconductor element.
  • the inventors of the present invention have made extensive studies in order to obtain a sealing material for optical semiconductor elements that is liquid, has a long working life, and is excellent in heat resistance and light resistance. Then, paying attention to the epoxy resin component itself, and as a result of repeated research centering on the improvement of the properties of triglycidyl isocyanurate used in the past, the cured product obtained when using allyl glycoluril which is a liquid epoxy resin Discovered that heat resistance and light resistance were improved without impairing high transparency, and reached the epoxy resin composition for sealing an optical semiconductor element according to the present invention.
  • an object of this invention is to provide the thermosetting resin composition containing a phenol compound.
  • the object of the present invention is to provide insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, and adhesives.
  • Another object of the present invention is to provide a thermosetting resin composition that is useful for paints and the like and provides a cured product that is not only excellent in flame retardancy but also excellent in heat resistance and toughness.
  • Another object of the present invention is to provide an alkali development type photocurable / thermosetting resin composition.
  • the present inventors achieved the intended purpose by using a photocurable thermosetting resin composition containing glycidyl glycoluril as an epoxy compound. As a result, the present invention has been completed.
  • the present invention provides a photocurable / thermosetting resin composition capable of obtaining a cured film having excellent flexibility and thermal shock resistance without impairing properties such as solder heat resistance, heat deterioration resistance, and acid resistance. And it aims at providing the printed wiring board which formed the soldering resist film (cured film) using these.
  • the 3rd invention by this invention is: (1) It is an object of the present invention to provide novel allyl glycolurils and various useful resin compositions using them.
  • Olefin resin composition It aims at providing the olefin resin composition suitable as a raw material of the olefin resin which has a crosslinked structure.
  • Curable composition with excellent adhesion uses tetraallylglycoluril as an essential component as an organic compound having an alkenyl group, so that the heat and light resistance of the cured product can be reduced without impairing heat resistance and light resistance.
  • An object of the present invention is to provide a curable composition that reduces stress and exhibits excellent adhesiveness.
  • Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril
  • the present inventors have identified both specific resin components as a resin component comprising a main agent (base polymer) and a curing agent (crosslinking agent).
  • thermosetting resin composition using a terminal allylic glycoluril ring-blocked organopolysiloxane polymer (base polymer) and a glycoluril ring-containing terminal hydrogen polysiloxane polymer (crosslinking agent) in combination with a curing accelerator,
  • base polymer terminal allylic glycoluril ring-blocked organopolysiloxane polymer
  • crosslinking agent glycoluril ring-containing terminal hydrogen polysiloxane polymer
  • the present invention relates to a thermosetting resin composition that can provide a semiconductor device that has almost no warpage and is excellent in heat resistance and moisture resistance even when a semiconductor element is sealed.
  • An object of the present invention is to provide a semiconductor device sealed with a resin composition.
  • Electron beam curable resin composition The present invention is suitable for molding a reflector, and an object thereof is to provide an electron beam curable resin composition from which a cured product having excellent heat resistance can be obtained.
  • Silicone resin composition An object of this invention is to provide the silicone resin composition from which the cured
  • group Z represents a carboxyalkyl group, a glycidyl group or an allyl group
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group
  • R 3 , R 4 and R 5 represent each Independently represents a hydrogen atom or the same group as group Z.
  • group Z is a carboxyalkyl group
  • R 3 , R 4 and R 5 represent the same carboxyalkyl group as group Z
  • group Z is an allyl group.
  • R 5 represents a hydrogen atom.
  • first, second and third inventions are provided based on the novel glycolurils having the functional group.
  • n 0 or 1
  • R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the formula:
  • a crosslinking agent for an epoxy resin as the use of the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril, and further, the crosslinking agent for an epoxy resin and an amine
  • An epoxy resin composition comprising a curing agent is provided.
  • 1,3,4,6-Tetrakis (carboxyalkyl) glycolurils according to the present invention are novel compounds in which all hydrogen atoms on four nitrogen atoms in a molecule are substituted with carboxylalkyl groups, ie molecules Glycolurils having 4 carboxyl groups in them.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention are tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, conventional bifunctional or trifunctional Therefore, it is possible to obtain an epoxy resin cured product having a higher crosslinking density than that when a functional crosslinking agent is used, and thus, for example, an epoxy resin cured product superior in hardness, heat resistance, moisture resistance, and the like. It is useful as a crosslinking agent or solder flux activator.
  • polyester resin composition for powder coatings comprises: (A) a polyester resin obtained by a polycondensation reaction between 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) and a glycol; (B) contains a ⁇ -hydroxyalkylamide curing agent.
  • Such a resin composition for powder coating can be a powder coating excellent in the weather resistance and smoothness of the coating film and low-temperature curability.
  • Second invention (1) Novel glycidyl glycoluril and epoxy resin composition containing the same According to the present invention, general formula (B)
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group
  • R 3 , R 4 and R 5 each independently represent a hydrogen atom or a glycidyl group.
  • an epoxy resin crosslinking agent As the utilization of the glycidyl glycoluril, there is provided an epoxy resin crosslinking agent, and further an epoxy resin composition containing the epoxy resin crosslinking agent.
  • the glycidyl glycoluril according to the present invention is a novel compound in which at least one hydrogen atom of hydrogen atoms bonded to four nitrogen atoms of the glycoluril is substituted with a glycidyl group.
  • such compounds are useful as intermediates for the synthesis of novel oxygen-containing compounds, and those having one glycidyl group in the molecule can be used, for example, as reactive diluents for epoxy resins. Useful.
  • numerator is useful as a crosslinking agent for epoxy resins, for example.
  • 1,3,4,6-tetraglycidyl glycoluril in which all hydrogen atoms on nitrogen atoms are substituted with glycidyl groups is tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, A cured epoxy resin having a higher crosslinking density than when a conventional bifunctional or trifunctional crosslinking agent is used, and therefore, an epoxy resin cured product superior in hardness, heat resistance, and the like can be obtained. .
  • Epoxy resin composition for sealing an optical semiconductor element comprises (1) an epoxy resin, and at least one component in the (1) epoxy resin is the above-mentioned These are glycidyl glycolurils represented by the general formula (B).
  • the epoxy resin composition for sealing an optical semiconductor element according to the present invention is preferably at least selected from a glass filler, a curing agent, a curing accelerator, a curing catalyst, a polyester resin, an organosiloxane, rubber particles, and an additive. It contains one component.
  • the glycidyl glycoluril has at least one glycidyl group (epoxy group) in the molecule and exhibits liquid properties at room temperature.
  • the resin composition is stored, the formation of crystalline substances is suppressed.
  • Tg glass transition temperature
  • the optical semiconductor device has high light transmittance, and is excellent in heat resistance and light resistance. Is obtained.
  • a highly reliable optical semiconductor device is obtained by sealing an optical semiconductor element with the resin composition according to the present invention.
  • the epoxy resin composition according to the present invention is liquid at the time of handling, it is excellent in handling properties at the time of sealing work. Accordingly, the epoxy resin composition according to the present invention can be preferably used as a resin composition for optical semiconductor encapsulation.
  • the epoxy resin composition according to the present invention includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sea lantern, a resist candy, a composite material, a transparent substrate, a transparent sheet, a transparent film, and an optical element , Optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.
  • thermosetting resin composition containing a phenol compound
  • the thermosetting resin composition according to the present invention contains glycidyl glycoluril represented by the general formula (B) and a phenol resin as components.
  • thermosetting resin composition according to the present invention provides a cured product having excellent flame retardancy, heat resistance and toughness, insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.) and laminated boards (printed wiring) Plate, build-up substrate, etc.) and various composite materials including CFRP, adhesives, paints and the like.
  • the alkali development type photocurable / thermosetting resin composition according to the present invention comprises: (A) Glycidyl glycoluril represented by the general formula (B), (B) A photosensitive prepolymer having two or more unsaturated double bonds in one molecule and (c) a photopolymerization initiator.
  • the alkali-developable photocurable / thermosetting resin composition according to the present invention preferably contains an epoxy compound or an epoxy resin excluding the glycidyl glycoluril represented by the general formula (B).
  • the alkali development type photocurable / thermosetting resin composition according to the present invention preferably contains a diluent, a polybutadiene compound and a polyurethane compound.
  • the photocurable / thermosetting resin composition according to the present invention has both flexibility and thermal shock resistance without impairing the basic characteristics required for solder resist coating such as solder heat resistance and heat degradation resistance. Therefore, it can be suitably used in the formation of a solder resist film for printed wiring boards for various applications.
  • the photocurable / thermosetting resin composition according to the present invention is superior in the flexibility of the cured film as compared with known photosensitive resin compositions used for flexible printed wiring boards, and is suitable for BGA or CSP. Compared to known photosensitive resin compositions used for printed wiring boards, the cured film has excellent thermal shock resistance.
  • novel allyl glycolurils are: General formula (C0)
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 and R 4 each independently represent a hydrogen atom or an allyl group.
  • allyl glycolurils according to the present invention are novel compounds in which 1 to 3 of nitrogen atoms of glycolurils are substituted with allyl groups.
  • glycolurils having one allyl group in the molecule are useful as such, for example, as synthetic intermediates, and two or Glycolurils having three allyl groups are expected to be useful as crosslinking agents for synthetic resins and synthetic rubbers.
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or an allyl group.
  • molded products such as films, sheets and cases (containers) obtained by crosslinking the olefin resin composition according to the present invention to obtain a crosslinked product (resin) and molding the product have excellent transparency. Furthermore, it has excellent resolution, electrical insulation, heat resistance, low moisture absorption, hydrolysis resistance, weather resistance, adhesion, mechanical properties such as elasticity, and the like.
  • Curable composition excellent in adhesiveness is: (A) an organic compound having an alkenyl group, (B) A curable composition comprising a compound having at least three or more hydrosilyl groups in one molecule and (C) a hydrosilylation catalyst, As said (A) component, general formula (C1)
  • X represents a hydrogen atom, an alkyl group or an aryl group.
  • X represents a hydrogen atom, an alkyl group or an aryl group.
  • the curable composition according to the present invention effectively reduces thermal stress while maintaining excellent heat resistance and light resistance, and provides a cured product having excellent adhesion and low warpage.
  • thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril
  • the thermosetting resin composition according to the present invention comprises: (A) General formula (C3) as alkenyl group-containing organopolysiloxane
  • each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, and p is an integer of 1 to 30.
  • each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, m is an integer of 0 to 5, and each siloxane repeating unit in the formula is bonded randomly. May be.
  • thermosetting resin composition according to the present invention preferably further comprises (D) an inorganic filler.
  • thermosetting resin composition according to the present invention has 0.8 to 4.0 moles of Si—H groups in the component (B) with respect to 1 mole of allyl groups in the component (A).
  • thermosetting resin composition according to the present invention gives a semiconductor device having almost no warping and excellent heat resistance and moisture resistance even when a semiconductor element is sealed.
  • Electron beam curable resin composition contains polyolefin resin and a crosslinking agent, and the said crosslinking agent is general formula (C5).
  • n is an integer of 0 or 1. It is an isocyanurate compound represented by these.
  • the electron beam curable resin composition according to the present invention contains a polyolefin resin and a crosslinking agent, and the crosslinking agent is an allyl glycoluril represented by the general formula (C).
  • the electron beam curable resin composition according to the present invention is suitable for molding a reflector and gives a cured product having excellent heat resistance.
  • the silicone resin composition according to the present invention comprises: (A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms; (B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms; (C) component: a hydrosilylation reaction catalyst; (D) component: including allyl glycoluril represented by the general formula (C),
  • the component (D) comprises 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).
  • the silicone resin composition according to the present invention preferably contains substantially no silicon compound having a silanol group.
  • the alkenyl group is preferably a vinyl group or a (meth) acryloyl group.
  • the silicone resin composition according to the present invention is particularly suitable as a resin composition for sealing an optical semiconductor element.
  • the silicone resin composition according to the present invention gives a cured product having excellent sulfidation resistance and transparency.
  • group Z represents a carboxyalkyl group, a glycidyl group or an allyl group
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group
  • R 3 , R 4 and R 5 represent each Independently represents a hydrogen atom or the same group as group Z.
  • group Z is a carboxyalkyl group
  • R 3 , R 4 and R 5 represent the same carboxyalkyl group as group Z
  • group Z is an allyl group.
  • R 5 represents a hydrogen atom.
  • the glycolurils according to the present invention are 1,3,4,6-tetrakis ⁇ carboxyalkyl> glycolurils when the group Z is a carboxylalkyl group in the above general formula ⁇ Z>, and the group Z is When it is a glycidyl group, it is mono, di, tri and tetraglycidyl glycolurils, and when the group Z is an allyl group, it is mono, di and triallyl glycolurils.
  • 1,3,4,6-tetrakis ⁇ carboxyalkyl> glycoluril and a resin composition using the same are the first invention
  • glycidyl glycoluril and a resin composition using the same are the second invention
  • the allyl glycoluril and a resin composition using the allyl glycoluril will be described in detail below as the third invention.
  • n 0 or 1
  • R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.
  • R 1 or R 2 is a lower alkyl group
  • the lower alkyl group is usually carbon.
  • the number of atoms is 1 to 5, preferably 1 to 3, and most preferably 1. Therefore, the most preferred lower alkyl group is a methyl group.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycolurils include, for example, 1,3,4,6-tetrakis (carboxylmethyl) glycoluril, 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril, 1,3,4,6-tetrakis (carboxylmethyl) -3a-methylglycoluril, 1,3,4,6-tetrakis (2-carboxylethyl) -3a-methylglycoluril, 1,3,4,6-tetrakis (carboxylmethyl) -3a, 6a-dimethylglycoluril, Examples include 1,3,4,6-tetrakis (2-carboxylethyl) -3a, 6a-dimethylglycoluril.
  • R 3 represents a lower alkyl group. It can obtain by making it react with the urea derivative (b) represented by these.
  • the ester group (—CO 2 R 3 ) in the urea derivative (b) is an ester group that is hydrolyzed during the reaction, and the group R 3 is preferably an alkyl group having 1 to 3 carbon atoms. And more preferably a methyl group or an ethyl group. Therefore, as the urea derivative (b), for example, N, N′-carbonylbis (glycinemethyl) and N, N′-carbonylbis (glycineethyl) are preferably used.
  • the urea derivative (b) is used in a proportion of 2 to 10 mole parts, preferably in a ratio of 2 to 4 mole parts, with respect to 1 mole part of the dicarbonyl compound (a).
  • dicarbonyl compound (a) for example, glyoxal, 2-oxopropanal, diacetyl and the like are used.
  • Examples of the acid used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. These acids are usually used in a proportion of 0.05 to 10 mol parts, preferably 0.1 to 1.0 mol parts, relative to 1 mol part of the dicarbonyl compound (a).
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • water methanol, ethanol , Alcohols such as isopropyl alcohol, aliphatic hydrocarbons such as hexane and heptane, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, benzene, toluene and xylene
  • Aromatic hydrocarbons methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol di Ethers such as til ether, formamide, N, N
  • the reaction of the dicarbonyl compound (a) and the urea derivative (b) is usually performed at a temperature in the range of ⁇ 10 to 150 ° C., preferably at a temperature in the range of 0 ° C. to 100 ° C.
  • the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.
  • the desired 1,3,4,6-tetrakis (carboxymethyl) is obtained from the obtained reaction mixture by an operation such as extraction. ) Glycolurils can be obtained. If necessary, the desired 1,3,4,6-tetrakis (carboxymethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.
  • Step 1 to obtain 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the following formula, then, the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is obtained Preferably, it can be obtained by passing through a second step of hydrolysis in the presence of an acid in an appropriate solvent.
  • acrylonitrile is usually in a ratio of 4.0 to 20.0 mole parts per mole of glycolurils (c). Preferably, it is used in a proportion of 4.0 to 8.0 mole parts.
  • Examples of the base in the first step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert.
  • An inorganic base such as butoxide or an organic base such as triethylamine, diisopropylethylamine, DBU (1,8-diazabicyclo [5.4.0] unde-7-cene) is used.
  • These bases are usually used in a proportion of 0.01 to 5.0 mol parts, preferably in a proportion of 0.01 to 1.0 mol parts, relative to 1 mol part of the glycolurils (c). It is done.
  • the solvent when used, it is not particularly limited as long as it does not inhibit the reaction.
  • the dicarbonyl compound (a) and the urea derivative (b) The same solvent as that used in the reaction can be used.
  • reaction temperature and reaction time in the first step are also the same as the reaction temperature and reaction time in the reaction of the dicarbonyl compound (a) and the urea derivative (b).
  • Examples of the acid used in the second step that is, hydrolysis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Can do. These acids are usually in a ratio of 0.1 to 20.0 mol parts, preferably 1.0 to 1 mol parts of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril. Used in a proportion of ⁇ 3.0 mol parts.
  • the solvent used in the second step is not particularly limited as long as the reaction is not inhibited.
  • the same solvent as used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) is used.
  • a solvent can be used.
  • the hydrolysis reaction of the 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is usually carried out at a temperature in the range of 0 to 150 ° C., preferably in the range of room temperature to 100 ° C.
  • a temperature of The reaction time is usually in the range of 1 to 36 hours, preferably in the range of 1 to 16 hours, although depending on the reaction temperature.
  • the target 1 is obtained from the resulting reaction mixture by an operation such as extraction. , 3,4,6-tetrakis (2-carboxyethyl) glycoluril can be obtained. If necessary, the desired 1,3,4,6-tetrakis (2-carboxyethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.
  • the 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention have four carboxyl groups in the molecule, as described above, and thus, for example, as crosslinkers for epoxy resins Useful.
  • the epoxy resin composition according to the present invention contains 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) as a crosslinking agent, and further contains a curing agent comprising amines. Including.
  • an epoxy resin composition containing 1,3,4,6-tetrakis (carboxyalkyl) glycoluril as a crosslinking agent and a curing agent comprising an amine is conventionally known.
  • the above-mentioned epoxy resin means an epoxy compound having two or more epoxy groups per molecule on average. Therefore, as is well known, as such an epoxy resin, for example, bisphenol A is used.
  • Polyglycidyl ethers obtained by reacting polychlorophenols such as bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohols such as glycerin and polyethylene glycol and epichlorohydrin, p-hydroxybenzoic acid, ⁇ -hydroxynaphthoic acid
  • Glycidyl ether esters obtained by reacting such a hydroxycarboxylic acid with epichlorohydrin polyglycidyl esters obtained by reacting a polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin, and epoxide Phenolic novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin
  • the curing agent comprising amines in the epoxy resin composition according to the present invention has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and a primary amino group, What is necessary is just to have at least one amino group selected from a secondary amino group and a tertiary amino group in the molecule.
  • the curing agent comprising such amines include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diaminodicyclohexylmethane.
  • Aromatic amines such as 4,4'-diaminodiphenylmethane, 2-methylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, Examples thereof include nitrogen-containing heterocyclic compounds such as piperidine and piperazine.
  • curing agent which consists of amines is not limited to the said illustration.
  • the epoxy resin composition according to the present invention may contain various additives such as a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, and an antioxidant as necessary. Good.
  • N, N′-carbonylbis (glycine methyl) was synthesized according to the method described in Synlett, Vol. 7, pages 1104 to 1106 (2010).
  • aqueous glyoxal solution 40% aqueous glyoxal solution, glycoluril and acrylonitrile were all manufactured by Tokyo Chemical Industry Co., Ltd., and DBU was manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 Synthesis of 1,3,4,6-tetrakis (carboxylmethyl) glycoluril
  • a 100 mL flask equipped with a thermometer was charged with 2.04 g (10.0 mmol) of N, N′-carbonylbis (glycine methyl), 726 mg (5.0 mmol) of 40% aqueous glyoxal solution, 10 mL of acetic acid and 49 mg (0.5 mmol) of sulfuric acid. I put it in.
  • the obtained 1,3,4,6-tetrakis (carboxylmethyl) glycoluril had a melting point of 223 ° -239 ° C.
  • the IR spectrum is shown in FIG. Further, the ⁇ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
  • Example 2 Synthesis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril
  • a 200 mL autoclave vessel equipped with a thermometer was charged with 13.54 g (95.3 mmol) of glycoluril, 35.38 g (666.8 mmol) of acrylonitrile, 0.58 g (3.8 mmol) of DBU and 54 mL of water.
  • the melting point of the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril was 139 to 141 ° C.
  • the IR spectrum is shown in FIG. Further, the ⁇ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
  • the melting point of the obtained 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril was 115 to 121 ° C.
  • the IR spectrum is shown in FIG. Further, the ⁇ value in the 1 H-NMR spectrum (D 2 O) was as follows.
  • polyester resin composition according to the present invention comprises: (A) a polyester resin obtained by a polycondensation reaction between 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) and a glycol; (B) A ⁇ -hydroxyalkylamide-based curing agent.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) is used as a carboxylic acid as a raw material for the polyester resin.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycoluril include the following: 1,3,4,6-tetrakis (carboxylmethyl) glycoluril, 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril, 1,3,4,6-tetrakis (carboxylmethyl) -3a-methylglycoluril, 1,3,4,6-tetrakis (2-carboxylethyl) -3a-methylglycoluril, 1,3,4,6-tetrakis (carboxylmethyl) -3a, 6a-dimethylglycoluril, Examples include 1,3,4,6-tetrakis (2-carboxylethyl) -3a, 6a-dimethylglycoluril.
  • isophthalic acid, terephthalic acid, 5-sodium sulfoisophthalic acid may be used as carboxylic acids separately from 1,3,4,6-tetrakis (carboxyalkyl) glycoluril.
  • Aromatic dicarboxylic acids such as acid, phthalic anhydride, naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dodecanedioic acid, trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid, Further, ester-forming derivatives of these acids may be used in combination with oxycarboxylic acids such as 4-hydroxybenzoic acid and ⁇ -caprolactone.
  • the glycols include neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, aliphatic diols such as 1,4-butanediol and 1,6-hexanediol, 1,4-cyclohexanedimethanol, And aromatic glycols such as alicyclic glycols such as 1,4-cyclohexanediol, trivalent or higher alcohols such as trimethylolpropane, pentaerythritol and glycerin, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol S, and the like. It is done.
  • the ratio of the total amount (total amount) of 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and glycols needs to be 80 to 100 mol% with respect to all components.
  • the total ratio is less than 80 mol%, the weather resistance of the coating film is insufficient.
  • the acid value of the polyester resin of the present invention is preferably 20 to 50 mgKOH / g, more preferably 25 to 40 mgKOH / g.
  • the acid value of the polyester resin is less than 20 mgKOH / g, the molecular weight of the resin becomes too high and the fluidity is lowered, so that the smoothness of the coating film is lowered and the adhesion to the material is deteriorated. .
  • the acid value exceeds 50 mgKOH / g, when blended as a raw material of a coating, the curing reaction with the curing agent is excessively increased, so that the smoothness of the coating film is deteriorated and the adhesion with the material is decreased. Absent.
  • the polyester resin of the present invention preferably has a melt viscosity at 160 ° C. of 100 to 800 dPa ⁇ s, and more preferably 150 to 700 dPa ⁇ s. If the melt viscosity at 160 ° C. of the polyester resin is less than 100 dPa ⁇ s, the melt viscosity becomes too low and the coating film is sagged. When melt viscosity exceeds 800 dPa * s, the smoothness of a coating film will fall and adhesiveness with a raw material will be impaired.
  • the polyester resin of the present invention uses the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and glycols (including their ester-forming derivatives) as raw materials, and has a temperature of 200 to 280 ° C. by a conventional method. After the esterification or transesterification reaction is performed at a temperature, the polycondensation reaction is performed at a temperature of 200 to 300 ° C., preferably 230 to 290 ° C. under a reduced pressure of 5 hPa or less.
  • 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and / or aromatic tricarboxylic acid is added, and at a reaction temperature of 230 to 290 ° C., preferably 250 to 280 ° C., A depolymerization step may be added for a reaction time of 2 to 5 hours, preferably 2.5 to 4 hours.
  • the depolymerization temperature is less than 230 ° C.
  • the depolymerizer does not react sufficiently, resulting in a polymer having a high degree of polymerization and poor smoothness.
  • the depolymerization temperature exceeds 290 ° C.
  • the thermal decomposition of the polymer proceeds. Even at a predetermined temperature, when the depolymerization time is less than 2 hours, the depolymerization agent does not react at all, so that the smoothness of the coating film is lowered and the adhesion with the material is deteriorated.
  • the depolymerization time exceeds 5 hours, the thermal history becomes long, so that the thermal decomposition of the polymer proceeds.
  • a known reaction catalyst can be used.
  • the performance of the coating film is further improved by blending the polyester resin of the present invention with a hydroxyalkylamide curing agent.
  • the type of the curing agent is not particularly limited, and examples thereof include “PrimidXL-552” manufactured by EMS.
  • the amount of the curing agent is preferably 0.7 to 1.2 times equivalent, more preferably 0.9 to 1 times equivalent to the acid value of the polyester resin.
  • the resin composition for powder coatings of the present invention can be mixed with a known leveling agent and other additives, for example, a mixture of pigments such as titanium dioxide, precipitated barium sulfate, carbon black, etc. Can be prepared by melting and kneading at 70 to 140 ° C.
  • the resin composition for powder coatings of the present invention is applied to an object to be coated, and is usually baked at a temperature of 150 to 190 ° C. for 15 to 25 minutes to form a coating film excellent in smoothness and adhesion to the material. give.
  • the polyester resin of the present invention since the acid value is low, the curing reaction is relatively slow, and the melt viscosity is low. Therefore, when used as a raw material for powder coating, it has excellent smoothness, and further 1,3,4 , 6-Tetrakis (carboxyalkyl) glycoluril and glycols have a high copolymerization ratio, so that a coating film having excellent weather resistance can be obtained.
  • Example 1 1,3,4,6-tetrakis (2-carboxyethyl) glycoluril 53.5 mol parts and neopentyl glycol 47.6 mol parts were charged into an esterification reaction vessel, pressure 0.3 MPaG, temperature 260 ° C. for 4 hours. An esterification reaction was performed.
  • Titanium pigment (“Taipek CR-90” manufactured by Ishihara Sangyo Co., Ltd.) was added in the amount (part by mass) shown in Table 1 and dry blended with a Henschel mixer (“FM10B type” manufactured by Mitsui Miike Seisakusho).
  • the product was melt-kneaded at 100 ° C. using a “PR-46 type” manufactured by the company, cooled, pulverized, and classified with a 140 mesh (106 ⁇ m) wire mesh to obtain a resin composition for powder coating.
  • the obtained resin composition for powder coating was electrostatically coated on a zinc phosphate-treated steel sheet so as to have a film thickness of 50 to 60 ⁇ m, and baked at 160 ° C. for 20 minutes.
  • the results of evaluating the performance of the coating film are shown in Table 1.
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or a glycidyl group.
  • the glycidyl glycoluril according to the present invention has the general formula (Ba)
  • R 1 and R 2 are the same as described above.
  • the lower alkyl group when R 1 or R 2 is a lower alkyl group, the lower alkyl group usually has 1 to 5, preferably 1 to 3, most preferably 1, and therefore the most preferred lower alkyl group is a methyl group.
  • glycidyl glycolurils include, for example, 1-glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidyl glycoluril, 1,6-diglycidyl glycoluril, 1,3,4-triglycidyl glycoluril, 1,3,4,6-tetraglycidylglycoluril, 1-glycidyl-3a-methylglycoluril, 1-glycidyl-6a-methyl-glycoluril, 1,3-diglycidyl-3a-methylglycoluril, 1,4-diglycidyl-3a-methylglycoluril, 1,6-diglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-6a-methylglycoluril, 1,3,4,6-tetraglycidyl-3a-methylglycoluril, 1-glycidyl-3
  • the glycidyl glycoluril represented by the general formula (B) according to the present invention is represented by the general formula (a)
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group
  • R 6 , R 7 and R 8 each independently represent a hydrogen atom or a glycidyl group.
  • a method of oxidizing a carbon-carbon double bond and epoxidizing is already well known, and in the present invention, such a method can be used.
  • a method using a peracid such as an oxone reagent, peracetic acid, and metachloroperbenzoic acid, and a method using hydrogen peroxide using sodium tungstate as a catalyst.
  • the peracid is preferably used as the oxidizing agent, the peracid is preferably used at a ratio of 1.0 to 5.0 equivalents relative to the allyl group of allyl glycoluril.
  • the reaction solvent is not particularly limited as long as it does not inhibit the reaction.
  • water alcohols such as methanol, ethanol and isopropyl alcohol, aliphatics such as hexane and heptane are used.
  • Hydrocarbons ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, chloro Halogenated hydrocarbons such as trifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, formamide, N, N-dimethyl Formamide, N, N- dimethylacetamide,
  • the reaction temperature when oxidizing allyl glycoluril using the peracid is usually in the range of ⁇ 10 to 150 ° C., and preferably in the range of 0 ° C. to 100 ° C.
  • the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.
  • the target glycidyl glycoluril can be obtained by extraction from the obtained reaction mixture, or crystallization from an appropriate solvent and filtration.
  • hydrogen peroxide is in a ratio of 1.0 to 5.0 equivalents relative to the allyl group of allyl glycoluril.
  • sodium tungstate is preferably used in a proportion of 0.001 to 0.5 equivalents relative to the allyl group of allyl glycoluril.
  • the reaction solvent is not particularly limited as long as it does not inhibit the reaction.
  • the same reaction solvent as in the above-described oxidation reaction using a peracid can be used.
  • the reaction temperature is usually in the range of ⁇ 10 to 150 ° C., preferably in the range of 0 ° C. to 100 ° C., as in the above-described oxidation reaction using peracid, and the reaction time is also the reaction temperature. However, it is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.
  • the objective is obtained by extracting from the obtained reaction mixture, or crystallizing from an appropriate solvent and filtering. Glycidyl glycoluril can be obtained.
  • the glycidyl glycoluril thus obtained can be purified as necessary by washing with a solvent such as water, activated carbon treatment, silica gel chromatography, and the like.
  • those having one glycidyl group in the molecule are useful, for example, as an intermediate for synthesizing oxygen-containing compounds and as a diluent for epoxy resins.
  • those having two or more glycidyl groups in the molecule are useful as, for example, a crosslinking agent for epoxy resins.
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, alicyclic epoxy resin, 3 ′, 4′- Cycloaliphatic epoxy resins such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, nitrogen-containing cyclic epoxies such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and hydantoin type epoxy resins Resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, dicyclo ring
  • epoxy resins naphthalene-type epoxy resins, halogenated epoxy resins, etc., epoxy-modified organopolysiloxan
  • the glycidyl glycoluril according to the present invention can be made into an epoxy resin composition by blending it with the above-described epoxy resin together with a curing agent and, if necessary, a curing accelerator.
  • the glycidyl glycoluril according to the present invention is usually used at a ratio of 0.1 to 150 parts by mass, preferably 10 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Used at a rate of 100 parts by weight.
  • the curing agent examples include compounds having phenolic hydroxyl groups, acid anhydrides, amines, mercaptan compounds such as mercaptopropionic acid esters and epoxy resin-terminated mercapto compounds, triphenylphosphine, diphenylnaphthylphosphine, diphenylethylphosphine, and the like.
  • examples thereof include organic phosphine compounds, aromatic phosphonium salts, aromatic diazonium salts, aromatic iodonium salts, and aromatic selenium salts.
  • Examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, and phenol.
  • Examples thereof include novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and resorcinol.
  • Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic acid anhydride , Hymic acid anhydride, methylnadic acid anhydride, methyldicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride And methylnorbornane-2,3-dicarboxylic acid.
  • examples of the amines include diethylenediamine, triethylenetetramine, hexamethylenediamine, dimer acid-modified ethylenediamine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenol ether, 1,8-diazabicyclo.
  • examples include [5.4.0] -7-undecene and the like, and imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.
  • the curing agent is usually used in a proportion of 10 to 300 parts by mass, preferably 100 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • curing accelerator examples include 1,8-diazabicyclo [5.4.0] -7-undecene, diethylenetriamine, triethylenetetramine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl).
  • Amine compounds such as phenol, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Organic phosphine compounds such as tetrabutylphosphonium bromide, phosphonium compounds such as tetrabutylphosphonium diethyl phosphorodithioate, tetrapheny Tetraphenylboron salts such as phosphonium tetraphenylborate, 2-methyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, aliphatic acid metals such as lead acetate, tin octylate and cobalt hexanoate
  • the curing accelerator is usually used in a proportion of 0.01 to 2.0 parts by weight, preferably 0.1 to 0.5 parts, per 100 parts by weight of the epoxy resin. Used in the ratio of parts by mass.
  • the epoxy resin composition according to the present invention may be filled with an inorganic material such as amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, as necessary.
  • an inorganic material such as amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, as necessary.
  • various polymers such as phenol resin and unsaturated polyester can be included.
  • the epoxy resin composition according to the present invention can contain various additives in addition to the above.
  • additives include aliphatic polyols such as ethylene glycol and propylene glycol, carbon dioxide generation inhibitors such as aliphatic or aromatic carboxylic acid compounds and phenol compounds, flexibility imparting agents such as polyalkylene glycol, and oxidation.
  • Inhibitors plasticizers, lubricants, silane-based coupling agents, inorganic filler surface treatment agents, flame retardants, antistatic agents, coloring agents, antistatic agents, leveling agents, ion trapping agents, sliding property improving agents , Various rubber, organic polymer beads, glass beads, impact modifiers such as inorganic fillers such as glass fibers, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusion Agents, ultraviolet absorbers, antioxidants, release agents, fluorescent agents, conductive fillers and the like.
  • Such epoxy resin compositions include paints for printed wiring boards and electronic components, sealing materials, adhesives, resist inks, etc., as well as coating materials for woodwork, optical fibers, plastics, and cans. The use as is expected.
  • the obtained reaction mixture was dried under reduced pressure.
  • the obtained dried product was subjected to liquid separation extraction with 400 mL of ethyl acetate and 400 mL of water.
  • the ethyl acetate layer was washed with 100 mL of water and then with 100 mL of saturated brine, and then dried over anhydrous sodium sulfate.
  • Ethyl acetate was distilled off under reduced pressure, and 1,3,4,6-tetraallylglycoluril 27. 4 g was obtained as a colorless oil. Yield 90%.
  • Example 1 Synthesis of 1,3-diglycidyl glycoluril
  • a 100 mL flask equipped with a thermometer and a stirrer was charged with 1.11 g (5.0 mmol) of 1,3-diallylglycoluril and 10 mL of dichloromethane, and 2.92 g of metachloroperbenzoic acid (purity 65%) under ice cooling. 11.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.
  • Example 2 Synthesis of 1,3,4,6-tetraglycidyl glycoluril
  • a 100 mL flask equipped with a thermometer and a stirrer was charged with 1.51 g (5.0 mmol) of 1,3,4,6-tetraallylglycoluril and 10 mL of dichloromethane, and this was cooled to ice with metachloroperbenzoic acid (purity 65 %) 5.84 g (22.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.
  • Example 3 Synthesis of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril
  • a 100 mL flask equipped with a thermometer and a stirrer was charged with 1.51 g (5.0 mmol) of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril and 10 mL of dichloromethane. After adding acid (purity 65%) 5.84g (22.0mmol), it heated up to room temperature and stirred all night.
  • FIG. 7 shows the IR spectrum of the obtained 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. Further, the ⁇ value in the 1 H-NMR spectrum (CDCl 3 ) was as follows.
  • Example 4 As shown in Table 2, hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as YX8000 in Table 1) is used as a curing agent in 80 parts by mass of 4-methylhexahydrophthalic anhydride / hexahydro.
  • phthalic anhydride mixture of 70/30 by weight, Rikacid MH-700 manufactured by Shin Nippon Chemical Co., Ltd., abbreviated as MH-700 in Table 1
  • tetra-n-butylphosphonium as a curing accelerator -O
  • o-diethyl phosphorodithionate Hishicolin PX-4ET manufactured by Nippon Chemical Industry Co., Ltd., abbreviated as PX-4ET in Table 1
  • TG-G 6-tetraglycidyl glycoluril
  • This epoxy resin composition was heated at a temperature of 120 ° C. for 6 hours to obtain a cured product.
  • Tg glass transition point
  • bending elastic modulus the bending strength
  • bending strength the result shown in Table 2 was obtained.
  • Tg was measured by DSC according to JISK7121.
  • the flexural modulus and flexural strength were measured according to JISK7203.
  • Comparative Example 1 As shown in Table 2, 100 parts by mass of hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Corporation) as a curing agent, 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride (70/30 mixture, new 80 parts by mass of Nippon Rika Co., Ltd. (Licacid MH-700) and tetra-n-butylphosphonium-o, o-diethylphosphorodithionate (Hishicolin PX-4ET, Nippon Chemical Industry Co., Ltd.) as a curing accelerator 5 parts by mass was blended and kneaded to prepare an epoxy resin composition.
  • hydrogenated bisphenol A type epoxy resin YX8000 manufactured by Mitsubishi Chemical Corporation
  • this epoxy resin composition was heated to obtain a cured product, and the glass transition point (Tg), bending elastic modulus and bending strength of this cured product were measured, and the results shown in Table 2 were obtained.
  • Example 4 instead of 20 parts by mass of the crosslinking agent 1,3,4,6-tetraglycidylglycoluril, triglycidyl isocyanuric acid (triglycidyl isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd., in Table 2, TG-ICA) An epoxy resin composition was prepared in the same manner as in Example 4 except that 20 parts by mass was used.
  • triglycidyl isocyanuric acid triglycidyl isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd., in Table 2, TG-ICA
  • this epoxy resin composition was heated to obtain a cured product, and the glass transition point (Tg), bending elastic modulus and bending strength of this cured product were measured, and the results shown in Table 2 were obtained.
  • the epoxy resin composition containing glycidyl glycoluril according to the present invention as a crosslinking agent is a cured product of an epoxy resin composition not containing a crosslinking agent (Comparative Example 1) or a crosslinking agent.
  • the cured epoxy resin composition containing triglycidyl isocyanuric acid Comparative Example 2
  • it has excellent heat resistance and excellent mechanical strength.
  • Epoxy resin composition for optical semiconductor element encapsulation comprises an epoxy resin (1), and at least one component in the epoxy resin is represented by the above general formula ( It is a glycidyl glycoluril represented by B).
  • the epoxy resin composition for sealing an optical semiconductor element according to the present invention contains the following component epoxy resin (1) as an essential component, and further includes the following components ( It may contain at least one selected from 2) to component (9).
  • the epoxy resin of component (1) is a component that forms the main component of the resin composition of the present invention. It is essential that the component (1) contains the glycidyl glycoluril represented by the general formula (B).
  • Specific examples of the glycidyl glycoluril represented by the chemical formula (B) include, for example, 1-glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidyl glycoluril, 1,6-diglycidyl glycoluril, 1,3,4-triglycidyl glycoluril, 1,3,4,6-tetraglycidylglycoluril, 1-glycidyl-3a-methyl-glycoluril, 1,3-diglycidyl-3a-methyl-glycoluril, 1,4-diglycidyl-3a-methyl-glycoluril, 1,6-diglycidyl-3a-methyl-glycoluril, 1,3,4-triglycidyl-3a
  • the glycidyl glycoluril represented by the general formula (B) may be used alone or in combination with one or more other epoxy resins.
  • the other epoxy resin is preferably liquid at room temperature, but even if it is solid at room temperature, it may be diluted with another liquid epoxy resin or diluent to be used in a liquid state. it can.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolac type epoxy resin and cresol novolak type epoxy resin, nitrogen-containing ring such as isocyanurate type epoxy resin and hydantoin type epoxy resin Epoxy resin, cycloaliphatic epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, which is the mainstream of low water absorption rate cured body type, A dicyclo ring type epoxy resin, a naphthalene type epoxy resin, etc. are mentioned.
  • the epoxy resin may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
  • the isocyanurate type epoxy resin includes 1,3,5-triglycidyl isocyanurate, 1-allyl-3,5-diglycidyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate, and the like. Is mentioned.
  • alicyclic epoxy resin more specifically, a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring represented by the following general formula (1) And a compound in which an epoxy group is directly bonded to the alicyclic ring represented by the following general formula (2) by a single bond.
  • R 6 represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, and an ester bond. , A carbonate group, an amide group, a group in which a plurality of these are linked, and the like.
  • n is an integer of 1 to 30
  • p is an integer of 1 to 10
  • R ′ is a group obtained by removing p —OH from a p-valent alcohol.
  • Representative examples of the alicyclic epoxy compound represented by the general formula (1) include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate.
  • Typical examples of the alicyclic epoxy compound represented by the general formula (2) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and the like. Is mentioned.
  • the content of the glycidyl glycoluril represented by the general formula (B) with respect to 100% by weight of the total amount of the epoxy group-containing compounds contained in the resin composition of the present invention is not particularly limited, but is 0.1 to 100% by weight. Is preferred.
  • Component (2) Glass filler
  • a known glass filler can be used, and is not particularly limited.
  • glass beads, glass flakes, glass powder, milled glass, glass fiber, A glass fiber cloth (for example, a glass cloth, a glass nonwoven fabric, etc.) etc. are mentioned.
  • glass beads, glass flakes, and glass powder are preferred from the viewpoints of easily increasing the filling rate and improving moisture absorption reflow resistance and thermal shock resistance.
  • glass which comprises a glass filler
  • T glass, E glass, C glass, A glass, S glass, L glass, D glass, NE glass, quartz glass, low dielectric constant glass examples thereof include high dielectric constant glass.
  • E glass, T glass, and NE glass are preferable because they have few ionic impurities and are excellent in heat resistance and electrical insulation.
  • one type of glass filler can be used alone, and two or more types of sentences can be used in combination.
  • the refractive index of the sodium D line (light having a wavelength of 589.29 nm) of the glass filler is not particularly limited, but is preferably 1.40 to 2.10. When the refractive index is out of this range, the transparency of the cured product tends to be remarkably lowered.
  • wire of a glass filler can be measured using an Abbe refractometer (measurement temperature: 25 degreeC), for example.
  • the average particle diameter thereof is not particularly limited, but is preferably 0.5 to 200 ⁇ m.
  • the average particle size of the glass filler is expressed by calculating the average value of the particle size of the glass filler (glass beads, glass filler, etc.) using, for example, a laser diffraction / scattering particle size distribution measuring device. Can do.
  • the method of weaving these filament knots is not particularly limited, and examples thereof include plain weave, Nanako weave, satin weave and twill weave.
  • the thickness of the glass fiber cloth (including the glass nonwoven fabric) is not particularly limited, but is preferably 20 to 200 ⁇ m.
  • a glass fiber cloth (including a glass nonwoven fabric) can be used alone, or a plurality of glass fiber cloths can be used.
  • the glass filler may have been surface-treated with a known surface treatment agent.
  • a surface treatment agent include silane coupling agents such as ⁇ -aminopropyl pyrethoxysilane and ⁇ -glycidoxypillylethoxysilane, surfactants, inorganic acids, and the like.
  • the content (blending amount) of the glass filler is not particularly limited, but is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.
  • Component (3) Curing Agent
  • the resin composition of the present invention may further contain a curing agent of component (3).
  • curing agent is a compound which has a function which hardens the compound which has an epoxy group, and can use a well-known hardening
  • the curing agent is preferably a liquid acid anhydride at room temperature, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride.
  • solid acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride are dissolved in a liquid acid anhydride at room temperature to form a liquid. By using this mixture, it can be preferably used as a curing agent in the practice of the present invention.
  • curing agent can be used individually by 1 type or in combination of 2 or more types.
  • a curing agent from the viewpoint of heat resistance, light resistance, and crack resistance of a cured product, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (a ring having a substituent such as an alkyl group bonded thereto) Including).
  • the curing agent trade names “Licacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), “Rikacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.), Commercial products such as “5500” (manufactured by Hitachi Chemical Co., Ltd.) can also be used.
  • the content (blending amount) of the curing agent is not particularly limited, but is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.
  • the resin composition of the present invention may further contain a component (4) curing accelerator.
  • the curing accelerator is a compound having a function of accelerating the curing rate when the compound having an epoxy group is cured by the curing agent.
  • a known curing accelerator can be used.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • a salt thereof for example, phenol salt, octylate
  • P-toluenesulfonate formate, tetraphenylborate salt
  • 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof for example, phenol salt, octylate, p- ⁇ ruene sulfonate, formate, tetraphenylborate salt
  • tertiary amines such as benzyldimethylamine, 2,4,6-4 , ris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine
  • 2-ethyl Imidazole such as -4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole;
  • the content (blending amount) of the curing accelerator is not particularly limited, but is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.
  • the resin composition of the present invention may further contain a curing catalyst of component (5).
  • the curing catalyst is a compound having a function of initiating a curing reaction of a compound having an epoxy group and / or accelerating the curing reaction. Although it does not specifically limit as a curing catalyst, Cationic catalyst (cationic polymerization initiator) which generate
  • a curing catalyst can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, and hexafluoroarsenate salt.
  • Examples of the cation catalyst that generates cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes.
  • a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a chelate of a metal such as aluminum or titanium and acetoacetic acid or diketone It may be a compound of a compound and a phenol such as bisphenol S.
  • the content (blending amount) of the curing catalyst is not particularly limited, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition.
  • the resin composition of the present invention preferably further contains a polyester resin of component (6).
  • a polyester resin By containing a polyester resin, the heat resistance and light resistance of the cured product are improved, and the light intensity of the optical semiconductor device tends to be suppressed.
  • the alicyclic polyester resin is a polyester resin having at least an alicyclic structure (aliphatic ring structure).
  • the alicyclic polyester resin is preferably an alicyclic polyester resin having an alicyclic ring (alicyclic structure) in the main chain.
  • the alicyclic structure in the alicyclic polyester resin is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Of these, a saturated monocyclic hydrocarbon structure and a saturated bridged ring hydrocarbon structure in which the alicyclic skeleton (carbon-carbon bond) is entirely composed of carbon-carbon single bonds are particularly preferable.
  • the alicyclic structure in the alicyclic polyester resin may be introduced into only one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both may be introduced, and particularly limited. Not.
  • the alicyclic polyester resin has a structural unit derived from a monomer component having an alicyclic structure.
  • the monomer having an alicyclic structure include diols and dicarboxylic acids having a known alicyclic structure, and are not particularly limited.
  • the alicyclic polyester resin may have a structural unit derived from a monomer component having no alicyclic structure.
  • the monomer having no alicyclic structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid, sebacic acid, azelaic acid, Aliphatic dicarboxylic acids such as succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3- Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-p
  • a monomer having an appropriate substituent for example, an alkyl group, an alkoxy group, or a halogen atom
  • a monomer having an appropriate substituent for example, an alkyl group, an alkoxy group, or a halogen atom
  • the ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin is not particularly limited, but is preferably 10 mol% or more.
  • the resin composition of the present invention preferably further contains an organosiloxane compound of component (7).
  • the organosiloxane compound is not particularly limited as long as it can be melt-mixed with the epoxy resin, and various polyorganosiloxanes, that is, solids without solvent or liquids at room temperature are used. be able to.
  • the polyorganosiloxane used in the present invention only needs to be capable of being uniformly dispersed in the cured product of the resin composition.
  • Examples of such polyorganosiloxane include those in which a siloxane unit as a constituent component is represented by the following general formula (3). This has a hydroxyl group or an alkoxy group bonded to at least one silicon atom in one molecule, and 10 mol% or more of the monovalent hydrocarbon group (R 7 ) bonded to the silicon atom is substituted or unsubstituted. It becomes an aromatic hydrocarbon group.
  • R 7 is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different.
  • R 8 is a hydrogen atom or 1 carbon atom. And may be the same or different, and m and l each represents an integer of 0 to 3.
  • the unsubstituted saturated monovalent hydrocarbon group specifically includes methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group A linear or branched alkyl group such as a decyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a dicyclopentyl group or a decahydronaphthyl group, and an aromatic group
  • Group tetrahydronaphthyl group, tolyl group, ethylphenyl group and other aryl groups, benzyl group, phenylethyl group, phenyl Examples include aralkyl groups such as a pill group and a methylbenzyl group.
  • R 7 of the general formula (3) as the substituted saturated monovalent hydrocarbon group, specifically, a part or all of the hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, amino And those substituted by an epoxy group, specifically, chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl And substituted hydrocarbon groups such as a group, a difluorophenyl group, a ⁇ -cyanoethyl group, a ⁇ -cyanopropyl group, and a ⁇ -cyanopropyl group.
  • (OR 8 ) in the general formula (3) is a hydroxyl group or an alkoxy group
  • R 8 when (OR 8 ) is an alkoxy group specifically, the above-mentioned R 7 is exemplified.
  • the polyorganosiloxane has a hydroxyl group or alkoxy group bonded to at least one silicon atom in one molecule, that is, at least one of the siloxane units constituting the silicone resin, (OR 8 ) of the general formula (3). It preferably has a group.
  • the amount of hydroxyl groups or alkoxy groups bonded to silicon atoms is preferably set in the range of 0.1 to 15% by weight in terms of OH groups.
  • a siloxane derivative having an epoxy group in the molecule can be used as the organosiloxane.
  • the heat resistance and light resistance of the cured product can be improved to a higher level.
  • the siloxane skeleton (Si-0-Si skeleton) in the siloxane derivative having two or more epoxy groups in the molecule is not particularly limited.
  • polysiloxane skeletons such as polysilsesquioxane.
  • a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity.
  • the siloxane derivative having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule or a linear silicone having two or more epoxy groups in the molecule.
  • numerator can be used individually by 1 type or in combination of 2 or more types.
  • siloxane derivative having two or more epoxy groups in the molecule examples include 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2. , 4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,2,4 , 6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -6,8-dipropyl-2,4 , 6,8-tetramethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,6-dipropyl-2,4,6 , 8-di
  • siloxane derivative having two or more epoxy groups in the molecule examples include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169, and single molecules described in JP-A-2008-19422.
  • An organopolysilsesquioxane resin or the like having at least two epoxy functional groups therein can also be employed.
  • the content (blending amount) of the siloxane derivative having two or more epoxy groups in the molecule is not particularly limited, but is 1 with respect to 100% by weight of the total amount of the compounds having epoxy groups contained in the resin composition of the present invention. ⁇ 100% by weight is preferred.
  • Component (8) Rubber Particles
  • the resin composition of the present invention may further contain a rubber particle of component (8).
  • the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber).
  • the rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) comprising a core portion having rubber elasticity and at least one shell layer covering the core portion.
  • core-shell structure multilayer structure
  • the rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and hydroxyl groups and functional groups capable of reacting with a compound having an epoxy group such as an epoxy resin on the surface. Rubber particles having a carboxyl group (one or both of a hydroxyl group and a carboxyl group) are preferred.
  • the cured product becomes clouded by a thermal shock such as a thermal cycle, and the transparency is lowered.
  • the polymer constituting the core part having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid steal such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. It is preferable to use an essential monomer component.
  • Polymers constituting the core portion having rubber elasticity include, for example, aromatic vinyls such as styrene and ⁇ -methylstyrene, nitriles such as acrylonitrile and methacrylonitrile, conjugated dienes such as butadiene and isoprene, ethylene, and propylene. , Isobutene and the like may be included as a monomer component.
  • the polymer which comprises the core part which has rubber elasticity combines the 1 type (s) or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include. That is, as the polymer constituting the core portion, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers; (meth) acrylic acid ester / aromatic Examples thereof include terpolymers such as vinyl / conjugated dienes.
  • the polymer constituting the core portion may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.
  • the polymer constituting the core portion is composed of other monomer components such as divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc.
  • the monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.
  • the core part of the rubber particle is a core part composed of a (meth) acrylate / aromatic vinyl binary copolymer (especially butyl acrylate / styrene). It is preferable in that the rate can be easily adjusted.
  • the core part of the rubber particles can be manufactured by a commonly used method, for example, by a method of polymerizing the above monomer by an emulsion polymerization method.
  • the whole amount of the monomer may be charged all at once and may be polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently to polymerize.
  • a polymerization method using seed particles may be used.
  • the polymer constituting the shell layer of rubber particles is preferably a polymer different from the polymer constituting the core portion.
  • the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with an epoxy group-containing compound such as an epoxy resin.
  • the polymer constituting the shell layer preferably contains (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
  • (meth) acrylic acid esters other than butyl acrylate for example, (meth) acrylic acid Methyl, ethyl (meth) acrylate, butyl methacrylate, etc. are preferably used.
  • Examples of monomer components that may be contained other than (meth) acrylic acid esters include aromatic vinyl such as styrene and ⁇ -methylstyrene, and nitriles such as acrylonitrile and methacrylonitrile.
  • the monomer component constituting the shell layer includes the (meth) acrylic acid ester alone or in combination of two or more, and particularly includes at least aromatic vinyl. It is preferable in that the refractive index of rubber particles can be easily adjusted.
  • the polymer constituting the shell layer may be a hydroxyl group-containing monomer (for example, a monomer component) to form a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an epoxy resin.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate
  • carboxyl group-containing monomers for example, ⁇ , s-unsaturated acids such as (meth) acrylic acid, ⁇ such as maleic anhydride) , ⁇ -unsaturated acid anhydride, etc.).
  • the polymer constituting the shell layer in the rubber particles contains, as a monomer component, one or more selected from the monomers together with (meth) acrylic acid ester. That is, the shell layer is formed of, for example, ternary co-polymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / ⁇ , ⁇ -unsaturated acid, etc.
  • a shell layer composed of coalescence or the like is preferable.
  • the polymer constituting the shell layer is divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, in addition to the above-mentioned monomers, in the same manner as the core part as other monomer components.
  • One monomer (one molecule) such as diallyl phthalate or butylene glycol diacrylate may contain a reactive crosslinking monomer having two or more reactive functional groups.
  • Rubber particles can be obtained by covering the core portion with a shell layer.
  • the method of coating the core part with the shell layer include, for example, a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method And a method of graph-polymerization using the core portion having rubber elasticity obtained by the above as a trunk component and each component constituting the shell layer as a branch component.
  • the average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm.
  • the refractive index of the rubber particles is, for example, cast into rubber molds and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. From the obtained flat plate, a test of 20 mm in length ⁇ 6 mm in width is performed. A multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) is used with the prism and the test piece in close contact using monobromonaphthalene as an intermediate solution. It can be obtained by measuring the refractive index at 20 ° C. and sodium D line.
  • a test piece having a length of 20 mm ⁇ width of 6 mm ⁇ thickness of 1 mm is cut out from a cured product obtained by the heat curing method described in the section of the optical semiconductor device below.
  • a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, and 20 ° C. It can be determined by measuring the refractive index at the sodium D line.
  • the content (blending amount) of the rubber particles in the resin composition of the present invention is not particularly limited, but is 100% by mass for 100 parts by mass of the total amount of the compounds having an epoxy group contained in the resin composition of the present invention. 5 to 30 parts by mass is preferable.
  • Component (9) Additive
  • the resin composition of the present invention may contain various additives of the component (9) within the range not impairing the effects of the present invention, in addition to those described above.
  • an additive for example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained, the reaction can be allowed to proceed slowly.
  • Other silane couplings such as silicone and fluorine antifoaming agents, leveling agents, ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired.
  • Conventional additives such as additives, surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, UV absorbers, ion adsorbents, pigments, phosphors, mold release agents, etc. be able to.
  • the resin composition of the present invention only needs to contain at least one epoxy resin as the component (1) described above, and the production method (preparation method) is not particularly limited.
  • the components can be prepared by mixing each component at a predetermined ratio and defoaming under vacuum as necessary, or glycolurils represented by the general formula (B)
  • a composition (sometimes referred to as an “epoxy resin”) containing a curing agent and a composition containing a curing agent and a curing accelerator, or a curing catalyst as an essential component (sometimes referred to as an “epoxy curing agent”) May be prepared separately, and the epoxy resin and the epoxy curing agent may be mixed at a predetermined ratio, and defoamed under vacuum as necessary.
  • the glass filler may be blended in advance as a component of the epoxy resin and / or the epoxy curing agent, or when the epoxy resin and the epoxy curing agent are mixed, the epoxy resin and the epoxy resin. You may mix
  • the temperature at the time of mixing when preparing the epoxy resin is not particularly limited, but is preferably 30 to 150 ° C. Further, the mixing temperature when preparing the epoxy curing agent is not particularly limited, but is preferably 30 to 100 ° C.
  • a known apparatus such as a rotation / revolution mixer, a planetary mixer, a kneader, or a dissolver can be used.
  • the resin composition of the present invention contains a curing agent and the polyester resin as essential components
  • the alicyclic polyester resin and the curing agent are mixed in advance from the viewpoint of obtaining a more uniform composition.
  • an epoxy curing agent was prepared by blending the mixture with a curing accelerator and other additives, and then an epoxy resin prepared separately from the epoxy curing agent. It is preferable to prepare by mixing.
  • the temperature at which the polyester resin and the curing agent are mixed is not particularly limited, but is preferably 60 ° C to 130 ° C.
  • the mixing time is not particularly limited, but is preferably 30 to 100 minutes. Although mixing is not specifically limited, It is preferable to carry out in nitrogen atmosphere. Moreover, the above-mentioned well-known apparatus can be used for mixing.
  • an appropriate chemical treatment for example, hydrogenation, terminal modification of the polyester resin, etc.
  • a part of the curing agent may react with the polyester resin (for example, a hydroxyl group of the polyester resin).
  • the heating temperature (curing temperature) at the time of curing is not particularly limited, but is preferably 45 to 200 ° C. Further, the heating time (curing time) during curing is not particularly limited, but is preferably 30 to 600 minutes.
  • the curing conditions depend on various conditions. For example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing condition can be appropriately adjusted by increasing the curing time. .
  • the resin composition of the present invention can be preferably used as a resin composition for optical semiconductor encapsulation.
  • an optical semiconductor device having a high heat resistance, light resistance, and thermal shock resistance in which an optical semiconductor element is sealed with a cured product that is particularly excellent in moisture absorption reflow resistance. can get.
  • this optical semiconductor device is equipped with a high-output, high-brightness optical semiconductor element, the light intensity is less likely to decrease over time, especially when it is heated in a reflow process after being stored under high-humidity conditions. However, deterioration such as a decrease in luminous intensity is unlikely to occur.
  • the optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the resin composition (resin composition for sealing an optical semiconductor) of the present invention.
  • the optical semiconductor element is sealed by injecting the resin composition prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened
  • the curing temperature and the curing time can be set in the same range as when the cured product is prepared.
  • Example 1 First, 1,3,4,6-tetraglycidylglycoluril (TG-G, manufactured by Shikoku Kasei Kogyo Co., Ltd.), trade name “Celoxide 2021P” (unit: parts by mass) shown in Table 3 Alicyclic epoxy compound (manufactured by Daicel Corporation) and trade name “Glass Beads CF0018WB15C” (glass filler, manufactured by Nippon Fritz Co., Ltd.) -250) to prepare an epoxy resin by mixing and defoaming uniformly.
  • TG-G 1,3,4,6-tetraglycidylglycoluril
  • trade name “Celoxide 2021P” unit: parts by mass
  • Table 3 Alicyclic epoxy compound (manufactured by Daicel Corporation) and trade name “Glass Beads CF0018WB15C” (glass filler, manufactured by Nippon Fritz Co., Ltd.) -250)
  • this epoxy resin composition is cast on an optical semiconductor lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm), and then heated in an oven (resin curing oven) at 120 ° C. for 5 hours to thereby produce this epoxy resin.
  • An optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the resin composition was obtained.
  • Examples 2 and 3 and Comparative Example 1 An epoxy resin composition was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3, and an optical semiconductor device in which an optical semiconductor element was sealed was produced.
  • ⁇ Luminance retention (%) ⁇ ⁇ Total luminous flux after 100 hours (Im) ⁇ / ⁇ total luminous flux after 100 hours (Im) ⁇ ⁇ 100 [Solder heat resistance test]
  • the optical semiconductor devices (two used for each epoxy resin composition) obtained in the examples and comparative examples were left to stand for 192 hours under conditions of a temperature of 30 ° C. and a relative humidity of 70% to perform a moisture absorption treatment.
  • the optical semiconductor device was put in a reflow furnace and heat-treated under the following heating conditions. Thereafter, this optical semiconductor device was taken out in a room temperature environment, allowed to cool, and then placed in a reflow furnace again and subjected to heat treatment under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.
  • Heating conditions (based on surface temperature of optical semiconductor device)] (1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: Above 217 ° C. for 60 to 150 seconds, maximum temperature 260 ° C. However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum. Then, using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), the optical semiconductor device was observed, whether or not a crack with a length of 90 ⁇ m or more occurred in the cured product, and the electrode It was evaluated whether or not peeling (peeling of the cured product from the electrode surface) occurred.
  • the number of optical semiconductor devices having a crack of 90 ⁇ m or longer in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Table 3, and electrode peeling occurred.
  • the number of optical semiconductor devices is shown in the column of “Solder heat resistance test [number of electrode peeling]” in Table 3.
  • Thermal shock test The optical semiconductor devices obtained in the examples and comparative examples (two used for each epoxy resin composition) were exposed in an atmosphere of ⁇ 40 ° C. for 30 minutes, and subsequently 30 ° C. in an atmosphere of 120 ° C. Thermal shock with one minute exposure was applied for 200 cycles using a thermal shock tester. After that, the length of cracks generated in the cured product in the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and cured among the two optical semiconductor devices. The number of optical semiconductor devices in which cracks having a length of 90 ⁇ m or more occurred in the object was measured. The results are shown in the column of “Thermal shock test [number of cracks]” in Table 3.
  • thermosetting resin composition containing a phenol compound
  • the thermosetting resin composition according to the present invention contains glycidyl glycoluril represented by the general formula (B) and a phenol resin as components.
  • thermosetting resin composition according to the present invention, as the glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidyl glycoluril, 1,6-diglycidyl glycoluril, 1,3,4-triglycidyl glycoluril, 1,3,4,6-tetraglycidylglycoluril, 1-glycidyl-3a-methyl-glycoluril, 1,3-diglycidyl-3a-methyl-glycoluril, 1,4-diglycidyl-3a-methyl-glycoluril, 1,6-diglycidyl-3a-methyl-glycoluril, 1,3,4-triglycidyl-3a-methyl-glycoluril, 1,3,4,6-tetraglycidyl-3a-methyl-glycoluril, 1-glycidyl-3a, 6a-dimethyl-glycoluril, 1,3-diglycidyl-3a, 6a-dimethyl-g
  • an epoxy compound (resin) having two or more epoxy groups in one molecule can be used in combination with the glycidyl glycol uril compound.
  • epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ether type epoxy resins, alicyclic epoxy resins, and heterocyclic type epoxy resins. Etc.
  • the blending ratio of the epoxy component in which the glycidyl glycoluril and the epoxy compound are combined is preferably 10 to 60% by mass, more preferably 20 to 50% by mass in the entire thermosetting resin composition. % By mass.
  • the phenol compound (resin) acts as a curing agent for the epoxy compound (resin).
  • phenol resins conventionally used as a curing agent for an epoxy compound specifically, a phenol resin such as a cresol novolac type resin or a phenol novolac type resin is mixed and used. can do.
  • a phenol resin or a cresol resin having a naphthol skeleton, a naphthalenediol skeleton, a biphenyl skeleton, or a dicyclopentadiene skeleton in the molecular structure is preferable.
  • phenol resins examples include SN-485 (trade name, hydroxyl equivalent 215, manufactured by Nippon Steel Chemical Co., Ltd.), which is a cresol novolak resin having an ⁇ -naphthol skeleton, and a phenol novolak resin containing a naphthalenediol skeleton.
  • SN-395 (trade name, hydroxyl equivalent 105, manufactured by Nippon Steel Chemical Co., Ltd.), MEH-7851-3H (trade name, hydroxyl equivalent 223, manufactured by Meiwa Kasei Co., Ltd.), which is a phenol novolac resin having a biphenyl skeleton, dicyclo And DPP-6125 (trade name, hydroxyl equivalent 185, manufactured by Nippon Petrochemical Co., Ltd.), which is a phenol novolac resin containing a pentadiene skeleton.
  • phenol resins may be used alone or in combination of two or more.
  • the amount of the phenolic resin is preferably in a range where the ratio of the number of phenolic hydroxyl groups possessed by the phenolic resin to the number of epoxy groups possessed by the epoxy resin [number of phenolic hydroxyl groups / number of epoxy groups] is 0.5 to 1.
  • the range of 8 to 1 is more preferable.
  • thermosetting resin composition of the present invention includes an inorganic filler, a curing accelerator, a flame retardant such as a metal hydroxide or zinc borate, an antifoaming agent, and a leveling agent as long as the effects of the present invention are not impaired.
  • a flame retardant such as a metal hydroxide or zinc borate
  • an antifoaming agent such as a metal hydroxide or zinc borate
  • a leveling agent as long as the effects of the present invention are not impaired.
  • Other commonly used additives can be blended as necessary.
  • Inorganic fillers include fused silica, synthetic silica, crystalline silica, alumina, zirconia, talc, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, titanium white, bengara, silicon carbide, boron nitride, silicon nitride, Examples thereof include powders such as aluminum nitride, beads obtained by spheroidizing these, single crystal fibers, and glass fibers. These can be used alone or in admixture of two or more.
  • silica can be used after being surface-treated with a silane-based or titanium-based coupling agent or the like, if necessary.
  • Silane coupling agents include epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropylmethyldiethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) and aminosilanes such as - ⁇ -aminopropyltrimethoxysilane.
  • the blending ratio of the inorganic filler is preferably 20 to 50% by mass, more preferably 30 to 40% by mass in the entire thermosetting resin composition. By making a mixture ratio 20 mass% or more, it can prevent that heat resistance falls.
  • curing accelerator examples include 2-heptadecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 4-methylimidazole, 4-ethylimidazole, 2-phenyl -4-hydroxymethylimidazole, 2-enyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Imidazole compounds such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, methyldiphenylphosphine Such as dibutylphenylphosphine, tricyclohexylphosphine
  • Organic phosphine compounds organic phosphine compounds; diazabicycloalkene compounds such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo (4,3,0) nonene-5; triethylamine, triethylenediamine And tertiary amine compounds such as benzyldimethylamine, ⁇ -methylbenzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol.
  • diazabicycloalkene compounds such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo (4,3,0) nonene-5
  • triethylamine triethylenediamine
  • tertiary amine compounds such as benzyldimethylamine, ⁇ -methylbenzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethyl
  • thermosetting resin composition in the present invention is prepared as a resin solution (varnish) by dissolving or dispersing in an appropriate solvent.
  • the solvent used for dissolving or dispersing the thermosetting resin composition is not particularly limited, but a solvent having a boiling point of 220 ° C. or lower is preferably used in order to minimize the amount remaining in the prepreg.
  • a solvent having a boiling point of 220 ° C. or lower is preferably used in order to minimize the amount remaining in the prepreg.
  • Specific examples of the solvent include ⁇ -butyrolactone, N-methyl-2-pyrrolidone, dimethylacetamide, methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone, propylene glycol monomethyl ether, and the like. A mixture of more than one species can be used.
  • propylene glycol monomethyl ether is preferably used.
  • the solid content concentration of the varnish is not particularly limited, but when it is too low, the amount of resin impregnated in the prepreg decreases, and when it is too high, the viscosity of the varnish increases and the appearance of the prepreg may deteriorate. Therefore, the range of 40 to 80% by mass is preferable, and 60 to 70% by mass is more preferable.
  • a prepreg can be produced by applying or impregnating the varnish to a substrate and then drying to remove the solvent.
  • the base material impregnated with varnish is preferably a woven or non-woven fabric made of glass fiber, aramid fiber, polyparabenzoxazole fiber, polyarylate fiber or the like.
  • the weaving method for the woven fabric is not particularly limited, but plain weaving is preferable from the viewpoint of flatness.
  • the amount of varnish impregnated in the prepreg is preferably in the range of 40 to 70% by mass as the solid content in the total amount with the base material.
  • 40 mass% or more it prevents that an unimpregnated part arises in a base material, and prevents a void and a blurring when it is set as a laminated board.
  • 70 mass% or less it will prevent that the dispersion
  • the method of impregnating or applying the varnish to the substrate and the method of drying after the impregnation or application are not particularly limited, and conventionally known methods can be employed.
  • a metal-clad laminate can be manufactured by stacking a metal foil such as a copper foil on one side or both sides of a prepreg in which a required number of layers are laminated and pressurizing under heating.
  • the printed wiring board of the present invention can be manufactured by laminating semiconductor chips such as silicon chips by etching the metal-clad laminate in a conventional manner.
  • the processing conditions for producing the laminate and the metal-clad laminate are not particularly limited, but usually a heating temperature of about 170 to 200 ° C., a pressure of about 5 to 50 MPa, and a heating / pressurizing time of 90 to It takes about 150 minutes.
  • the main raw materials used in the examples and comparative examples and the evaluation tests adopted in the examples and comparative examples are as follows.
  • [Main ingredients] (I) Epoxy compound, 1,3,4,6-tetraglycidylglycoluril, product name “TG-G”, manufactured by Shikoku Kasei Kogyo Co., Ltd., bisphenol F type epoxy resin, product name “YDF8170”, Toto Kasei Co., Ltd. ⁇ Naphthalene epoxy resin, product name “HP4032D”, manufactured by DIC Corporation ⁇ Naphthol aralkyl epoxy resin, product name “ESN-175”, manufactured by Toto Kasei Co., Ltd.
  • Solder heat resistance It evaluated based on JISC6481. The evaluation was performed by performing PCT moisture absorption treatment at 121 ° C., 100% for 2 hours, and then immersing in a solder bath at 288 ° C. for 30 seconds, and then checking for an appearance abnormality.
  • Example 1 Preparation of varnish> Propylene glycol as a solvent with 20 parts by mass of 1,3,4,6-tetraglycidylglycoluril, 50 parts by mass of novolac type phenolic resin, 40 parts by mass of fused silica, and 0.5 parts by mass of imidazole curing accelerator Monomethyl ether was added and stirred using a high-speed stirrer to obtain a resin varnish whose resin composition was 70% by mass on the basis of solid content.
  • the entire surface of the double-sided copper-clad laminate was etched to produce a 5 mm ⁇ 20 mm test piece, and the linear expansion coefficient was measured.
  • a 100 mm ⁇ 20 mm test piece was prepared from the double-sided copper-clad laminate, and the peel strength was measured.
  • the surface electrolytic copper foil layer was subjected to blackening treatment, and a ⁇ 60 ⁇ m via hole for interlayer connection was formed with a carbon dioxide laser.
  • a swelling solution at 70 ° C. (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further in an aqueous solution of potassium permanganate at 80 ° C. (Atotech Japan, Concentrate Compact CP) for 15 minutes. After soaking, neutralization was performed, and desmear treatment in the via hole was performed.
  • electroless copper plating is performed with a thickness of 0.5 ⁇ m
  • a resist layer for electrolytic copper plating is formed with a thickness of 18 ⁇ m
  • pattern copper plating is performed.
  • the film was post-cured by heating at 60 ° C. for 60 minutes.
  • a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 20 ⁇ m was formed on the circuit surface to obtain a multilayer printed wiring board.
  • the alkali development type photocurable / thermosetting resin composition according to the present invention comprises: (A) Glycidyl glycoluril represented by the general formula (B), (B) A photosensitive prepolymer having two or more unsaturated double bonds in one molecule and (c) a photopolymerization initiator.
  • the glycidyl glycoluril is a glycol glycoluril represented by the general formula (B), that is, an epoxy compound, 1-glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidyl glycoluril, 1,6-diglycidyl glycoluril, 1,3,4-triglycidyl glycoluril, 1,3,4,6-tetraglycidylglycoluril, 1-glycidyl-3a-methylglycoluril, 1,3-diglycidyl-3a-methylglycoluril, 1,4-diglycidyl-3a-methylglycoluril, 1,6-diglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-3a-methylglycoluril, 1,3,4,6-tetraglycidyl-3a-methylglycoluril, 1-glycidyl-3a, 6a-dimethylglycoluril
  • epoxy resin an epoxy compound or an epoxy resin excluding the glycidyl glycoluril (hereinafter referred to as “epoxy resin” together), bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, diglycidyl ether of propylene glycol or polypropylene glycol, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane glycidyl ether, phenyl-1 , 3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol glycidyl ether, ethylene glycol 1 such as diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, penta
  • S-triazine compounds such as melamine as reaction accelerators
  • imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole and derivatives thereof
  • known curing accelerators for epoxy resins such as phenol compounds
  • the photosensitive prepolymer having two or more unsaturated double bonds in one molecule is a polymer or oligomer having two or more epoxy groups in one molecule, for example, in one molecule.
  • Polyfunctional epoxy compound having two or more epoxy groups see the above-mentioned epoxy resin
  • Photosensitivity obtained by reacting an unsaturated monocarboxylic acid having an unsaturated double bond with a copolymer of glycidyl (meth) acrylate and the like, followed by addition reaction of an unsaturated or saturated polycarboxylic acid anhydride
  • the photosensitive prepolymer has many free carboxyl groups in the side chain, development with a dilute aqueous alkali solution is possible, and at the same time, after exposure / development, the film is post-heated to provide another thermosetting compounding component. As a result, an addition reaction takes place between the epoxy group of the added epoxy compound and the free carboxyl group of the side chain, resulting in a cured film with excellent properties such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical properties. Obtainable.
  • the total content of glycoluril and epoxy resin excluding glycoluril is preferably 0.01 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.
  • examples of the photopolymerization initiator include benzoins such as benzyl, benzoin, benzoin methyl ether, and benzoin isopropyl ether and zonzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, N, N— Acetophenones such as dimethylaminoacetophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone Anthraquinones such as 2-aminoanthraquinon
  • the photopolymerization initiator may be a known photosensitizer such as a tertiary amine such as triethylamine or triethanolamine, or a benzoic acid ester such as ethyl-4-dimethylaminobenzoate or 2- (dimethylamino) ethylbenzoate. You may use it in combination with 1 type, or 2 or more types of a sensitizer. Further, a titanocene photopolymerization initiator such as Irgacure 784 (manufactured by Ciba Specialty Chemicals) that initiates radical polymerization in the visible region, a leuco dye, or the like may be used in combination as a curing aid.
  • a titanocene photopolymerization initiator such as Irgacure 784 (manufactured by Ciba Specialty Chemicals) that initiates radical polymerization in the visible region, a leuco dye, or the like may be used in
  • the content of the photopolymerization initiator is preferably 0.01 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.
  • a photopolymerizable vinyl monomer and / or an organic solvent can be used as the diluent used in the practice of the present invention.
  • Examples of the photopolymerizable vinyl monomer include mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; Acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide addition of these phenols Acrylates such as hexane; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol Polyols, polyhydric alcohols such as tris-hydroxyethyl isocyanurate, or polyvalent acrylates of these ethylene oxide or propylene oxide adduct
  • the content of the photopolymerizable vinyl monomer is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.
  • organic solvent examples include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, and acetic acid esterified products of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more.
  • the content of the organic solvent is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.
  • the purpose of using the photopolymerizable vinyl monomer is to enhance the photopolymerizability and dilute the photosensitive prepolymer to facilitate application.
  • the purpose of using the organic solvent is to dissolve and dilute the photosensitive prepolymer and thereby apply it as a liquid. Therefore, depending on the type of diluent, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the film is adopted.
  • polyurethane fine particles As the polyurethane compound used in the practice of the present invention, known polyurethane fine particles can be employed.
  • the particle diameter of the polyurethane fine particles is preferably 0.01 to 100 ⁇ m.
  • Polyurethane fine particles are obtained by mechanically crushing solid polyurethane at low temperature, by precipitating and drying from an aqueous polyurethane emulsion, spray drying, and by adding a poor solvent to solution-polymerized polyurethane to precipitate polyurethane into granules. It can be prepared by a method such as drying to remove the solvent.
  • the surface of the polyurethane fine particles may be coated with a hydrophobic silica coating or a fluorine compound-treated silica.
  • polybutadiene compound used in the practice of the present invention is to make the film flexible.
  • polybutadiene containing one or more internal epoxy groups (hereinafter referred to as “epoxidized polybutadiene”) undergoes a cross-linking reaction due to having an internal epoxy group and is polymerized, so that it has heat resistance, chemical resistance, and electroless resistance. Flexibility can be imparted without impairing properties such as gold plating properties.
  • Examples of the epoxidized polybutadiene include polybutadiene containing one or more oxirane oxygens bonded to carbon in the polybutadiene main chain.
  • the epoxidized polybutadiene may contain one or more side groups and / or epoxy groups as end groups.
  • the content of the polybutadiene compound is preferably 0.4 to 60 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.
  • the resin composition of the present invention includes various antifoaming agents, leveling agents, extender pigments such as silica, alumina, barium sulfate, calcium carbonate, calcium sulfate, and talc, and pigments such as titanium oxide, azo, and phthalocyanine. Additives can be included.
  • the resin composition of the present invention can contain a photosensitive prepolymer other than the photosensitive prepolymer.
  • a photosensitive prepolymer other than the photosensitive prepolymer.
  • Other photosensitive prepolymers can be used without particular limitation as long as they have an unsaturated group and a carboxyl group.
  • the cured product of the resin composition of the present invention preferably has an elastic modulus at room temperature of 500 to 2000 MPa and an elongation of 5 to 100%.
  • the elastic modulus is less than 500 MPa, the flexibility and the thermal shock resistance are excellent, but the characteristics such as solder heat resistance may be deteriorated.
  • the elastic modulus exceeds 2000 MPa or the elongation is less than 5%, flexibility and thermal shock resistance may be reduced.
  • the resin composition is first adjusted to a viscosity suitable for the coating method, and then printed on a circuit pattern previously formed.
  • a film can be formed by applying to a wiring board by a screen printing method, a curtain coating method, a roll coating method, a spray coating method or the like, and if necessary, a drying treatment at a temperature of 60 to 100 ° C., for example.
  • the film can be formed by a method such as making the resin composition into a dry film and directly laminating it on a printed wiring board. Then, it selectively exposes with actinic light through the photomask which formed the predetermined exposure pattern. It is also possible to directly expose and draw in a pattern with a laser beam. Next, the unexposed portion can be developed with an aqueous alkali solution to form a resist pattern. Further, for example, by heating to 140 to 180 ° C. and thermosetting, the photosensitive resin can be photosensitive in addition to the curing reaction of the thermosetting component. Polymerization of the resin component is promoted, and the resulting resist film can be improved in heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT (pressure cooker test) resistance, adhesion, electrical characteristics, etc. it can.
  • PCT pressure cooker test
  • an aqueous solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like can be used.
  • a xenon lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, or the like is suitable.
  • laser beams and the like can also be used as actinic rays.
  • part means “part by mass” unless otherwise specified.
  • Synthesis example 1 The epoxy equivalent is 217, and an average of 7 phenol nucleus residues in one molecule and 1 equivalent of a cresol novolac type epoxy resin having an epoxy group combined with 1.05 equivalent of acrylic acid are reacted. The resulting reaction product was reacted with 0.67 equivalent of tetrahydrophthalic anhydride by a conventional method to obtain a photosensitive prepolymer.
  • the obtained photosensitive prepolymer was a viscous liquid containing 35 parts of carbitol acetate, and the acid value as a mixture was 65 mgKOH / g.
  • Photosensitive prepolymer / photosensitive prepolymer synthesized in Synthesis Example 1 (hereinafter referred to as “prepolymer”) (3) Photopolymerization initiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 907, hereinafter “Irgacure 907” ”) 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name: DETX-S, hereinafter referred to as “DETX-S”)
  • Diluent, dipentaerythritol hexaacrylate hereinafter referred to as “DPHA”
  • Diluentaerythritol hexaacrylate hereinafter referred to as “DPHA”
  • diethylene glycol monoethyl ether acetate hereinafter referred to as “carbitol acetate”
  • Example 1 A photocurable / thermosetting resin composition was prepared by mixing and dispersing each component with a three-roll mill so as to have the composition (parts by mass) shown in Table 5.
  • Comparative Example 1 A photocurable / thermosetting resin composition having the composition shown in Table 5 was prepared in the same manner as in Example 1 except that YX-4000 was used instead of TG-G.
  • Example 1 The resin composition obtained in Example 1 and Comparative Example 1 was applied to the entire surface of a printed wiring board on which a pattern was formed by etching a glass-epoxy-based copper-clad laminate laminated with a 35 ⁇ m copper foil. It apply
  • FIG. 1 The resin composition obtained in Example 1 and Comparative Example 1 was applied to the entire surface of a printed wiring board on which a pattern was formed by etching a glass-epoxy-based copper-clad laminate laminated with a 35 ⁇ m copper foil. It apply
  • test piece 1 Thereafter, a desired negative film is adhered to the test piece 1 and irradiated with ultraviolet rays of 600 mJ / cm 2 from above, followed by development with a 1.0 wt% aqueous sodium carbonate solution for 60 seconds, and hot air circulation drying A test piece 2 having a cured film formed by thermosetting under a condition of 150 ° C./60 minutes using a machine was obtained.
  • test piece 1 and test piece 2 the test results were as shown in Table 5.
  • test piece 2 was coated with rosin flux and immersed in a solder bath at 260 ° C. for 10 seconds, and then the cured film was subjected to a peeling test using a cellophane tape to evaluate the state of the cured film thereafter. When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.
  • test piece 2 was immersed in 10% hydrochloric acid for 30 minutes, the state of the cured film was visually observed. When there was no change, it was judged as ⁇ , and when it was swollen and peeled, it was judged as ⁇ .
  • the elastic modulus and elongation were measured by a tensile-compression tester (manufactured by Shimadzu Corporation).
  • the test piece 2 was judged in a state of being bent 180 °. When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.
  • the test piece 2 was allowed to stand at 125 ° C. for 5 days, and then judged in a state of being bent at 180 ° C. When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.
  • Thermal shock resistance The test piece 2 was subjected to 300 cycles of cooling / heating at ⁇ 65 ° C./30 minutes and 150 ° C./30 minutes, and then judged by the presence or absence of cracks in the cured film. When there was no crack, it was judged as “good”, and when there was a crack, it was judged as “poor”.
  • Electroless gold plating resistance Using a commercially available electroless nickel plating bath and electroless gold plating bath, after plating the test piece 2 under the same conditions as those for obtaining a thickness of nickel 0.5 ⁇ m and gold 0.03 ⁇ m, tape peeling Thus, the presence or absence of peeling of the cured film was evaluated. When there was no peeling, it was judged as ⁇ , when there was a slight peeling, ⁇ , and when there was peeling, it was judged as x.
  • the photocurable / thermosetting resin composition of the present invention is useful for forming a solder resist film used for printed wiring boards for various applications.
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 and R 4 each independently represent a hydrogen atom or an allyl group.
  • R 1 or R 2 when R 1 or R 2 is a lower alkyl group, the lower alkyl group usually has 1 carbon atom. -5, preferably 1-3, most preferably 1, so the most preferred lower alkyl group is a methyl group.
  • allyl glycolurils include, for example, 1-allyl glycoluril, 1,3-diallylglycoluril, 1,4-diallylglycoluril, 1,6-diallylglycoluril, 1,3,4-triallylglycoluril, 1-allyl-3a-methylglycoluril, 1,3-diallyl-3a-methylglycoluril, 1,4-diallyl-3a-methylglycoluril, 1,6-diallyl-3a-methylglycoluril, 1,3,4-triallyl-3a-methylglycoluril, 1-allyl-3a, 6a-dimethylglycoluril, 1,3-diallyl-3a, 6a-dimethylglycoluril, 1,4-diallyl-3a, 6a-dimethylglycoluril, 1,6-diallyl-3a, 6a-dimethylglycoluril, 1,6-diallyl-3a, 6a-dimethylglycoluril, 1,3,4-tri
  • the allyl glycolurils represented by the general formulas (C0a) to (C0e) can be usually obtained by the following first step and second step.
  • 1-allylglycoluril reacts urea and glyoxal in the first step, usually in water in the presence of a base catalyst, and then the reaction product thus obtained is usually submerged in water in the second step. It can be obtained by reacting with allylurea in the presence of an acid catalyst.
  • 1,3-diallylglycoluril is obtained by reacting urea and glyoxal in the first step, usually in water in the presence of a base catalyst, and then the reaction product thus obtained.
  • the second step usually by reacting with diallyl urea in water in the presence of an acid catalyst.
  • triallyl glycolurils for example, 1,3,4-triallylglycoluril
  • allylurea and glyoxal are usually reacted in water in the presence of a base catalyst
  • the reaction product thus obtained can be obtained in the second step by reacting with diallylurea usually in water in the presence of an acid catalyst.
  • glyoxal is used relative to 1 mol part of urea or allylurea. In general, it is used in the range of 0.5 to 2.0 mole parts, preferably in the range of 0.8 to 1.5 mole parts.
  • Examples of the base catalyst used in the first step include hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate and potassium carbonate. These base catalysts are usually used in the range of 0.1 to 1.0 mole part per mole part of urea or allylurea.
  • the solvent when used, it is not particularly limited as long as the reaction is not inhibited.
  • alcohols such as water, methanol, ethanol, isopropyl alcohol
  • Aliphatic hydrocarbons such as hexane and heptane
  • ketones such as acetone and 2-butanone
  • esters such as ethyl acetate and butyl acetate
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • methylene chloride Halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene
  • ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether
  • Amides such as muamide, N, N-dimethylformamide, N, N,
  • the reaction temperature in the first step is usually in the range of ⁇ 10 to 150 ° C., preferably in the range of 0 ° C. to 100 ° C.
  • the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.
  • reaction product as a concentrate, which may be subjected to the second step, or obtained after the completion of the first step.
  • the reaction mixture obtained may be used as it is in the second step.
  • allyl urea or diallyl urea is usually used in a range of 0.5 to 2.0 mol parts, preferably 1 mol part of urea or allyl urea used in the first step. , 0.8 to 1.5 mole parts.
  • Examples of the acid catalyst used in the second step include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid and the like. These acid catalysts can be used alone or in combination of two or more. These acid catalysts are usually used in the range of 0.1 to 100 parts by mole with respect to 1 part by mole of urea or allylurea used in the first step.
  • the solvent is not particularly limited as long as it does not inhibit the reaction, and the same solvent as in the first step can be used.
  • the reaction temperature in the second step is usually in the range of ⁇ 10 to 200 ° C., preferably in the range of 0 ° C. to 150 ° C.
  • the reaction time depends on the reaction temperature, it is usually in the range of 1 to 24 hours, preferably in the range of 1 to 12 hours.
  • the produced allyl glycoluril can be appropriately taken out from the obtained reaction mixture by an extraction operation or the like. If necessary, the obtained allyl glycoluril can be further purified by washing with a solvent such as water, activated carbon treatment, silica gel chromatography and the like.
  • urea, allyl urea, and 40% glyoxal aqueous solution were manufactured by Tokyo Chemical Industry Co., Ltd., and diallyl urea was manufactured by Sigma-Aldrich.
  • Example 1 (Synthesis of 1-allylglycoluril) A 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to the resulting mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. The resulting reaction mixture was then concentrated under reduced pressure. To the obtained concentrate, 5.01 g (50.0 mmol) of allylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added and stirred at 110 ° C. overnight. The resulting reaction mixture was cooled to room temperature, 50 mL of acetone was added, the oil was separated and dried to give 1.86 g of 1-allylglycoluril as a white viscous oil. Yield 20%.
  • Example 2 Synthesis of 1,3-diallylglycoluril
  • a 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution.
  • Two drops of 40% aqueous sodium hydroxide solution were added to the obtained mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour.
  • the resulting reaction mixture was then concentrated under reduced pressure.
  • 7.00 g (50.0 mmol) of diallylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C. overnight.
  • 50 mL of acetone was added, and the oil was separated and dried to obtain 4.28 g of 1,3-diallylglycoluril as a white viscous oil. Yield 39%.
  • FIG. 9 shows the IR spectrum of the obtained 1,3-diallylglycoluril. Further, the ⁇ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
  • Example 3 Synthesis of 1,3,4-triallylglycoluril
  • a 100 mL flask equipped with a thermometer was charged with 3.00 g (30.0 mmol) of allylurea and 5.22 g (36.0 mmol) of 40% aqueous glyoxal solution.
  • Two drops of 40% aqueous sodium hydroxide solution were added to the obtained mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour.
  • the resulting reaction mixture was then concentrated under reduced pressure.
  • 4.21 g (30.0 mmol) of diallylurea, 30 mL of acetic acid and 294 mg (3.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C.
  • FIG. 10 shows the IR spectrum of the obtained 1,3,4-triallylglycoluril. Further, the ⁇ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
  • the olefin resin composition according to the present invention includes allyl glycoluril represented by the general formula (C) and an olefin polymer.
  • the olefin polymer used in the olefin resin composition according to the present invention refers to a polymer of an olefin monomer, a polymer of a polar monomer, a copolymer of an olefin monomer and a polar monomer, and the like.
  • olefin monomer examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4-methyl.
  • ⁇ -olefin compound having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Cyclopentene, cycloheptene, 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-
  • a cyclic olefin compound having 3 to 20 carbon atoms Aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, substituted allylnaphthalenes; Alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, allyl norbornane; Silane unsaturated compounds such as allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-decene; Examples thereof include conjugated or non-con
  • polar monomer examples include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acids and their metal salt compounds such as sodium, potassium, lithium, zinc, magnesium, calcium
  • the olefin polymers exemplified in these may be used alone or in combination of two or more.
  • allyl glycoluril represented by the general formula (C) is used as a crosslinking aid.
  • R 1 and R 2 are lower alkyl groups
  • the carbon number thereof is preferably 1 to 3, and more preferably 1. That is, R 1 and R 2 are more preferably methyl groups.
  • allyl glycolurils 1-allyl glycoluril, 1,3-diallylglycoluril, 1,4-diallylglycoluril, 1,6-diallylglycoluril, 1,3,4-triallylglycoluril, 1,3,4,6-tetraallylglycoluril, 1-allyl-3a-methylglycoluril, 1,3-diallyl-3a-methylglycoluril, 1,4-diallyl-3a-methylglycoluril, 1,6-diallyl-3a-methylglycoluril, 1,3,4-triallyl-3a-methylglycoluril, 1,3,4,6-tetraallyl-3a-methylglycoluril, 1-allyl-3a, 6a-dimethylglycoluril, 1,3-diallyl-3a, 6a-dimethylglycoluril, 1,4-diallyl-3a, 6a-dimethylglycoluril, 1,6-diallyl-3a, 6a-dimethylg
  • Such unsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl glycidyl isocyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate; Poly (meth) acryloxy compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate; Examples include divinylbenzene.
  • the crosslinking aid is preferably blended at a rate of 0.1 to 100 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the olefin polymer. More preferred.
  • the crosslinking of the olefin-based resin composition of the present invention can be performed by adopting a method of mixing and heating a peroxide or a method of irradiating active energy rays.
  • the heating temperature in the case of heating by adding a peroxide is not particularly limited, but is preferably set in the range of 50 to 300 ° C.
  • peroxide illustrated in these may be used independently and may be used in combination of 2 or more types.
  • Examples of the active energy rays include particle beams and electromagnetic waves.
  • Examples of the particle beams include electron beams (EB) and ⁇ rays.
  • Examples of electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, ⁇ rays, and X rays. Etc.
  • electron beams and ultraviolet rays are preferably used as active energy rays.
  • active energy rays can be irradiated using a known apparatus.
  • the acceleration voltage is preferably 0.1 to 10 MeV, and the irradiation dose is preferably 1 to 500 kGy.
  • ultraviolet rays a lamp having a radiation wavelength of 200 to 450 nm can be used as the radiation source.
  • tungsten filament In the case of an electron beam, for example, a tungsten filament is used, and in the case of ultraviolet light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultraviolet mercury lamp, a carbon arc lamp, a xenon lamp, a zirconium lamp, and the like.
  • ultraviolet light for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultraviolet mercury lamp, a carbon arc lamp, a xenon lamp, a zirconium lamp, and the like.
  • a photopolymerization initiator When ultraviolet rays are used as the active energy ray, a photopolymerization initiator can be further blended.
  • the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2.
  • Acetophenones such as morpholinopropan-1-one; Benzoins such as benzyldimethyl ketal; Benzophenones such as benzophenone, 4-phenylbenzophenone, hydroxybenzophenone; Thioxanthones such as isopropylthioxanthone and 2,4-diethylthioxanthone; And methylphenylglyoxylate.
  • the photopolymerization initiators exemplified in these may be used alone or in combination of two or more.
  • the photopolymerization initiator is blended, it is preferably blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the olefin copolymer.
  • photopolymerization accelerators such as benzoic acids such as 4-dimethylaminobenzoic acid and tertiary amines can be used in combination.
  • a silane coupling agent can be blended in order to enhance the adhesion when compounded with materials of different materials.
  • silane coupling agents examples include ⁇ -chloropropylmethoxysilane, vinylethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and ⁇ -glycidoxypropyl.
  • silane coupling agents exemplified in these may be used alone or in combination of two or more, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the olefin copolymer. It is preferable to mix
  • an antioxidant in the olefin resin composition of the present invention, an antioxidant, a light stabilizer (ultraviolet absorber) and the like can be blended in order to prevent deterioration due to ultraviolet rays in sunlight.
  • a light stabilizer ultraviolet absorber
  • phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, Monophenol compounds such as stearyl- ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t -Butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis ⁇ 1,1-dimethyl-2- [ ⁇ - (3-tert-butyl-4-hydroxy-) Bisphenol compounds such as 5-methylphenyl) propionyloxy] ethyl ⁇ 2,4,8,10-tetraoxaspiro [5.5] undecane; 1,1,3-
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2, 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentane Tetraylbi (2,4-di-tert-butyl-4-methylphenyl) phosphite, bis ⁇ 2-tert-butyl-6-methyl-4- [2- (
  • the light stabilizer examples include salicylic acid compounds such as phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, Benzophenone compounds such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′- Di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-
  • the antioxidants and light stabilizers exemplified in these are preferably blended at a ratio of 0.1 to 3 parts by mass with respect to 100 parts by mass of the olefin polymer.
  • a fatty acid salt of a metal such as cadmium or barium can be added to the olefin resin composition of the present invention as an anti-discoloration agent.
  • pigments, dyes, inorganic fillers and the like can be blended for the purpose of coloring and the like. Examples of these include white pigments such as titanium oxide and calcium carbonate, blue pigments such as ultramarine, black pigments such as carbon black, and glass beads and light diffusing agents.
  • additives are preferably blended at a ratio of 0.5 to 50 parts by mass with respect to 100 parts by mass of the olefin polymer.
  • the olefin resin composition of the present invention for example, using a tank mixer, a high-speed stirrer, a closed kneader, an internal mixer, a single screw extruder, a twin screw extruder, etc., if necessary, under a nitrogen atmosphere, At an appropriate temperature, the olefin polymer and the allyl glycoluril represented by the general formula (C), if necessary, together with a peroxide, a photopolymerization initiator, and other optional components, It can be prepared by wet mixing, dry mixing or melt mixing.
  • the peroxide When using the peroxide to crosslink the olefin resin composition of the present invention, it can be cross-linked during the melt mixing.
  • the olefin-based resin composition of the present invention is suitably used as a raw material to be processed into various shapes of molded products such as films, sheets, cases (containers), etc. by a known molding method.
  • Known molding methods include, for example, inflation molding method, T-die molding method, tubular stretch molding method, tenter stretch molding method, extrusion laminate molding method, dry laminate molding method, calendar molding method, bank molding method, injection molding method. , Compression molding method, injection compression molding method, compressed air molding method, vacuum molding method, pipe molding method, profile extrusion molding method, hollow molding method, injection hollow molding method, injection stretch hollow molding method and the like.
  • the olefin resin composition of the present invention is Various rubber materials such as packing and sealing materials for automobiles, Solar cell encapsulant (EVA), Insulation coatings and adhesives for electrical and electronic equipment and parts, Wire coating materials, Laminates, structural composite materials, adhesives and anticorrosive materials for civil engineering, paints, Molded products such as various switches, relays, transformers, coil bobbins, connectors, etc. for electronic components that require heat resistance at a level that does not cause melting deformation when soldering, LED sealing material, Various plastic materials for optical materials such as reflectors and lenses, Suitable for applications such as automobiles, electrical / electronic parts, etc.
  • EVA Solar cell encapsulant
  • Insulation coatings and adhesives for electrical and electronic equipment and parts Wire coating materials, Laminates, structural composite materials, adhesives and anticorrosive materials for civil engineering, paints, Molded products such as various switches, relays, transformers, coil bobbins, connectors, etc. for electronic components that require heat resistance at
  • polybutylene terephthalate resin which is a crystalline thermoplastic polyester resin with excellent mechanical properties, electrical properties, and other physical and chemical properties and good workability.
  • Example 1 100 parts by mass of ethylene / vinyl acetate copolymer (vinyl acetate content: 25%, melt index value: 4) as an olefin polymer, 1 part by mass of dicumyl peroxide as a peroxide, 1,3 as a crosslinking aid 5,4,6-tetraallylglycoluril and 5 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane as a silane coupling agent were mixed to prepare an olefin-based resin composition.
  • a sheet having a thickness of 0.5 mm was prepared for a test piece at a processing temperature of 100 ° C. using a profile extruder.
  • Examples 2-6 and Comparative Examples 1-2 A sheet having the composition shown in Table 6 was prepared in the same manner as in Example 1, and the haze value and total light transmittance were measured and shown in Table 6.
  • Curable composition excellent in adhesiveness is: (A) an organic compound having an alkenyl group, (B) A curable composition comprising a compound having at least three or more hydrosilyl groups in one molecule and (C) a hydrosilylation catalyst, As said (A) component, general formula (C1)
  • X represents a hydrogen atom, an alkyl group or an aryl group.
  • X represents a hydrogen atom, an alkyl group or an aryl group.
  • the component (B) is preferably (B-1) an organic compound having at least two alkenyl groups and (B-2) a chain having at least two hydrosilyl groups in one molecule. And / or (B-3) an organically modified silicone compound obtained by a hydrosilylation reaction with a cyclic organohydrogensiloxane.
  • the component (B-1) is preferably polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, trivinylcyclohexane, triallyl isocyanurate, methyldiallyl isocyanurate and the general formula ( C2)
  • R 1 , R 2 , R 3 and R 4 are all organic groups, at least two of which are alkenyl groups, and X represents a hydrogen atom, an alkyl group or an aryl group.
  • the component (B-1) is preferably a tetraallyl glycoluril represented by the general formula (C1).
  • the component (B-2) is a cyclic and / or chain polyorganosiloxane having at least two hydrosilyl groups in one molecule, and preferably a cyclic polyorganosiloxane having at least two hydrosilyl groups in one molecule.
  • Organosiloxane Organosiloxane.
  • the organic compound having an alkenyl group in the present invention is not particularly limited as long as it is an organic compound having at least one alkenyl group in one molecule.
  • the organic compound does not contain a siloxane unit such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and may contain only C, H, N, O, S and halogen atoms as constituent elements. preferable.
  • the bonding position of the alkenyl group is not particularly limited, and may be present at any position in the skeleton.
  • component (A) examples include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, di Arylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, monoallyl dimethyl isocyanurate, 1,2,4-trivinylcyclohexane, diallyl monomethyl isocyanurate, divinylbenzenes (having a purity of 50 to 100%, preferably Has a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably In addition to the allyl ether of novolak phenol, allylated polyphenyl,
  • the tetraallylglycoluril from the viewpoint of adhesion to a substrate when the curable composition is cured with the substrate, it is preferable to use the tetraallylglycoluril, and further, a balance of heat and light resistance. From the viewpoint of reducing the thermal stress effectively, it is preferable to use the tetraallylglycolurils.
  • tetraallyl glycoluril 1,3,4,6-tetraallylglycoluril, 1,3,4,6-tetraallyl-3a-methyl-glycoluril, 1,3,4,6-tetraallyl-3a, 6a-dimethyl-glycoluril
  • examples include 1,3,4,6-tetraallyl-3a, 6a-diphenyl-glycoluril and the like.
  • the skeleton of the component (A) may have a functional group other than an alkenyl group, but from the viewpoint of compatibility with the component (B), a straight chain such as a methyl group, an ethyl group, or a propyl group.
  • a functional group having a low polarity such as the above aliphatic hydrocarbon group is preferred.
  • these (A) components may be used alone or in combination of two or more, but from the viewpoint of controlling the physical properties of the cured product, it is preferable to use two or more in combination, and heat resistance as described above. From the viewpoint of balance between light resistance and adhesiveness, it is more preferable to use tetraallyl glycoluril.
  • the component (B) in the present invention is mainly used as a curing agent, and is not particularly limited as long as it is an organosiloxane having at least three hydrosilyl groups in the molecule.
  • an organohydrogenorganosiloxane an organic compound having at least two alkenyl groups (component (B-1)), and a chain and / or cyclic structure having at least two hydrosilyl groups in one molecule.
  • organohydrogenorganosiloxane an organic compound having at least two alkenyl groups
  • component (B-2) organically modified silicone compounds obtained by hydrosilylation reaction of organohydrogenorganosiloxane
  • the organohydrogenorganosiloxane refers to a siloxane compound having a hydrocarbon group or a hydrogen atom on a silicon atom.
  • an organically modified silicone compound (B-3) from the viewpoint of compatibility with the component (A) which is an organic compound.
  • organohydrogenorganosiloxane examples include a chain or cyclic group represented by the general formula (1), the general formula (2) or the general formula (3), and a polyhedral polysiloxane containing a hydrosilyl group. .
  • R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.
  • R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.
  • R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.
  • organically modified silicone as the component (B-3), various types can be synthesized and used by combining the components (B-1) and (B2).
  • the component (B-1) is not particularly limited as long as it is an organic compound having at least two alkenyl groups. Specific examples thereof include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, Pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes ( Having a purity of 50 to 100%, preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl monoglycidyl isocyanurate, diallyl monomer Ruisocyanurate, diallyl ether of bisphenol A, diallyl ether
  • the component (B-1) is preferably an organic compound having a heterocyclic skeleton from the viewpoint that a cured product having good characteristics can be obtained.
  • the organic compound having a heterocyclic skeleton is not particularly limited as long as it is a compound having a hetero element in the cyclic skeleton, but those containing Si in the atoms forming the ring are excluded.
  • heterocyclic ring examples include epoxy, oxetane, furan, thiophene, pyralol, oxazole, furazane, triazole, tetrazole, pyran, pyridine, oxazine, thiazine, pyridazine,
  • glycoluril-based ones may be mentioned, but glycoluril-based heterocycles are preferable in that the effects of the present invention are dramatically achieved.
  • the component (B-1) it is preferable to use the glycoluril represented by the general formula (C2), and it is more preferable to use the tetraallylglycoluril.
  • allyl glycoluril including the tetraallyl glycoluril, 1-allyl glycoluril, 1,3-diallylglycoluril, 1,4-diallylglycoluril, 1,6-diallylglycoluril, 1,3,4-triallylglycoluril, 1,3,4,6-tetraallylglycoluril, 1-allyl-3a-methyl-glycoluril, 1,3-diallyl-3a-methyl-glycoluril, 1,4-diallyl-3a-methyl-glycoluril, 1,6-diallyl-3a-methyl-glycoluril, 1,3,4-triallyl-3a-methyl-glycoluril, 1,3,4,6-tetraallyl-3a-methyl-glycoluril, 1-allyl-3a, 6a-dimethyl-glycoluril, 1,3-diallyl-3a, 6a-dimethyl-glycoluril, 1,4-diallyl-3a, 6a-tetraally
  • the component (B-2) in the present invention is not particularly limited as long as it is an organohydrogensiloxane compound having at least two hydrosilyl groups in one molecule.
  • an organohydrogensiloxane compound having at least two hydrosilyl groups in one molecule For example, it is described in International Publication No. 96/15194 pamphlet.
  • a compound having at least two hydrosilyl groups in one molecule can be used.
  • a linear and / or cyclic organopolysiloxane having at least two hydrosilyl groups in one molecule is preferable, and the compatibility in the silicone-based curable composition is good.
  • cyclic organopolysiloxane is preferable.
  • cyclic siloxanes containing hydrosilyl groups examples include 1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetra.
  • Siloxane 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5, 7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11 -Hexamethylcyclosiloxane and the like are exemplified, but 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability.
  • the molecular weight of the component (B-2) is not particularly limited and any can be used, but from the viewpoint of fluidity, those having a low molecular weight are preferably used.
  • the lower limit of the molecular weight is 58, and the upper limit is 100,000, more preferably 1,000, and still more preferably 700.
  • solid platinum is supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black, etc .; platinum-vinylsiloxane complex ⁇ for example, Pt n (ViMe 2 SiOSiMe 2 Vi ) N , Pt [(MeViSiO) 4 ] m ⁇ ; platinum-phosphine complex ⁇ eg Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 ⁇ ; platinum-phosphite complex ⁇ eg Pt [P (OPh) 3 ] 4 , Pt [P (OBu) 3 ] 4 ⁇ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer), Pt ( acac) 2 Also, platinum-hydrocarbon complexes described in Ashby et al., US Pat. Nos. 3,159,
  • catalysts other than platinum compounds include RhCl (PPh 3 ) 3 , RhCl 3 , Rh / Al 3 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 .2H 2 O, NiCl 2. , TiCl 4 , and the like.
  • catalysts may be used alone or in combination of two or more.
  • chloroplatinic acid platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) 2 and the like are preferable.
  • the catalyst amount of component (C) is not particularly limited, but is preferably in the range of 10 ⁇ 1 to 10 ⁇ 8 mol per mol of alkenyl group in component (A), and is preferably 10 ⁇ 2 to 10 ⁇ . More preferably, it is used in the range of 6 moles. When the amount is less than 10 ⁇ 8 mol, hydrosilylation may not proceed sufficiently. When an amount exceeding 10 ⁇ 1 mol is used, the storage stability of the composition may be deteriorated. In addition, these (C) components may be used independently and may use 2 or more types together.
  • the curable composition in the present invention is not particularly limited as long as it is a composition that cures by a hydrosilylation reaction and contains a compound having an alkenyl group, a compound having a hydrosilyl group, and a hydrosilylation catalyst.
  • the composition ratio of the component (A) and the component (B) in the curable composition is not particularly limited, but from the viewpoint of efficiently proceeding the curing reaction, the molar ratio is in the range of 0.5 to 2.0. Preferably, it is in the range of 0.7 to 1.5, more preferably in the range of 0.8 to 1.3. (However, the molar ratio represents (number of moles of hydrosilyl group of component (B)) / (number of moles of alkenyl group of component (A)).)
  • the molar ratio is less than 0.5, for example, when the composition is cured, excessive alkenyl groups may remain in the system, which may cause problems with the heat resistance of the cured product. Is more than 1.3, excess hydrosilyl groups may remain in the system. For example, a condensation reaction between hydrosilyl groups may occur during a long-term heat test, and the properties of the cured product may deteriorate. .
  • the viscosity of the curable composition is preferably 2000 cP or less, more preferably 1000 cP or less, and further preferably 500 cP or less from the viewpoint of handling properties.
  • a curing retarder can be used for the purpose of improving the storage stability of the curable composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction during the production process.
  • the curing retardant include compounds having an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin-based compounds, organic peroxides, and the like, and these may be used in combination.
  • Examples of the compound having an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like.
  • Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.
  • Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like.
  • Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like.
  • tin compounds include stannous halide dihydrate and stannous carboxylate.
  • organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
  • benzothiazole thiazole, dimethyl malate, and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good retarding activity and easy availability of raw materials.
  • an adhesion-imparting agent can be added as an additive for the purpose of improving the adhesion to an adherend.
  • a silane coupling agent, a boron-based coupling agent, titanium A coupling agent, an aluminum coupling agent, or the like can be used.
  • silane coupling agent examples include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group.
  • a silane coupling agent having a group is preferred.
  • this functional group it is more preferable that they are an epoxy group, a methacryl group, and an acryl group from the point of sclerosis
  • organosilicon compounds having an epoxy functional group and a silicon atom-bonded alkoxy group 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl
  • examples include trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.
  • organosilicon compound having a methacrylic group or an acrylic group and a silicon atom-bonded alkoxy group examples include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- Examples include acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.
  • boron coupling agent examples include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, Trinormal butyl borate, tri-sec borate -Butyl, boric acid tri-tert. -Butyl, triisopropyl borate, trinormalpropyl borate, triallyl borate, boron methoxyethoxide.
  • titanium coupling agent examples include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i- Propoxy (2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, Tetra-i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) Chirenchitaneto,
  • Examples of the aluminum coupling agent include aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.
  • adhesiveness-imparting agents may be used alone or in combination of two or more.
  • the addition amount of the adhesion-imparting agent is preferably 5 parts by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B).
  • additives can be used for the purpose of imparting tackiness and adhesion to a cured product obtained by curing the curable composition of the present invention.
  • a compound which has an alkenyl group or a hydrosilyl group Comprising: At the time of hardening by hydrosilylation, (A) component or (B ) It is preferable to use a compound capable of forming a chemical bond with the component.
  • Examples of the compound having an alkenyl group include a dimethylpolysiloxane blocked with a dimethylvinylsiloxy group at both ends of the molecular chain having an alkenyl group, a dimethylpolysiloxane blocked with a methylphenylvinylsiloxy group at both ends of the molecular chain, and a dimethylvinylsiloxy group blocked at both ends of the molecular chain.
  • additives can be used either individually or in combination of two or more. Moreover, it is preferable that the addition amount of these additives is 5 mass parts or less with respect to a total of 100 mass parts of (A) component and (B) component. In addition, depending on the type or amount of the additive, the influence on the hydrosilylation reaction must be considered.
  • the cured product of the present invention is excellent in heat resistance and light resistance, and also has excellent adhesion to various substrates because of its small curing shrinkage after curing. Therefore, it can be used as a resin layer for various optical devices. it can.
  • the cured product of the present invention preferably has a glass transition temperature of 150 ° C. or lower, more preferably 145 ° C. or lower, and even more preferably 140 ° C. or lower.
  • the glass transition temperature exceeds 150 ° C., thermal stress at the time of curing or in a high temperature environment increases, and for example, warping may occur when cured on a base material, or adhesion to the base material may be reduced. is there.
  • the cured product of the present invention preferably has a storage elastic modulus at 150 ° C. of 500 MPa or less, more preferably 200 MPa or less, and 100 MPa or less from the viewpoint of reducing thermal stress. More preferably.
  • the storage elastic modulus exceeds 500 MPa, the thermal stress increases, and there is a possibility that warping may occur or the adhesion to the substrate may be reduced when cured on the substrate.
  • Various methods can be employed for measuring the glass transition temperature, and examples include dynamic viscoelasticity measurement and thermomechanical measurement, and the storage elastic modulus can be measured by dynamic viscoelasticity measurement. it can.
  • a light emitting diode can be produced using the curable composition of the present invention.
  • the light emitting diode can be coated with the light emitting element with the curable composition of the present invention.
  • the light emitting element is a light emitting element used in a conventionally known light emitting diode.
  • a semiconductor material is laminated on a substrate provided with a buffer layer of GaN, AlN or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth. Things.
  • Various materials can be used as the substrate in this case, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and a GaN single crystal. Among these, it is preferable to use sapphire from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.
  • Examples of the semiconductor material to be stacked include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, SiC, and the like. Of these, nitride-based compound semiconductors (Inx GayAlz N) are preferable from the viewpoint of obtaining high luminance. Such a material may contain an activator or the like.
  • Examples of the structure of the light-emitting element include a MIS junction, a pn junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure. Moreover, it can also be set as a single or multiple quantum well structure.
  • the light emitting element may or may not be provided with a passivation layer.
  • An electrode can be formed on the light emitting element by a conventionally known method.
  • the electrode on the light emitting element can be electrically connected to the lead terminal etc. by various methods.
  • a material having good ohmic mechanical connectivity with the electrode of the light emitting element is preferable, and examples thereof include a bonding wire using gold, silver, copper, platinum, aluminum, or an alloy thereof.
  • a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used.
  • a light-emitting element can be obtained as described above.
  • any light intensity can be used as long as the light intensity in the vertical direction is 1 cd or more.
  • the effect of the present invention is more remarkable when a light emitting element of 2 cd or more is used, and the effect of the present invention is further remarkable when a light emitting element of 3 cd or more is used.
  • the light emission output of the light emitting element can be arbitrarily selected without any particular limitation.
  • the light emission wavelength of the light emitting element may be various wavelengths from the ultraviolet region to the infrared region.
  • the light-emitting element to be used may emit a single color with a single type of light-emitting element, or a combination of a plurality of light-emitting elements may emit a single color or multiple colors.
  • the lead terminal used in the light emitting diode of the present invention preferably has good adhesion to an electrical connecting member such as a bonding wire, electrical conductivity, etc., and the electrical resistance of the lead terminal is preferably 300 ⁇ -cm or less. More preferably, it is 3 ⁇ -cm or less.
  • these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those plated with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted as appropriate in order to obtain a good light spread.
  • the light-emitting diode of the present invention can be produced by coating the light-emitting element with the curable composition of the present invention.
  • the coating is not limited to the one directly sealing the light-emitting element, but indirectly. It also includes the case of coating.
  • the light emitting device may be sealed by various methods conventionally used directly with the curable composition of the present invention, and conventionally used epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, etc. After sealing the light emitting element with the sealing resin or glass, the top or the periphery thereof may be coated with the curable composition of the present invention.
  • the light emitting element after sealing the light emitting element with the curable composition of the present invention, it may be molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like.
  • Various effects such as a lens effect can be provided by the difference in refractive index and specific gravity by the above method.
  • a liquid composition may be injected into a cup, cavity, package recess, or the like in which a light emitting element is arranged at the bottom by a dispenser or other method and cured by heating, or a solid or highly viscous liquid composition
  • the material may be heated and flowed, and similarly injected into the package recesses and further heated to be cured.
  • the package in this case can be made using various materials, such as polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, ABS resin, polybutylene terephthalate resin, polyphthalamide resin, and the like. be able to.
  • a method of injecting a composition into a mold form in advance, dipping a lead frame or the like on which the light emitting element is fixed, and then curing the composition can be adopted.
  • the sealing layer made of the composition may be molded and cured by injection with a dispenser, transfer molding, injection molding or the like.
  • a composition that is simply in a liquid or fluid state may be dropped or coated into a light emitting element shape and cured.
  • the curable resin can be molded and cured by applying it on the light emitting element through stencil printing, screen printing or a mask.
  • a method in which a composition partially cured or cured in a plate shape or a lens shape in advance is fixed on the light emitting element may be used.
  • it can be used as a die bond agent for fixing the light emitting element to a lead terminal or a package, or can be used as a passivation film on the light emitting element. It can also be used as a package substrate.
  • the shape of the covering portion is not particularly limited, and may be various shapes. Examples thereof include a lens shape, a plate shape, a thin film shape, and a shape described in JP-A-6-244458. These shapes may be molded by molding and curing the composition, or may be molded by post-processing after curing the composition.
  • the light emitting diode of the present invention can be of various types, for example, any type such as a lamp type, an SMD type, and a chip type.
  • Various types of SMD type and chip type package substrates are used, and examples thereof include epoxy resin, BT resin, and ceramic.
  • various conventionally known methods can be applied to the light emitting diode of the present invention.
  • a method of providing a layer for reflecting or condensing light on the back surface of the light emitting element a method of forming a complementary colored portion at the bottom corresponding to yellowing of the sealing resin, a thin film that absorbs light having a wavelength shorter than the main emission peak
  • a method in which the light-emitting element is sealed with a soft or liquid sealing material, and the periphery is molded with a hard material, and a phosphor that absorbs light from the light-emitting element and emits longer wavelength fluorescence A method in which the light emitting element is sealed with a material containing, and then the periphery is molded.
  • a method that increases luminous efficiency as a special shape a method that makes the package a two-stage recess to reduce uneven brightness, a method that inserts and fixes light emitting diodes in through holes, Examples include a method of forming a thin film that absorbs light having a wavelength shorter than the light wavelength, and a method of extracting light from the substrate direction by connecting the light emitting element to a lead member by flip chip connection using a solder bump or the like. .
  • the light emitting diode of the present invention can be used for various known applications. Specific examples include a backlight, illumination, sensor light source, vehicle instrument light source, signal light, indicator light, display device, planar light source, display, decoration, various lights, and the like.
  • Adhesion test Cross-cut method 3 cc of the curable composition was coated on a 10 cm ⁇ 10 cm glass substrate, coated to a thickness of 40-60 ⁇ m using a bar coater, and cured by convection oven at 150 ° C. for 1 hour. A coated film was obtained. Using the obtained coating material, a cross-cut test was conducted in accordance with JIS 5600-5-6, and the adhesion was evaluated in six stages from 0 to 5 according to the criteria of the same standard.
  • Synthesis example 1 A stirrer, a condenser tube and a dropping funnel were attached to a 5 L two-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the mixture was heated and stirred in an oil bath at 120 ° C. To this solution, 240 g of 1,3,4,6-tetraallylglycoluril, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours.
  • the product is a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with 1,3,4,6-tetraallylglycoluril. I understood.
  • the modified product thus obtained was used as the component (A) in Examples and Comparative Examples.
  • Synthesis example 2 To a 5 L separable flask, 1380 g of toluene and 1360 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated to an internal temperature of 100 ° C. Thereto was added dropwise a mixture of 330 g of 1,3,4,6-tetraallylglycoluril, 1.36 mL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 300 g of toluene. The dropping was completed in 30 minutes. During the dropping, the internal temperature rose to 109 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure.
  • the obtained product was obtained by reacting part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane with 1,3,4,6-tetraallylglycoluril. I found out.
  • the modified product thus obtained was used as the component (B) in Examples and Comparative Examples.
  • Synthesis example 3 A stirrer, a condenser tube and a dropping funnel were attached to a 5 L two-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the mixture was heated and stirred in an oil bath at 120 ° C. To this solution, 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours.
  • the examples show excellent adhesion without impairing the heat and light resistance, but the comparative examples have insufficient heat stress and light resistance due to insufficient reduction of thermal stress.
  • the curable composition in the present invention gives a cured product having excellent heat and light resistance without impairing the adhesion to various substrates.
  • thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril
  • the thermosetting resin composition according to the present invention comprises: (A) General formula (C3) as alkenyl group-containing organopolysiloxane
  • each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, and p is an integer of 1 to 30.
  • each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, m is an integer of 0 to 5, and each siloxane repeating unit in the formula is bonded randomly. May be.
  • thermosetting resin composition according to the present invention is an organopolysiloxane having an alkenyl group-containing organopolysiloxane as a main agent (base polymer) in which both molecular chain ends represented by the general formula (C3) are blocked with an allyl glycoluril ring.
  • a siloxane polymer that is, an organopolysiloxane polymer having an alkenyl group (allyl group) at both ends of the molecular chain, is used as a curing agent (crosslinking agent) at the end of the siloxane chain represented by the general formula (C4).
  • the component (A) is an organopolysiloxane polymer having an allyl glycoluril ring structure at both ends of the molecular chain represented by the general formula (C3).
  • the organopolysiloxane polymer represented by the general formula (C3) is used as the alkenyl group-containing organopolysiloxane which is the main agent (base polymer).
  • R independently of each other is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and the curing characteristics, flexibility, and synthesis of the composition From the standpoint of ease, it is preferably a methyl group, and 50 mol% or more (50 to 100 mol%) of all R groups are preferably methyl groups.
  • p is an integer of 1 to 30, preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.
  • the weight average molecular weight of the organopolysiloxane polymer is usually 500 to 10,000, preferably 600 to 5,000.
  • the viscosity of the organopolysiloxane polymer at 25 ° C. is usually 0.5 to 1,000 Pa ⁇ s, preferably 1 to 100 Pa ⁇ s.
  • the weight average molecular weight can be determined by, for example, gel permeation chromatography analysis using toluene, THF or the like as a developing solvent, and the viscosity can be determined by, for example, a rotational viscometer (BL type, BH type, BS type, cone plate). Type etc.) (hereinafter the same).
  • the component (A) glycoluril ring-containing organopolysiloxane polymer includes, for example, tetraallylglycoluril represented by the following chemical formula (1) and terminal hydrogensiloxy group-capped organopolysiloxane represented by the following general formula (2): (Hereinafter referred to as the first terminal hydrogensiloxy group-blocked organopolysiloxane) can be obtained by a hydrosilylation addition reaction by a conventionally known method.
  • the reaction temperature is usually room temperature (25 ° C.) to 250 ° C., preferably 50 to 180 ° C.
  • the reaction time is usually 0.1 to 120 hours, preferably 1 to 10 hours.
  • the tetraallyl glycoluril and the first terminal hydrogensiloxy group-capped organopolysiloxane are the first terminal hydrogensiloxy group-capped organopolysiloxane with respect to 1 equivalent of the allyl group in the tetraallylglycoluril molecule.
  • the reaction is carried out in such an amount that the Si—H group in the molecule is 0.1 to 0.9 equivalent, preferably 0.4 to 0.7 equivalent (allyl group excess system).
  • an organopolysiloxane polymer having diallyl glycoluril rings at both ends hereinafter sometimes referred to as a glycoluril ring-containing organopolysiloxane polymer
  • a platinum group metal compound containing platinum, rhodium, or palladium can be used as a catalyst.
  • compounds containing platinum are preferred, such as hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol.
  • a complex, platinum supported on activated carbon, or the like can be used.
  • the amount of the catalyst blended (in terms of metal mass) is preferably 0.01 to 10,000 ppm, more preferably 0.1 to 100 ppm, based on the tetraallylglycoluril (mass). preferable.
  • a solvent can be added as necessary.
  • the solvent toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether and the like can be used.
  • Component (B) is a glycoluril ring-containing organohydrogenpolysiloxane polymer having hydrogen atoms (Si—H groups) bonded to at least two silicon atoms at the ends of the siloxane chain represented by the general formula (C4). It is.
  • a glycoluril ring-containing organohydrogenpolysiloxane polymer represented by the general formula (C4) is used as a curing agent (crosslinking agent).
  • an organohydrogenpolysiloxane (hereinafter referred to as glycoluril) having at least two hydrogen atoms (Si—H groups) bonded to a silicon atom at the end of the siloxane chain (that is, in a monofunctional siloxy unit) Ring-containing terminal hydrogen polysiloxane polymer)), and a hydrogen atom ((H) (R) bonded to the terminal silicon atom of the highly reactive siloxane chain)
  • glycoluril organohydrogenpolysiloxane having at least two hydrogen atoms (Si—H groups) bonded to a silicon atom at the end of the siloxane chain (that is, in a monofunctional siloxy unit) Ring-containing terminal hydrogen polysiloxane polymer)
  • a hydrogen atom ((H) (R) bonded to the terminal silicon atom of the highly reactive siloxane chain)
  • R independently of each other is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and the curing characteristics, flexibility, and ease of synthesis of the composition.
  • a methyl group is preferable, and 50 mol% or more (50 to 100 mol%) of all R is preferably a methyl group.
  • the weight average molecular weight of the organohydrogenpolysiloxane polymer as the component (B) is usually 500 to 10,000, preferably 600 to 5,000.
  • the viscosity of the organohydrogenpolysiloxane polymer at 25 ° C. is usually 0.1 to 100 Pa ⁇ s, preferably 0.5 to 10 Pa ⁇ s.
  • the glycoluril ring-containing terminal hydrogen polysiloxane polymer as the component (B) includes, for example, tetraallylglycoluril represented by the chemical formula (1) and a terminal hydrogensiloxy group-blocked organo group represented by the following general formula (3).
  • Polysiloxane (hereinafter referred to as second terminal hydrogensiloxy group-blocked organopolysiloxane) can be obtained by hydrosilylation addition reaction by a conventionally known method.
  • the reaction temperature is usually room temperature (25 ° C.) to 250 ° C., preferably 50 to 180 ° C.
  • the reaction time is usually 0.1 to 120 hours, preferably 1 to 10 hours.
  • the tetraallyl glycoluril and the second terminal hydrogensiloxy group-blocked organopolysiloxane are the same in the second terminal hydrogensiloxy group-blocked organopolysiloxane molecule with respect to 1 equivalent of the allyl group in the tetraallylglycoluril molecule.
  • the Si—H group is reacted in an amount of 1.1 to 5.0 equivalents, preferably 1.1 to 3.5 equivalents (Si—H group excess system).
  • glycoluril ring-containing organohydrogenpolysiloxane polymer having at least two hydrogensiloxy groups at the end of the siloxane chain can be obtained.
  • Examples of the second terminal hydrogensiloxy-blocked organopolysiloxane include those represented by chemical formulas or general formulas (4) to (6).
  • a platinum group metal compound containing platinum, rhodium, or palladium can be used as a catalyst.
  • compounds containing platinum are preferred, such as hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol.
  • a complex, platinum supported on activated carbon, or the like can be used.
  • the amount of the catalyst (in terms of metal mass) is preferably 0.01 to 10,000 ppm with respect to tetraallylglycoluril (mass) represented by the chemical formula (1), preferably 0.1 to 100 ppm. It is more preferable to set the ratio.
  • a solvent can be added as necessary.
  • the solvent toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether and the like can be used.
  • organohydrogenpolysiloxane polymer obtained by the above-described method examples include those represented by the following general formula (7).
  • the blending amount of the glycoluril ring-containing terminal hydrogen polysiloxane polymer as the component (B) is in the component (B) with respect to 1 mol of allyl groups in the allyl glycoluril ring-blocked organopolysiloxane polymer as the component (A).
  • the amount of Si—H groups is 0.8 to 4.0 moles, and the “Si—H group / allyl group” ratio is preferably 1.0 to 3.0.
  • Crosslinks between the (A) component and the (B) component glycoluril ring-containing organopolysiloxane polymer provide excellent low elasticity, mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, and gas permeability. Cured product can be provided.
  • the organopolysiloxane polymer represented by the general formula (C3) that is the main agent (base polymer) and the organohydrogenpolysiloxane polymer represented by the general formula (C4) that is the curing agent (crosslinking agent) are a semiconductor.
  • halogen ions such as chlorine and alkali ions such as sodium are preferably reduced as much as possible. Normally, when extracted at 120 ° C., all ions are 10 ppm or less. It is desirable.
  • a hydrosilylation addition reaction catalyst can be used, and it is preferable to use a platinum group metal catalyst such as a platinum-based catalyst or a palladium-based catalyst, iron oxide, or the like.
  • platinum group metal catalysts are preferable, and platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of cost and the like, platinum-based metal catalysts such as platinum, platinum black, and chloroplatinic acid are used.
  • the addition amount of the curing accelerator is a catalyst amount (effective amount of curing acceleration), but the addition amount of the platinum group metal catalyst is in terms of mass of the platinum group metal with respect to the total of the component (A) and the component (B). About 0.1 to 500 ppm is preferable. In other addition ranges, there is a concern that poor curing occurs, curing is too fast, and the viscosity rises rapidly, resulting in a decrease in workability.
  • inorganic filler of component is not particularly limited
  • the amount of inorganic filler such as silica of (D) component added to the thermosetting resin composition of the present invention is the allyl end of component (A) which is the main component. 30 to 900 parts by weight, preferably 40 to 40 parts by weight per 100 parts by weight in total of the glycoluril ring-blocked organopolysiloxane polymer and the glycoluril ring-containing terminal hydrogen polysiloxane polymer of component (B) as a curing agent.
  • the resin component the total of the components (A) and (B)
  • the resin component is less than 30 parts by mass
  • sufficient strength cannot be obtained, and when it exceeds 900 parts by mass.
  • the fluidity is lowered due to the thickening, and it becomes difficult to seal the semiconductor elements arranged on the submount due to the poor filling property.
  • thermosetting resin composition of the present invention can be further blended into the thermosetting resin composition of the present invention as necessary.
  • additives for example, curing suppression of organic silicon-based adhesion improvers having epoxy groups, organic phosphorus-containing compounds such as ethynylmethyldecylcarbinol, triphenylphosphine, organic nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole
  • colorants such as various carbon blacks such as acetylene black and furnace black can be added arbitrarily as long as the effects of the present invention are not impaired.
  • thermosetting resin composition of the present invention can be prepared by uniformly mixing the above components by a conventional method.
  • thermosetting resin composition is cured by heating, and the curing conditions are 110 to 200 ° C., particularly 120 to 180 ° C., 1 to 6 hours, particularly 2 to 3 hours. can do.
  • the semiconductor can be similarly sealed by a method such as transfer molding.
  • thermosetting resin composition of the present invention can provide a cured product having excellent low elasticity, mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, gas permeability, and the like. It is a material suitable as a sealing material.
  • thermosetting resin composition of the present invention can provide a semiconductor device that is suppressed in warpage and excellent in heat resistance and moisture resistance even when a semiconductor element is sealed.
  • the semiconductor device manufacturing method is not particularly limited.
  • room temperature shows 25 degreeC and a part shows a mass part.
  • Synthesis example 1 400 g (1.79 mol) of tetraallylglycoluril, 400 g of toluene, and 0.32 g of toluene solution of chloroplatinate (containing 0.5 mass% as platinum) were charged into a 2 L separable flask and heated to 100 ° C. 1,3,3-tetramethyldisiloxane (120 g, 0.89 mol) was added dropwise and stirred at 100 ° C. for 8 hours, and then toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid.
  • chloroplatinate containing 0.5 mass% as platinum
  • Synthesis example 2 900 g (2.73 mol) of tris (dimethylhydrogensiloxy) phenylsilane and 900 g of toluene were charged into a 3 L separable flask, heated to 100 ° C., and 0.71 g of toluene chloroplatinate solution (0.5% by mass as platinum). Content) was added dropwise, and then 300 g (1.34 mol) of tetraallylglycoluril and 300 g of toluene were added dropwise. After stirring at 100 ° C. for 8 hours, toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid.
  • Example 1 A resin composition in which the blending ratio of the main agent and the curing agent was 1.0 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.
  • thermosetting resin composition was obtained.
  • Example 2 A resin composition in which the blending ratio of the main agent and the curing agent was 1.8 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.
  • thermosetting resin composition was obtained.
  • Example 3 A resin composition in which the mixing ratio of the main agent and the curing agent was 2.2 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.
  • thermosetting resin composition was obtained.
  • Comparative Example 1 The main agent is vinylpolysiloxane, the curing agent is branched organohydrogenpolysiloxane, the blending ratio of the main agent and curing agent is 2.0 in the ratio of Si-H group / Si-Vi group, and the silica filler filling amount A resin composition with a high loading of 82% by mass was prepared as shown below.
  • thermosetting resin composition was obtained.
  • Viscosity Viscosity measurement at room temperature was performed with a Brookfield programmable rheometer type: DV-III ultra viscometer (cone spindle CP-51 / 1.0 rpm).
  • both ends of allyl glycoluril ring-blocked organopolysiloxane polymer (compound A) and glycoluril ring-containing terminal hydrogen polysiloxane polymer (compound B) are used as skeletons.
  • the resin compositions of Examples 1 to 3 using only the resin can be obtained by changing the ratio of Si—H group / allyl group in the resin to 1.0, 1.8, and 2.2.
  • the cured product used had good heat resistance and tensile shear adhesion.
  • Electron beam curable resin composition contains polyolefin resin and a crosslinking agent, and the said crosslinking agent is general formula (C5).
  • n 0 or 1. It is an isocyanurate compound represented by these.
  • the electron beam curable resin composition according to the present invention preferably contains a polyolefin resin and a crosslinking agent, and the crosslinking agent is represented by the general formula (C).
  • R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group
  • R 3 , R 4 and R 5 each independently represent a hydrogen atom or an allyl group.
  • the electron beam curable resin composition according to the present invention contains a polyolefin resin and a specific crosslinking agent.
  • the polyolefin resin used in the practice of the present invention is a polymer of an olefin monomer, a polymer of a polar monomer, or a copolymer of an olefin monomer and a polar monomer.
  • olefin monomer examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, ⁇ -olefin compounds having 2 to 20 carbon atoms, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Cyclopentene, cycloheptene, 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-
  • polar monomer examples include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, etc.
  • ⁇ , ⁇ -unsaturated carboxylic acids and metal salt compounds thereof such as sodium, potassium, lithium, zinc, magnesium, calcium
  • the polymer of olefin monomers, the polymer of polar monomers, or the copolymer of olefin monomers and polar monomers may be used alone or in combination of two or more.
  • polymethyl-1-pentene resins in particular, a homopolymer of 4-methyl-1-pentene or a copolymer with other olefin monomer containing 90 mol% or more of 4-methyl-1-pentene (polymethylpentene) Since the refractive index is 1.46, which is close to the refractive index of silica particles, it is possible to suppress the inhibition of optical properties such as reflectance even when blended, and it can be used as a reflector for semiconductor light emitting devices. It is suitable for.
  • a polymethylpentene containing a cross-linking agent made of an isocyanurate compound or glycoluril is irradiated with an electron beam, thereby exhibiting sufficient heat resistance even in a reflow process. As a result, it can be used as a reflector of a semiconductor light emitting device.
  • the crosslinking agent used in the practice of the present invention is the isocyanurate compound represented by the general formula (C5) or the general formula (C6) and the glycoluril represented by the general formula (C).
  • isocyanurate compound represented by the general formula (C5) Ethylene bis (diallyl isocyanurate), Trimethylene bis (diallyl isocyanurate), Tetramethylene bis (diallyl isocyanurate), Pentamethylene bis (diallyl isocyanurate), Hexamethylene bis (diallyl isocyanurate), Heptamethylenebis (diallyl isocyanurate), Octamethylene bis (diallyl isocyanurate), Nonamethylene bis (diallyl isocyanurate), Decamethylene bis (diallyl isocyanurate), Examples include dodecamethylene bis (diallyl isocyanurate). You may use these individually or in combination of 2 or more types.
  • isocyanurate compound represented by the general formula (C6) examples thereof include oxydiethylene bis (diallyl isocyanurate) and 1,2-bis (3,5-diallyl isocyanurethoxy) ethane, and each may be used alone or in combination.
  • allyl glycoluril represented by the general formula (C)
  • 1-allyl glycoluril, 1,3-diallylglycoluril, 1,4-diallylglycoluril, 1,6-diallylglycoluril, 1,3,4-triallylglycoluril, 1,3,4,6-tetraallylglycoluril 1-allyl-3a-methylglycoluril, 1,3-diallyl-3a-methylglycoluril, 1,4-diallyl-3a-methylglycoluril, 1,6-diallyl-3a-methylglycoluril, 1,3,4-triallyl-3a-methylglycoluril, 1,3,4,6-tetraallyl-3a-methylglycoluril, 1-allyl-3a, 6a-dimethylglycoluril, 1,3-diallyl-3a, 6a-dimethylglycoluril, 1,4-diallyl-3a, 6a-dimethylglycoluril, 1,6-diallyl-3
  • the amount of the crosslinking agent used is preferably 0.1 to 50 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably.
  • the unsaturated compound which has an allyl group, a (meth) acryloxy group, etc. can also be used together as another crosslinking agent.
  • Such unsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl glycidyl isocyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, tetraallyl glycoluril; ethylene glycol diacrylate, Examples include poly (meth) acryloxy compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; divinylbenzene and the like.
  • the electron beam curable resin composition of the present invention preferably contains a white pigment or other inorganic particles.
  • the white pigment titanium oxide, zinc sulfide, zinc oxide, barium sulfide or the like can be used alone or in combination of two or more, and titanium oxide is particularly preferable.
  • the amount of the white pigment used is preferably 1 to 500 parts by mass and more preferably 5 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the average particle size of the white pigment is preferably 0.10 to 1.00 ⁇ m in the primary particle size distribution and 0.10 to 0.50 ⁇ m from the viewpoint of obtaining high reflectivity in consideration of moldability. Is more preferable.
  • An average particle diameter can be calculated
  • inorganic particles include spherical fused silica particles, modified cross-section glass fibers, and other glass fibers. Spherical fused silica particles and / or modified cross-section glass fibers are preferred.
  • the spherical fused silica particles and the modified cross-section glass fibers may be blended with ordinary thermoplastic resin compositions or thermosetting resin compositions such as epoxy resins, acrylic resins, and silicone resins, alone or in combination of two or more. Can be used.
  • Spherical fused silica particles are prepared, for example, through a process in which a silicon dioxide powder raw material such as silica is entrained in a powdered state with a carrier gas such as air in a flame formed in a melting zone in a furnace and injected from a burner.
  • a carrier gas such as air in a flame formed in a melting zone in a furnace and injected from a burner.
  • the volume average particle diameter of the spherical fused silica particles is preferably 0.1 to 500 ⁇ m, and more preferably 1 to 300 ⁇ m.
  • the volume average particle diameter can be obtained as a mass average value D50 in particle size distribution measurement by a laser light diffraction method.
  • the irregular cross-section glass fiber is a fiber having a cross-sectional shape having a different major axis and minor axis, and can be reinforced almost equally in the resin flow direction (MD) and its vertical direction (TD). Excellent in preventing warping.
  • the cross-sectional shape has a minor axis (D1) of 0.5 to 25 ⁇ m, a major axis (D2) of 0.6 to 300 ⁇ m, and a ratio D2 / D1 of D2 to D1 of 1.2 to 30.
  • Glass fibers having an average fiber length of 0.75 to 300 ⁇ m are preferable.
  • the fiber diameter and the fiber length can be obtained by randomly extracting a predetermined amount of glass fiber from an arbitrary point of the glass fiber laminate, pulverizing the extracted fiber with a mortar or the like, and measuring with an image processing apparatus.
  • the content of the spherical fused silica particles and / or the modified cross-section glass fibers is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the electron beam curable resin composition of the present invention is prepared by blending a polyolefin resin and a crosslinking agent and, if necessary, a white pigment or other inorganic particles in the above-mentioned predetermined ratio.
  • the electron beam curable resin composition containing a white pigment or other inorganic particles is particularly suitable for a reflector.
  • additives can be blended in the electron beam curable resin composition of the present invention as long as the effects of the present invention are not impaired.
  • Additives such as antioxidants such as isocyanurates, phenols, salicylic acids, oxalic anilides, benzoates, hindered amines, benzotriazoles, and light stabilizers such as hindered amines, benzoates Can be blended.
  • the electron beam curable resin composition of the present invention is a known material such as a three-roll, two-roll, homogenizer, planetary mixer, or other stirrer, polylab system, or melt kneader such as a lab plast mill. It is obtained by mixing using the means. These may be performed at normal temperature, cooling state, heating state, normal pressure, reduced pressure state, or pressurized state.
  • molded products can be molded using the electron beam curable resin composition of the present invention as a raw material, and molded products such as thinner reflectors can also be produced.
  • Such a molded body is prepared by using the electron beam curable resin composition of the present invention as a raw material, an injection molding process at a cylinder temperature of 200 to 400 ° C., a mold temperature of 20 to 100 ° C., and before or after the injection molding process. It is preferable to produce by the shaping
  • the acceleration voltage of the electron beam can be appropriately selected according to the resin used and the thickness of the layer. For example, in the case of a molded product having a thickness of about 1 mm, it is preferable to cure the uncured resin layer usually at an acceleration voltage of about 250 to 2000 kV. In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam, the electron beam transmission depth and the resin layer thickness are made equal. By appropriately selecting the acceleration voltage, it is possible to suppress the irradiation of the electron beam to the base material and to minimize the deterioration of the base material due to the excess electron beam.
  • the absorbed dose when irradiating with an electron beam is appropriately set depending on the composition of the resin composition, but is preferably such that the crosslink density of the resin layer is saturated, preferably 10 to 400 kGy, and preferably 50 to 200 kGy. More preferably.
  • an electron beam source Various electron beam accelerators, such as a Cockloft Walton type, a resonance transformation type, an insulated core transformer type, a bande graft type, a linear type, a dynamitron type, a high frequency type, can be used.
  • the cured product of the electron beam curable resin composition of the present invention includes a heat-resistant insulating film, a heat-resistant release sheet, a heat-resistant transparent substrate, a solar cell light reflecting sheet, LED lighting, and a light source for TV. It can be applied to various uses such as a reflector.
  • the reflector resin frame of the present invention is made of a cured product obtained by molding the above-described electron beam curable resin composition.
  • the resin frame for a reflector of the present invention can be produced by forming the electron beam curable resin composition of the present invention into a pellet and forming a resin frame by injection molding.
  • the thickness of the resin frame for the reflector is preferably 0.1 to 5.0 mm, more preferably 0.1 to 2.0 mm.
  • a thinner resin frame can be produced as compared with a resin frame using anisotropic glass fibers. Specifically, a resin frame having a thickness of 0.1 to 3.0 mm can be produced.
  • the reflector resin frame of the present invention does not generate warp due to the inclusion of an anisotropic filler such as glass fiber even when the thickness is reduced. It is what
  • the resin frame for a reflector of the present invention can be made into a semiconductor light emitting device by mounting an LED element on the reflector, sealing it with a known sealing agent, and forming it into a desired shape by die bonding.
  • the resin frame for reflectors of the present invention functions not only as a reflector but also as a package for fixing the semiconductor light emitting device.
  • the resin frame for a reflector of the present invention since spherical fused silica particles are contained, foaming due to water is suppressed in the manufacturing process of the frame as compared with the case where porous silica particles are blended. Micropores that cause defects are not formed. Therefore, in a product such as a semiconductor light-emitting element using the frame, defects due to the fine holes that have been a problem in the past are reduced, so that durability as the product can be improved.
  • the reflector of the present invention is made of a cured product of the electron beam curable resin composition described above.
  • the reflector of the present invention may be used for a semiconductor light emitting device described later, or may be used in combination with a semiconductor light emitting device such as an LED mounting substrate made of other materials.
  • the reflector of the present invention mainly has a function of reflecting light from the LED element in the semiconductor light emitting device toward the lens of the light emitting part.
  • the details of the reflector are the same as those of the reflector applied to the semiconductor light-emitting device of the present invention, and are omitted here.
  • the reflector of the present invention by containing spherical fused silica particles, compared with the case where porous silica particles are blended, in the manufacturing process of the reflector, since foaming due to water is suppressed, a defect is caused. The resulting micropores are not formed. Therefore, in a product such as a semiconductor light emitting device using the reflector, defects due to the fine holes, which has been a problem in the past, are reduced, so that the durability of the product can be improved.
  • the micropores that cause defects in the reflector are not formed. Therefore, since the defects caused by the fine holes, which has been a problem in the past, are reduced, the durability as a product is improved.
  • the semiconductor light-emitting device of the present invention includes an optical semiconductor element such as an LED element and at least a part of which is fixed around the optical semiconductor element and reflects light from the optical semiconductor element in a predetermined direction.
  • a reflector formed of a cured product of the resin composition is provided on the substrate.
  • an optical semiconductor element is an n-type hexahedron having an active layer made of AlGaAs, AlGaInP, GaP, GaN, or the like that emits UV or blue radiant light.
  • the shape of the reflector conforms to the shape of the joint portion of the lens, and there are a circular shape, a rectangular shape, an elliptical shape, or a cylindrical shape, but it is generally a cylindrical shape (annular shape) and all end faces of the reflector. Is in contact with and fixed to the surface of the substrate.
  • the inner surface of the reflector may be tapered upward to improve the directivity of light from the optical semiconductor element.
  • the reflector can also function as a lens holder when the end portion on the lens side is processed into a shape corresponding to the shape of the lens.
  • the light reflection surface side may be a light reflection layer made of a cured product of the electron beam curable resin composition of the present invention.
  • the thickness of the light reflection layer is 500 ⁇ m from the viewpoint of reducing thermal resistance and the like. It is preferable to set it as follows, and it is more preferable to set it as 300 micrometers or less.
  • the member in which a light reflection layer is formed can be comprised with well-known heat resistant resin.
  • a lens is provided on the reflector, but this is usually made of resin, and various structures and colors are adopted depending on the purpose and application.
  • the space formed by the substrate, the reflector, and the lens may be a gap or a transparent sealing part, but is generally a transparent sealing part filled with a material that provides translucency and insulation.
  • the lead wire may be short-circuited from the connection portion with the optical semiconductor element and / or the connection portion with the electrode due to pressure caused by direct contact with the lead wire and indirectly applied vibration, impact, etc. Therefore, it is possible to reduce electrical problems caused by disconnection or cutting.
  • the optical semiconductor element can be protected from dust, moisture, etc., and reliability can be maintained over a long period of time.
  • the transparent sealing agent used for this material there are usually epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, polyimide resin, polycarbonate resin and the like. Of these, silicone resins are preferred from the viewpoints of discoloration resistance, heat resistance, weather resistance, and low shrinkage.
  • ⁇ Preparation of electron beam curable resin composition > 2 parts by mass of the isocyanurate compound or glycoluril shown in Table 9 as the cross-linking agent, 100 parts by mass of polymethylpentene resin (trade name: TPX RT18, molecular weight MW 500,000 to 600,000) manufactured by Mitsui Chemicals, Inc.
  • a molded body was formed by press-molding to ⁇ 750 mm ⁇ thickness 0.2 mm.
  • the compact was irradiated with an electron beam at an acceleration voltage of 250 kV and an absorbed dose of 100 kGy, and this was used as a test piece.
  • the electron beam curable resin composition of the present invention is excellent in long-term heat resistance and the shape change due to reflow heating is significantly reduced. Therefore, the electron beam curable resin composition of the present invention is useful as a reflector or a reflective material for a semiconductor light emitting device.
  • the silicone resin composition according to the present invention comprises: (A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms; (B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms; (C) component: a hydrosilylation reaction catalyst; Component (D): General formula (C)
  • R 1 and R 2 each independently represents a hydrogen atom, a lower alkyl group or a phenyl group, a R 3, R 4 and R 5 independently represent hydrogen atom or an allyl group.
  • allyl glycoluril represented by The component (D) is contained in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
  • the component (A) used in the practice of the present invention is not particularly limited as long as it is an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a polysiloxane structure as a main chain.
  • a component is the main ingredient (base polymer) of the silicone resin composition of this invention.
  • the component (A) preferably has 2 or more alkenyl groups bonded to a silicon atom in one molecule, more preferably 2 to 20, more preferably 2 to 10 More preferably, it has.
  • the component (A) may be a polysiloxane having one vinyl group and / or hydrosilyl group in one molecule from the viewpoint that the viscosity of the composition is low.
  • the alkenyl group can be bonded to a silicon atom via an organic group.
  • the organic group is not particularly limited, and can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • alkenyl group examples include an unsaturated hydrocarbon group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group; and a (meth) acryloyl group.
  • a vinyl group or a (meth) acryloyl group is preferable, and a vinyl group is more preferable.
  • the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group.
  • Examples of the bonding position of the alkenyl group include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane.
  • the alkenyl group can be bonded to one end or both ends of the polysiloxane molecular chain.
  • Examples of the organic group bonded to the silicon atom other than the alkenyl group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; phenyl group, tolyl group, xylyl group, Aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group, cyclopentyl group, cyclohexyl group and the like And the like. Of these, a methyl group and a phenyl group are preferable from the viewpoint of excellent heat resistance.
  • polysiloxane as the component (A) may have a hydrosilyl group.
  • organopolysiloxane As the main chain of the component (A), for example, organopolysiloxane can be mentioned. Specific examples include polydimethylsiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane. Of these, polydimethylsiloxane is preferred from the viewpoint of excellent heat resistance and light resistance. In addition, in this invention, light resistance means durability (for example, discoloration and a burning hardly occur) with respect to the light emission from LED.
  • Component is not particularly limited in terms of molecular structure. Examples thereof include a straight chain, a partially branched straight chain, a ring, a branched chain, and a three-dimensional network. One preferred embodiment is linear.
  • the component (A) is mentioned as one of the preferred embodiments in which the main chain is composed of repeating diorganosiloxane units.
  • the structure of the component (A) may have an alkylene group and / or a phenylene skeleton.
  • the molecular terminal of the component (A) can be terminated with a silanol group (silicon atom-bonded hydroxyl group) or an alkoxysilyl group, or can be blocked with a triorganosiloxy group such as a trimethylsiloxy group or a vinyl group.
  • R 1 , R 2 and R 3 each independently represent an alkenyl group
  • R 4 independently represents a monovalent hydrocarbon group other than an alkenyl group, a hydroxy group or an alkoxy group
  • each R represents an independent group.
  • a + b + n represents an integer of 2 or more
  • a and b each independently represent an integer of 0 to 3
  • m and n each independently represents an integer of 0 or more.
  • Examples of the polysiloxane having an unsaturated hydrocarbon group as an alkenyl group include a siloxane unit represented by the formula: (R 1 ) 3 SiO 1/2 and a formula: (R 1 ) 2 R 2 SiO 1/2.
  • the polysiloxane is a polysiloxane having an unsaturated hydrocarbon group as an alkenyl group
  • the polysiloxane structure may have an alkylene group and / or a phenylene skeleton.
  • R 1 in the above formula is a monovalent hydrocarbon group other than an alkenyl group.
  • the monovalent hydrocarbon group other than the alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • Aryl groups such as a group; aralkyl groups such as a benzyl group and a phenethyl group; and halogenated alkyl groups such as a chloromethyl group, a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group.
  • R 2 in the formula is an unsaturated hydrocarbon group.
  • the unsaturated hydrocarbon group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.
  • the component (A) has a vinyl group as an alkenyl group, it is excellent in curability.
  • the polysiloxane having a vinyl group as an alkenyl group may be hereinafter referred to as “vinyl group-containing polysiloxane”.
  • the component (A) is a polysiloxane having a (meth) acryloyl group as an alkenyl group, it is excellent in curability.
  • the polysiloxane having a (meth) acryloyl group as an alkenyl group may be hereinafter referred to as “(meth) acryloyl group-containing polysiloxane”.
  • Examples of the (meth) acryloyl group-containing polysiloxane include those represented by the following average composition formula (2).
  • R 1 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms or an aryl group
  • R 2 is represented by CH 2 ⁇ CR 3 —CO—O— (CH 2 ) c —.
  • .CH 2 CR 3 -CO-O- (CH 2)
  • c- R 3 medium representing the (meth) acryloxy group is a hydrogen atom or a methyl group
  • c is an integer of 2-6, More preferably, it is 2, 3 or 4.
  • a is from 0.8 to 2.4, more preferably from 1 to 1.8
  • b is from 0.1 to 1.2, and More preferably, it is 2 to 1, more preferably 0.4 to 1.
  • a + b is 2 to 2.5, and more preferably 2 to 2.2.
  • examples of the alkyl group for R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • examples of the aryl group for R 1 include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Of these, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable, and a methyl group is more preferable.
  • the molecular weight (weight average molecular weight) of component (A) is preferably 500 to 100,000, and preferably 1,000 to 100,000 from the viewpoint of excellent curability, toughness, elongation and workability. Is more preferably 5,000 to 50,000.
  • a weight average molecular weight is a polystyrene conversion value by GCP (gel permeation column chromatography).
  • the viscosity of component (A) at 23 ° C. is preferably 5 to 10,000 mPa ⁇ s because the physical properties of the resulting silicone resin are good and the handling workability of the silicone resin composition is good. More preferably, it is ⁇ 1,000 mPa ⁇ s. In the present invention, the viscosity is measured with an E-type viscometer at 23 ° C.
  • a component can be used individually or in combination of 2 or more types.
  • Component (A) is not particularly limited with respect to its preparation method, and conventionally known components can be used.
  • Component (B) used in the practice of the present invention is an organohydrogenpolysiloxane having at least two hydrogen groups bonded to silicon atoms (that is, SiH groups) in one molecule and having a polysiloxane structure as the main chain. If it is, it will not be restrict
  • the component (B) preferably has 2 to 300 hydrogen groups bonded to silicon atoms in one molecule, and more preferably 3 to 150 hydrogen groups.
  • Examples of the molecular structure of the component (B) include linear, branched, cyclic, and three-dimensional network structures.
  • examples of the bonding position of the hydrogen group bonded to the silicon atom include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane. Further, the hydrogen group bonded to the silicon atom can be bonded to one end or both ends of the molecular chain of the polysiloxane.
  • component (B) examples include organohydrogenpolysiloxanes represented by the following average composition formula (3).
  • R 3 independently represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond.
  • a and b are 0 ⁇ a ⁇ 2, 0.8 ⁇ b ⁇ 2 and 0 .8 ⁇ a + b ⁇ 3, a number satisfying 0.05 ⁇ a ⁇ 1, 0.9 ⁇ b ⁇ 2, and 1.0 ⁇ a + b ⁇ 2.7 is more preferable.
  • the number of silicon atoms is 2 to 300, more preferably 3 to 200.
  • examples of the unsubstituted or substituted monovalent hydrocarbon group R 3 not containing an aliphatic unsaturated bond include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • halogenated alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, a phenyl group, or a 3,3,3-trifluoropropyl group is preferable.
  • component (B) for example, molecular chain both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-capped methyl Hydrogen polysiloxane, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogen polysiloxane with both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane copolymers; (R 3) or 2 HSiO 1/2 units and SiO 4/2 units It optionally (R 3) 3 SiO 1/2 units, (R 3) 2 SiO 1/2
  • examples of the component (B) include those represented by the following general formulas (4) to (7).
  • each R 3 independently represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c represents 0 or an integer of 1 or more, and d represents an integer of 1 or more. .)
  • a component can be used individually or in combination of 2 or more types.
  • Component (B) can be prepared by a conventionally known method. Specifically, for example, the following chemical formulas: R 3 SiHCl 2 and (R 3 ) 2 SiHCl (wherein R 3 is the same as the unsubstituted or substituted monovalent hydrocarbon group not containing the aliphatic unsaturated bond). .
  • the mixing ratio of atoms (SiH groups) is preferably 0.1 to 5 mol, more preferably 0.5 to 2.5 mol, and more preferably 1.0 to 2.0 mol More preferably.
  • SiH group When the amount of SiH group is 0.1 mol or more, a rubber cured product (silicone resin) that is sufficiently cured and strong can be obtained. When the amount of SiH groups is 5 mol or less, the cured product does not become brittle and a strong rubber cured product can be obtained.
  • the component (A) and the component (B) can be used as a mixture of the component (A) and the component (B).
  • the component (C) used in the practice of the present invention promotes the addition reaction between the alkenyl group of the component (A) and the hydrogen atom (that is, SiH group) bonded to the silicon atom of the component (B). It is a reaction catalyst.
  • the silicone resin composition of this invention can be made into the composition excellent in sclerosis
  • the component (C) is not particularly limited, and conventionally known components can be used.
  • platinum group metals such as platinum (including platinum black), rhodium, palladium, etc .; H 2 PtCl 4 ⁇ nH 2 O, H 2 PtCl 6 ⁇ nH 2 O, NaHPtCl 6 ⁇ nH 2 O, KHPtCl 6 ⁇ nH 2 O, Na 2 PtCl 6 ⁇ nH 2 O, K 2 PtCl 4 ⁇ nH 2 O, PtCl 4 ⁇ nH 2 O, PtCl 2 , Na 2 HPtCl 4 ⁇ nH 2 O (where n is an integer of 0 to 6) And preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat.
  • the amount of the component (C) used is a blending ratio of 0.1 to 500 ppm in terms of the mass of the platinum group metal with respect to the total amount of the components (A) and (B) from the viewpoint of achieving excellent curability.
  • the blending ratio is preferably 10 to 100 ppm.
  • the component (D) used in the practice of the present invention is allyl glycoluril represented by the general formula (C).
  • allyl glycoluril represented by the general formula (C).
  • the component (D) is blended in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), so that the cured product has resistance to sulfur. Can be granted. Thereby, discoloration (corrosion) of silver can be prevented and the transparency of the cured product can be maintained.
  • the cured product obtained by using the silicone resin composition of the present invention is excellent in sulfidation resistance even if the resin is not hardened, so that it can be made into a silicone resin which is not easily cracked. For this reason, when hardened
  • the amount of the component (D) used is the amount of the component (A) and the component (B) from the viewpoint of suppressing coloring by heat and exhibiting transparency and sulfidation resistance.
  • the blending ratio is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total.
  • (D) component can be used individually or in combination of 2 or more types.
  • an additive may be used in combination with the silicone resin composition of the present invention within a range not impairing the effects of the present invention.
  • additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property imparting agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, physical property modifiers, adhesion imparting agents, adhesion assistants, and the like, and known ones can be used.
  • adhesion-imparting agent or adhesion assistant examples include known epoxy silane coupling agents, bis (alkoxy) alkanes, isocyanurate derivatives, and the like, and bis (alkoxy) alkanes and / or isocyanurate derivatives are preferred.
  • Examples of the bis (alkoxy) alkane include 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8- It is preferably at least one selected from the group consisting of bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. More preferred is 6-bis (trimethoxysilyl) hexane.
  • the method for preparing the silicone resin composition of the present invention is not particularly limited.
  • the silicone resin composition of this invention can be made into 1 liquid type or 2 liquid type.
  • the silicone resin composition of the present invention is a two-component type, it is divided into a first liquid containing the component (B) and the component (C) and a second liquid containing the component (A) and the component (D). Can be prepared.
  • the additive can be added to one or both of the first liquid and the second liquid.
  • the silicone resin composition of the present invention is prepared at a temperature of 23 ° C. for 24 hours after mixing the liquid containing the component other than the component (B) with the component (B) from the viewpoint that the length of the pot life is appropriate.
  • the subsequent viscosity is preferably 5 to 10,000 mPa ⁇ s, and more preferably 5 to 5,000 mPa ⁇ s.
  • the silicone resin composition of the present invention is mixed and placed under a condition of 23 ° C., and the viscosity measurement performed on the composition 24 hours after mixing is performed using an E-type viscometer at 23 ° C. and a humidity of 55%. It is done under conditions.
  • Examples of the method of using the silicone resin composition of the present invention include applying the composition of the present invention to a substrate (for example, an optical semiconductor element) and curing the composition.
  • a substrate for example, an optical semiconductor element
  • the method for applying and curing the silicone resin composition of the present invention is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, injection molding and the like.
  • the silicone resin composition of the present invention can be cured by heating.
  • the heating temperature for curing the silicone resin composition of the present invention by heating is usually 100 ° C. or higher, and is preferably 120 ° C. or higher, and preferably 120 to 200 ° C. from the viewpoint of being excellent in curability. More preferably, it is 120 to 180 ° C.
  • silicone resin composition of the present invention is not particularly limited.
  • the sealing material composition for electronic materials the sealing material composition for buildings, the sealing material composition for motor vehicles, the adhesive composition, etc. are mentioned.
  • Electronic materials include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members; optical semiconductor elements; active elements such as semiconductor chips, transistors, diodes, thyristors; capacitors, resistors, Examples include passive elements such as coils.
  • the silicone resin composition of the present invention is used in applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. be able to.
  • the silicone resin composition of the present invention can be substantially free of a silicon compound having a silanol group from the viewpoint of storage stability.
  • the silicone resin composition of the present invention can be used in the presence of silver.
  • silver discoloration corrosion
  • the transparency of the resulting silicone resin can be maintained.
  • the silicone resin of the present invention can be obtained by curing the silicone resin composition.
  • a silicone resin having excellent sulfidation resistance can be obtained.
  • the silicone resin of the present invention can be obtained by curing the silicone resin composition by heating.
  • the curing time and pot life can be set to appropriate lengths, suppress foaming, suppress cracks in the silicone resin, and smooth the silicone resin. From the viewpoint of excellent moldability and physical properties, a method of curing the silicone resin composition at 120 to 180 ° C. (preferably 150 ° C.) within 20 hours (preferably 12 hours) is preferable.
  • the silicone resin of the present invention can be used as a sealing material for LED chips.
  • the LED chip is not particularly limited with respect to its emission color. For example, blue, red, yellow, green, and white are mentioned.
  • the LED chips can be used alone or in combination of two or more.
  • the LED chip is sealed with the silicone resin.
  • the silicone resin used for the sealed optical semiconductor element of the present invention is not particularly limited as long as it is the silicone resin of the present invention.
  • the sealed optical semiconductor element of the present invention exhibits excellent performance in sulfidation resistance, rubber elasticity and flexibility by using the silicone resin composition.
  • the LED chip used in the sealed optical semiconductor element of the present invention is not particularly limited with respect to the emission color.
  • a blue LED chip can be coated with a silicone resin composition of the present invention containing a fluorescent material such as yttrium, aluminum, and garnet to form a white LED.
  • each LED chip is sealed with the silicone resin composition of the present invention, and the LED chips of these three colors are sealed.
  • the body can be used. Further, the LED chips of three colors can be combined and sealed with the silicone resin composition of the present invention to form one light source.
  • the size and shape of the LED chip are not particularly limited.
  • the type of the LED chip is not particularly limited, and examples thereof include a high power LED, a high luminance LED, a general luminance LED, a white LED, and a blue LED.
  • optical semiconductor element used for the sealed optical semiconductor element of the present invention examples include, in addition to LEDs, organic electroluminescent elements (organic EL), laser diodes, and LED arrays.
  • optical semiconductor element for example, an optical semiconductor element bonded to a substrate such as a lead frame by die bonding and connected to the substrate or the like by chip bonding, wire bonding, wireless bonding, or the like can be used. .
  • the cured product used for the sealed optical semiconductor element of the present invention only needs to seal the optical semiconductor element.
  • the optical semiconductor element sealing body of the present invention for example, when the cured product directly seals the optical semiconductor element, when it is a shell type, when it is a surface mounting type, a plurality of optical semiconductor element sealing bodies The case where it fills between is mentioned.
  • the sealed optical semiconductor element of the present invention includes a coating step of coating the LED chip with the silicone resin composition of the present invention, and curing the silicone resin composition by heating the LED chip coated with the silicone resin composition. It can be manufactured by a curing step.
  • the coating method is not particularly limited, and examples thereof include potting, transfer molding, injection molding, and screen printing.
  • the LED chip coated with the silicone resin composition can be heated to cure the silicone resin composition to obtain a cured product.
  • the temperature which heats the said silicone resin composition is the same as the conditions shown at the process of manufacturing the said silicone resin.
  • the production of the sealed optical semiconductor element of the present invention is not particularly limited except that the silicone resin of the present invention is used as the silicone resin.
  • the heating temperature at the time of producing the sealed optical semiconductor element of the present invention is the same as the heating temperature at the time of curing the silicone resin composition of the present invention, so that excellent curability can be exhibited. To preferred.
  • sealed optical semiconductor element of the present invention includes, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. Etc., but is not particularly limited.
  • Component (A) Both end vinyl-blocked dimethylpolysiloxane (“DMS-V31” manufactured by Gelest, hereinafter abbreviated as (A))
  • Component (B) Hydrogen polysiloxane (“KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as (B))
  • Component (C) Platinum-cyclovinylmethylsiloxane complex (“SIP6832.2” manufactured by Gelest, hereinafter abbreviated as (C))
  • Component (D) 1,3,4,6-tetraallylglycoluril (“TA-G” manufactured by Shikoku Kasei Kogyo Co., Ltd., hereinafter abbreviated as (D))
  • the transmittance retention was calculated from the obtained transmittance according to the following formula.
  • Transmittance retention rate (%) (transmittance of cured product after heat test) / (transmittance of initial cured product) ⁇ 100 [Heat resistant coloring stability test]
  • the obtained silicone resin composition was sandwiched between glass plates (length 10 cm, width 10 cm, thickness 4 mm), and cured at 150 ° C. for 4 hours so as to obtain a cured product having a thickness of 2 mm.
  • the obtained initial cured product and the cured product after the heat resistance test obtained by further heating the initial cured product at 150 ° C. for 10 days are visually observed, and the cured product after the heat test is compared with the initial cured product. It was evaluated whether it turned yellow.

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Abstract

L'invention concerne des glycoluriles représentés par la formule générale (Z). (Z) (Dans la formule, le groupe Z est un groupe carboxyalkyle, un groupe glycidyle ou un groupe allyle, R1 et R2 sont chacun indépendamment de l'autre un atome d'hydrogène, un groupe alkyle inférieur ou un groupe phényle, R3, R4 et R5 sont chacun indépendamment de l'autre un atome d'hydrogène ou le même groupe que le groupe Z, à la condition que, quand le groupe Z est un groupe carboxyalkyle, R3, R4 et R5 soient chacun un groupe carboxyalkyle identique au groupe Z et que, quand Z est un groupe allyle, R5 soit un atome d'hydrogène). L'invention concerne aussi différentes compositions de résine comprenant les glycoluriles, par exemple une composition de résine de polyester, une composition de résine époxy ou une composition de résine de silicone.
PCT/JP2014/081009 2013-11-25 2014-11-25 Glycoluriles ayant un groupe fonctionnel et leur utilisation Ceased WO2015076399A1 (fr)

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US15/038,506 US10000622B2 (en) 2013-11-25 2014-11-25 Glycolurils having functional groups and use thereof
EP14864012.1A EP3075735B1 (fr) 2013-11-25 2014-11-25 Glycoluriles ayant un groupe fonctionnel et leur utilisation
CN201480064419.1A CN105745213A (zh) 2013-11-25 2014-11-25 具有官能团的甘脲类及其利用
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WO2015163355A1 (fr) * 2014-04-23 2015-10-29 株式会社ダイセル Composition de résine durcissable, produit durci correspondant, dérivé du glycoluril et procédé de production correspondant
WO2015163352A1 (fr) * 2014-04-23 2015-10-29 株式会社ダイセル Composition de résine durcissable et produit durci de celle-ci
CN105085532A (zh) * 2015-09-07 2015-11-25 山西医科大学 一种四甲氧甲基甘脲衍生物及其制备方法
WO2016139989A1 (fr) * 2015-03-04 2016-09-09 エア・ウォーター株式会社 Agent de réglage de la dilatation thermique, utilisation comme agent de réglage de la dilatation thermique, composition de résine thermodurcissable, matériau isolant, matériau d'étanchéité, et pâte conductrice contenant ladite composition de résine thermodurcissable, matériau durci obtenu par durcissement de ladite composition de résine thermodurcissable, matériau de substrat comprenant ladite composition de résine thermodurcissable, préimprégné comprenant un matériau de base imprégné de ladite composition de résine thermodurcissable, élément comprenant ledit préimprégné à base de ladite composition de résine thermodurcissable préalablement durci, procédé de réglage du taux de dilatation thermique et élément fabriqué en faisant appel audit procédé de réglage
JP2016206661A (ja) * 2015-04-22 2016-12-08 奇美實業股▲分▼有限公司 感光性樹脂組成物、画素層、保護膜、スペーサー、薄膜トランジスタ、カラーフィルター、および液晶表示装置
CN106324987A (zh) * 2015-06-30 2017-01-11 奇美实业股份有限公司 感光性树脂组合物及其应用
JP2017008017A (ja) * 2015-06-26 2017-01-12 四国化成工業株式会社 チオエーテル結合とシリル基を有するグリコールウリル化合物、該化合物の合成方法およびポリオルガノシロキサン組成物
JP2017137408A (ja) * 2016-02-03 2017-08-10 クラスターテクノロジー株式会社 白色リフレクター用硬化性エポキシ樹脂組成物及びその硬化物、光半導体素子搭載用基板、並びに光半導体装置
WO2017170696A1 (fr) * 2016-03-30 2017-10-05 日産化学工業株式会社 Composition de formation de film de sous-couche de photorésine qui contient un composé présentant un squelette de glycolurile comme additif
JP2018055095A (ja) * 2016-09-27 2018-04-05 東レ株式会社 カラーフィルタ用感光性組成物およびそれを用いたカラーフィルタ基板
JP2022089761A (ja) * 2020-12-04 2022-06-16 ダウ・東レ株式会社 硬化性シリコーン組成物
EP4474435A1 (fr) * 2023-06-05 2024-12-11 Siemens Aktiengesellschaft Formulation de peinture, isolation de celle-ci et utilisation de celle-ci

Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3159662A (en) 1962-07-02 1964-12-01 Gen Electric Addition reaction
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
FR2032087A5 (fr) * 1969-02-18 1970-11-20 Akad Wissenschaften Ddr Procede de fabrication de matieres a base de resines epoxydes
US3775452A (en) 1971-04-28 1973-11-27 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
JPS54103881A (en) * 1978-01-31 1979-08-15 Teijin Ltd Novel di(isocyanuro) compound
US4176027A (en) * 1977-09-13 1979-11-27 Raychem Corporation Shaped article of radiation crosslinked triazine-trione polymeric composition
JPH01141904A (ja) 1987-11-30 1989-06-02 Taiyo Ink Seizo Kk 感光性熱硬化性樹脂組成物及びソルダーレジストパターン形成方法
JPH02196860A (ja) 1975-05-19 1990-08-03 General Electric Co <Ge> 硬化性組成物
JPH02222165A (ja) 1989-02-23 1990-09-04 Nitto Denko Corp 光半導体装置およびそれに用いる光半導体封止用エポキシ樹脂組成物
JPH03277645A (ja) 1990-03-27 1991-12-09 Shin Etsu Chem Co Ltd 硬化性樹脂組成物
JPH05148543A (ja) 1991-11-29 1993-06-15 Kawasaki Steel Corp 厚肉鋼板の加速冷却型製造方法
JPH073030A (ja) 1986-08-27 1995-01-06 Hercules Inc 有機珪素重合体
JPH07207211A (ja) 1994-01-17 1995-08-08 Nippon Kayaku Co Ltd フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
WO1996015194A1 (fr) 1994-11-15 1996-05-23 Kanegafuchi Chemical Industry Co., Ltd. Composition de resine expansible, mousse produite a partir de cette derniere et son procede de production
JPH08274445A (ja) 1995-03-31 1996-10-18 Taiyo Ink Mfg Ltd アルカリ現像型の光硬化性・熱硬化性樹脂組成物
JPH095997A (ja) 1995-06-14 1997-01-10 Tamura Kaken Kk 感光性樹脂組成物、その硬化塗膜及び回路基板
JPH09291214A (ja) 1996-04-25 1997-11-11 Nippon Paint Co Ltd 硬化性樹脂組成物及びその硬化物
JPH09302095A (ja) 1996-05-10 1997-11-25 Kanegafuchi Chem Ind Co Ltd 硬化性組成物、成形体及び製造方法
JPH10228249A (ja) 1996-12-12 1998-08-25 Nichia Chem Ind Ltd 発光ダイオード及びそれを用いたｌｅｄ表示装置
JPH11171887A (ja) 1997-12-12 1999-06-29 Shikoku Chem Corp １，３，４，６−テトラアリルグリコールウリル化合物および該化合物の合成方法
JP2000017148A (ja) 1998-07-01 2000-01-18 Ajinomoto Co Inc 熱硬化性樹脂組成物及びこれを用いたプリント配線板用層間接着フィルム
JP2000051337A (ja) * 1998-08-17 2000-02-22 Fuji Photo Film Co Ltd 脱臭剤
JP2000114727A (ja) 1998-10-09 2000-04-21 Ibiden Co Ltd 多層プリント配線板
JP2000243864A (ja) 1999-02-18 2000-09-08 Seiko Epson Corp 半導体装置及びその製造方法、回路基板並びに電子機器
JP2001200161A (ja) 1999-11-11 2001-07-24 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
WO2002053648A1 (fr) 2000-12-27 2002-07-11 Kaneka Corporation Agents de durcissement, compositions durcissables, compositions pour materiaux optiques, materiaux optiques, leur production, afficheurs a cristaux liquides et diodes electroluminescentes ainsi obtenues
JP2003119256A (ja) 2001-10-12 2003-04-23 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP2004099751A (ja) 2002-09-10 2004-04-02 Nippon Unicar Co Ltd イソシアヌル酸誘導体基含有オルガノポリシロキサン、エポキシ樹脂組成物および半導体装置
JP2004182851A (ja) 2002-12-03 2004-07-02 Sumitomo Bakelite Co Ltd 樹脂組成物、プリプレグおよびそれを用いたプリント配線板
JP2006037015A (ja) 2004-07-29 2006-02-09 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP2006206700A (ja) 2005-01-27 2006-08-10 Jsr Corp ポリシロキサン組成物およびその製造方法、それから得られるフィルムおよびその製造方法、ならびに封止材
JP2006282988A (ja) 2005-03-08 2006-10-19 Sanyo Chem Ind Ltd 光半導体素子封止用エポキシ樹脂組成物
JP2006291044A (ja) 2005-04-11 2006-10-26 Kaneka Corp 硬化性組成物
JP2007009041A (ja) 2005-06-30 2007-01-18 Kaneka Corp 硬化性組成物及びその硬化物
JP2007224089A (ja) 2006-02-21 2007-09-06 Shin Etsu Chem Co Ltd 加熱硬化型オルガノポリシロキサン組成物
JP4073223B2 (ja) 2002-03-19 2008-04-09 株式会社カネカ 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2008143954A (ja) 2006-12-06 2008-06-26 Jsr Corp イソシアヌル環含有重合体、その製造法およびそれを含有する組成物
JP2008150506A (ja) 2006-12-18 2008-07-03 Jsr Corp 硬化性樹脂組成物及びその用途
JP4216512B2 (ja) 2002-03-08 2009-01-28 株式会社カネカ 硬化性組成物、電子材料用組成物、半導体装置、および半導体装置の製造方法
WO2011102230A1 (fr) * 2010-02-17 2011-08-25 日本化成株式会社 Agent de réticulation pour élastomère réticulé, et application de celui-ci
JP2013166926A (ja) 2012-01-17 2013-08-29 Dainippon Printing Co Ltd 電子線硬化性樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形体の製造方法

Patent Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159662A (en) 1962-07-02 1964-12-01 Gen Electric Addition reaction
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
FR2032087A5 (fr) * 1969-02-18 1970-11-20 Akad Wissenschaften Ddr Procede de fabrication de matieres a base de resines epoxydes
US3775452A (en) 1971-04-28 1973-11-27 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
JPH02196860A (ja) 1975-05-19 1990-08-03 General Electric Co <Ge> 硬化性組成物
US4176027A (en) * 1977-09-13 1979-11-27 Raychem Corporation Shaped article of radiation crosslinked triazine-trione polymeric composition
JPS54103881A (en) * 1978-01-31 1979-08-15 Teijin Ltd Novel di(isocyanuro) compound
JPH073030A (ja) 1986-08-27 1995-01-06 Hercules Inc 有機珪素重合体
JPH01141904A (ja) 1987-11-30 1989-06-02 Taiyo Ink Seizo Kk 感光性熱硬化性樹脂組成物及びソルダーレジストパターン形成方法
JPH02222165A (ja) 1989-02-23 1990-09-04 Nitto Denko Corp 光半導体装置およびそれに用いる光半導体封止用エポキシ樹脂組成物
JPH03277645A (ja) 1990-03-27 1991-12-09 Shin Etsu Chem Co Ltd 硬化性樹脂組成物
JPH05148543A (ja) 1991-11-29 1993-06-15 Kawasaki Steel Corp 厚肉鋼板の加速冷却型製造方法
JPH07207211A (ja) 1994-01-17 1995-08-08 Nippon Kayaku Co Ltd フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
WO1996015194A1 (fr) 1994-11-15 1996-05-23 Kanegafuchi Chemical Industry Co., Ltd. Composition de resine expansible, mousse produite a partir de cette derniere et son procede de production
JPH08274445A (ja) 1995-03-31 1996-10-18 Taiyo Ink Mfg Ltd アルカリ現像型の光硬化性・熱硬化性樹脂組成物
JPH095997A (ja) 1995-06-14 1997-01-10 Tamura Kaken Kk 感光性樹脂組成物、その硬化塗膜及び回路基板
JPH09291214A (ja) 1996-04-25 1997-11-11 Nippon Paint Co Ltd 硬化性樹脂組成物及びその硬化物
JPH09302095A (ja) 1996-05-10 1997-11-25 Kanegafuchi Chem Ind Co Ltd 硬化性組成物、成形体及び製造方法
JPH10228249A (ja) 1996-12-12 1998-08-25 Nichia Chem Ind Ltd 発光ダイオード及びそれを用いたｌｅｄ表示装置
JPH11171887A (ja) 1997-12-12 1999-06-29 Shikoku Chem Corp １，３，４，６−テトラアリルグリコールウリル化合物および該化合物の合成方法
JP2000017148A (ja) 1998-07-01 2000-01-18 Ajinomoto Co Inc 熱硬化性樹脂組成物及びこれを用いたプリント配線板用層間接着フィルム
JP2000051337A (ja) * 1998-08-17 2000-02-22 Fuji Photo Film Co Ltd 脱臭剤
JP2000114727A (ja) 1998-10-09 2000-04-21 Ibiden Co Ltd 多層プリント配線板
JP2000243864A (ja) 1999-02-18 2000-09-08 Seiko Epson Corp 半導体装置及びその製造方法、回路基板並びに電子機器
JP2001200161A (ja) 1999-11-11 2001-07-24 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
WO2002053648A1 (fr) 2000-12-27 2002-07-11 Kaneka Corporation Agents de durcissement, compositions durcissables, compositions pour materiaux optiques, materiaux optiques, leur production, afficheurs a cristaux liquides et diodes electroluminescentes ainsi obtenues
JP2003119256A (ja) 2001-10-12 2003-04-23 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP4216512B2 (ja) 2002-03-08 2009-01-28 株式会社カネカ 硬化性組成物、電子材料用組成物、半導体装置、および半導体装置の製造方法
JP4073223B2 (ja) 2002-03-19 2008-04-09 株式会社カネカ 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2004099751A (ja) 2002-09-10 2004-04-02 Nippon Unicar Co Ltd イソシアヌル酸誘導体基含有オルガノポリシロキサン、エポキシ樹脂組成物および半導体装置
JP2004182851A (ja) 2002-12-03 2004-07-02 Sumitomo Bakelite Co Ltd 樹脂組成物、プリプレグおよびそれを用いたプリント配線板
JP2006037015A (ja) 2004-07-29 2006-02-09 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP2006206700A (ja) 2005-01-27 2006-08-10 Jsr Corp ポリシロキサン組成物およびその製造方法、それから得られるフィルムおよびその製造方法、ならびに封止材
JP2006282988A (ja) 2005-03-08 2006-10-19 Sanyo Chem Ind Ltd 光半導体素子封止用エポキシ樹脂組成物
JP2006291044A (ja) 2005-04-11 2006-10-26 Kaneka Corp 硬化性組成物
JP2007009041A (ja) 2005-06-30 2007-01-18 Kaneka Corp 硬化性組成物及びその硬化物
JP2007224089A (ja) 2006-02-21 2007-09-06 Shin Etsu Chem Co Ltd 加熱硬化型オルガノポリシロキサン組成物
JP2008143954A (ja) 2006-12-06 2008-06-26 Jsr Corp イソシアヌル環含有重合体、その製造法およびそれを含有する組成物
JP2008150506A (ja) 2006-12-18 2008-07-03 Jsr Corp 硬化性樹脂組成物及びその用途
WO2011102230A1 (fr) * 2010-02-17 2011-08-25 日本化成株式会社 Agent de réticulation pour élastomère réticulé, et application de celui-ci
JP2013166926A (ja) 2012-01-17 2013-08-29 Dainippon Printing Co Ltd 電子線硬化性樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形体の製造方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE REGISTRY [online] "IMIDAZO[4,5-D]IMIDAZOLE-1,3,4,6(2H,5H)-TETRAPROPANOIC ACID, DIHYDRO-2,5-DIOXO- (CA INDEX NAME)", XP055346766, accession no. STN Database accession no. 1454838-83-5 *
DATABASE REGISTRY [online] "MIDAZO[4,5-D]IMIDAZOLE-2,5(1H,3H)-DIONE, TETRAHYDRO-1,3,4,6-TETRAKIS(2-OXIRANYLMETHYL)- (CA INDEX NAME)", XP055346776, accession no. STN Database accession no. 1454838-82-4 *
LI, C.Q.: "POLY[[L-AQUA-TRIAQUA[L6-1,3,4,6-TETRAKIS- (CARBOXYLATOMETHYL)-7,8-DIPHENYLGLYCOLURIL] DIZINC] MONOHYDRATE]", ACTA CRYSTALLOGRAPHICA SECTION E, vol. E67, 2011, pages M1818 - M1819, XP055345073 *
RIVOLLIER J.: "EXTENSION OF THE BAMBUS[N]URIL FAMILY: MICROWAVE SYNTHESIS AND REACTIVITY OF ALLYLBAMBUS[N]URILS", ORGANIC LETTERS, vol. 15, no. 3, 15 January 2013 (2013-01-15), pages 480 - 483, XP055345083 *
SYNLETT., vol. 7, 2010, pages 1104 - 1106

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* Cited by examiner, † Cited by third party
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WO2015163355A1 (fr) * 2014-04-23 2015-10-29 株式会社ダイセル Composition de résine durcissable, produit durci correspondant, dérivé du glycoluril et procédé de production correspondant
JPWO2016139989A1 (ja) * 2015-03-04 2017-12-07 エア・ウォーター株式会社 熱膨張性調整剤、熱膨張性調整剤としての使用、熱硬化性樹脂組成物、当該熱硬化性樹脂組成物を含有する絶縁材、封止剤および導電ペースト、当該熱硬化性樹脂組成物を硬化させた硬化物、当該熱硬化性樹脂組成物を有する基板材料、当該熱硬化性樹脂組成物を基材に含浸させたプリプレグ、当該プリプレグの熱硬化性樹脂組成物を硬化させた部材、熱膨張率の調整方法、ならびに当該調整方法を用いて製造された部材
US10400086B2 (en) 2015-03-04 2019-09-03 Air Water Inc. Thermal expandability adjuster, use as thermal expandability adjuster, thermoset resin composition, insulating material, sealing material and conductive paste each containing thermoset resin composition, cured products, prepreg and member obtained by curing thermoset resin composition of prepreg, method of adjusting thermal expansion rate, and member manufactured using method of adjusting
WO2016139989A1 (fr) * 2015-03-04 2016-09-09 エア・ウォーター株式会社 Agent de réglage de la dilatation thermique, utilisation comme agent de réglage de la dilatation thermique, composition de résine thermodurcissable, matériau isolant, matériau d'étanchéité, et pâte conductrice contenant ladite composition de résine thermodurcissable, matériau durci obtenu par durcissement de ladite composition de résine thermodurcissable, matériau de substrat comprenant ladite composition de résine thermodurcissable, préimprégné comprenant un matériau de base imprégné de ladite composition de résine thermodurcissable, élément comprenant ledit préimprégné à base de ladite composition de résine thermodurcissable préalablement durci, procédé de réglage du taux de dilatation thermique et élément fabriqué en faisant appel audit procédé de réglage
US20180030242A1 (en) 2015-03-04 2018-02-01 Air Water Inc. Thermal expandability adjuster, use as thermal expandability adjuster, thermoset resin composition, insulating material, sealing material and conductive paste each containing thermoset resin composition, cured products, prepreg and member obtained by curing thermoset resin composition of prepreg, method of adjusting thermal expansion rate, and member manufactured using method of adjusting
JP2016206661A (ja) * 2015-04-22 2016-12-08 奇美實業股▲分▼有限公司 感光性樹脂組成物、画素層、保護膜、スペーサー、薄膜トランジスタ、カラーフィルター、および液晶表示装置
JP2017008017A (ja) * 2015-06-26 2017-01-12 四国化成工業株式会社 チオエーテル結合とシリル基を有するグリコールウリル化合物、該化合物の合成方法およびポリオルガノシロキサン組成物
CN106324987A (zh) * 2015-06-30 2017-01-11 奇美实业股份有限公司 感光性树脂组合物及其应用
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JP2017137408A (ja) * 2016-02-03 2017-08-10 クラスターテクノロジー株式会社 白色リフレクター用硬化性エポキシ樹脂組成物及びその硬化物、光半導体素子搭載用基板、並びに光半導体装置
WO2017170696A1 (fr) * 2016-03-30 2017-10-05 日産化学工業株式会社 Composition de formation de film de sous-couche de photorésine qui contient un composé présentant un squelette de glycolurile comme additif
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JPWO2017170696A1 (ja) * 2016-03-30 2019-02-07 日産化学株式会社 グリコールウリル骨格を持つ化合物を添加剤として含むレジスト下層膜形成組成物
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US11131928B2 (en) 2016-03-30 2021-09-28 Nissan Chemical Corporation Resist underlayer film forming composition which contains compound having glycoluril skeleton as additive
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