[go: up one dir, main page]

WO2012117786A1 - Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé - Google Patents

Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé Download PDF

Info

Publication number
WO2012117786A1
WO2012117786A1 PCT/JP2012/051878 JP2012051878W WO2012117786A1 WO 2012117786 A1 WO2012117786 A1 WO 2012117786A1 JP 2012051878 W JP2012051878 W JP 2012051878W WO 2012117786 A1 WO2012117786 A1 WO 2012117786A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
photosensitive
compound
solder resist
photosensitive composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/051878
Other languages
English (en)
Japanese (ja)
Inventor
有岡　大輔
冨澤　秀樹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2012117786A1 publication Critical patent/WO2012117786A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention is a photosensitive composition suitably used for a solder resist, a photosensitive solder resist composition using the photosensitive composition, a photosensitive solder resist film using the photosensitive solder resist composition, and
  • the present invention relates to a high-definition permanent pattern (a protective film, an interlayer insulating film, a solder resist, etc.), a formation method thereof, and a printed board.
  • such a build-up wiring board is formed by laminating a film made of a thermosetting resin on an insulating board made of glass fiber and epoxy resin, and thermosetting the film to form an insulating layer.
  • An opening is formed, and then the surface of the insulating layer is chemically roughened and a copper film is deposited using an electroless copper plating method and an electrolytic copper plating method, thereby forming a conductor layer in the opening and insulating.
  • the wiring conductor layer is formed on the surface of the layer, and the insulating layer and the wiring conductor layer are repeatedly formed.
  • solder resist layer having a thickness of 20 ⁇ m to 50 ⁇ m is deposited on the surface of the wiring board in order to prevent oxidation and corrosion of the wiring conductor layer and to protect the insulating layer from heat when mounting electronic components on the wiring board. Is formed.
  • This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin that has good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a coefficient of thermal expansion that is the same as that of the insulating layer and the wiring conductor layer. In order to match the expansion coefficient, the inorganic filler is contained in an amount of 5 to 75% by mass.
  • this solder resist layer generally contains a hydroxyl group or a carboxyl group in order for the alkali-soluble photocrosslinkable resin to be contained to develop developability when an opening is formed in the solder resist layer by exposure and development.
  • the water absorption rate is high and the moisture in the air is gradually absorbed, and this moisture reduces the insulation resistance of the solder resist layer to 10 8 ⁇ or less, causing short circuit between the wiring conductor layers.
  • the conductor layer is corroded, and as a result, the electrical reliability of the wiring board is deteriorated.
  • a technique for containing a nitrogen-containing heterocyclic compound (imidazole compound, triazole compound, etc.) in the solder resist layer is known.
  • this technique although the heat resistance of the solder resist layer is increased, there is a problem that the plating resistance is lowered.
  • the smoothness of the side surface of the resist pattern is poor, a gap is formed between the solder and the side surface of the resist pattern when soldering, and the gap expands due to heating, causing problems such as peeling of the solder. Then, there exists a problem that the smoothness of the resist pattern side surface is not enough.
  • a technique using a triazole compound in a photosensitive composition it has a carboxyl group-containing polymer binder, an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring.
  • a photosensitive composition containing a compound, a photopolymerizable monomer, and a photopolymerization initiator has been proposed (see, for example, Patent Document 1). According to this proposed technique, a composition with good adhesion can be obtained by suppressing development residue, but with this proposed technique, the insulation, plating resistance, and smoothness of the resist pattern side surface required for the solder resist layer are obtained. There is a problem that sex is not obtained.
  • an object of the present invention is to provide a photosensitive composition that is excellent in insulation, plating resistance, and smoothness of the side surface of a resist pattern.
  • the photosensitive composition of the present invention includes a compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. It is characterized by containing.
  • the present invention it is possible to provide a photosensitive composition that can solve the above-mentioned problems and achieve the above-mentioned object, and that is excellent in insulation, plating resistance, and smoothness of the resist pattern side surface.
  • the photosensitive composition of the present invention comprises at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring, a polymerizable compound, a photopolymerization initiator, and thermal crosslinking.
  • An agent preferably a carboxyl group-containing polymer compound and, if necessary, other components.
  • the compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring includes at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent, and triazole. If it is a compound which has at least a ring, there will be no restriction
  • Examples of the group capable of reacting with the radical include an acryloyloxy group, a methacryloyloxy group, a vinylphenyl group, and an allyl group.
  • Examples of the group capable of reacting with the thermal crosslinking agent include a carboxyl group, an amino group, and a mercapto group.
  • the triazole ring may be any of 1,2,3-triazole ring and 1,2,4-triazole ring.
  • 1,2,3-triazole and 1,2,4-triazole are compounds represented by the following structural formula.
  • the compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring is, in other words, at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent.
  • the bonding position of the organic group to the triazole ring is not particularly limited and may be appropriately selected depending on the purpose, and may be bonded to a nitrogen atom of the triazole ring or bonded to a carbon atom. May be.
  • a compound represented by the following general formula (I) is preferable.
  • X represents a triazole ring.
  • Y represents an organic group having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent.
  • n represents an integer of 1 to 3. When n is 2 to 3, Y may be the same or different.
  • Y may be bonded to a nitrogen atom of the triazole ring which is X, or may be bonded to a carbon atom.
  • n is preferably 1 to 2, and more preferably 2. When n is 2, it is advantageous in terms of insulation.
  • Y in the general formula (I) is preferably a group represented by the following general formula (II).
  • Y 1 represents an m + 1 valent organic group having 2 to 25 carbon atoms.
  • Z 1 represents any of a carboxyl group, an acryloyloxy group, and a methacryloyloxy group.
  • m represents an integer of 1 to 2. When m is 2, Z 1 may be the same or different.
  • the m + 1 valent organic group having 2 to 25 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of a urea bond, an amide bond, an ester bond, and a thiourea bond is selected. And an m + 1 valent organic group having 2 to 25 carbon atoms.
  • the carbon number of the organic group is preferably 2 to 20, and more preferably 2 to 15.
  • the molecular weight of the compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring is not particularly limited and may be appropriately selected depending on the intended purpose. 1,000 is preferable, and 100 to 800 is more preferable.
  • Specific examples of the compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring include compounds represented by the following formulas.
  • the content of the compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring in the photosensitive composition is not particularly limited and is appropriately selected depending on the purpose. 1.0 mass% to 20 mass% is preferable with respect to the solid content of the photosensitive composition, and 1.5 mass% to 10 mass% is more preferable. When the content is less than 1.0% by mass, sufficient insulating properties may not be exhibited. When the content exceeds 20% by mass, heat resistance may be deteriorated. When the content is within the more preferable range, it is advantageous in terms of both heat resistance and insulating properties.
  • numerator is preferable.
  • at least one selected from monomers having a (meth) acryl group is more preferable.
  • the polymerizable compound is a compound different from a compound having at least one of a group capable of reacting with the radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring.
  • polyethyleneglycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth)
  • Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanedi (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol hexa (meth) acrylate, dip
  • Urethane acrylates ; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; epoxy resins and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products.
  • dicyclopentanyl dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Is more preferable.
  • the content of the polymerizable compound in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. It is 2% by mass to 50% with respect to the solid content of the photosensitive composition. % By mass is preferable, 3% by mass to 40% by mass is more preferable, and 4% by mass to 35% by mass is particularly preferable.
  • the content of the polymerizable compound is less than 2% by mass, pattern formation may not be possible, and when it exceeds 50% by mass, crack resistance may be inferior.
  • the content of the polymerizable compound is within the particularly preferable range, it is advantageous in that the pattern formability and crack resistance are improved.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected according to the purpose.
  • a halogenated hydrocarbon derivative, phosphine oxide, hexa examples include arylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.
  • halogenated hydrocarbon derivative examples include a halogenated hydrocarbon derivative having a triazine skeleton and a halogenated hydrocarbon derivative having an oxadiazole skeleton.
  • the halogenated hydrocarbon derivative having a triazine skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. For example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A-53-133428, German Patent No. 3337024 Compounds, F.I. C. J. Schaefer et al. Org. Chem.
  • halogenated hydrocarbon derivative having an oxadiazole skeleton examples include compounds described in US Pat. No. 4,221,976.
  • the oxime derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0085” of JP-A-2007-2030.
  • the ketone compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0087” of JP-A-2007-2030.
  • examples of photopolymerization initiators other than the above include compounds described in paragraph “0086” of JP-A-2007-2030.
  • a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
  • the sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
  • the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the compounds described in paragraph “0089” of JP2007-2030A.
  • the combination of the photopolymerization initiator and the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • an electron transfer type initiation system described in JP-A-2001-305734 [ (1) Electron donating initiator and sensitizing dye, (2) Electron accepting initiator and sensitizing dye, (3) Electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiation system) ] Etc. are mentioned.
  • the content of the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05% by mass to 30% by mass with respect to the solid content of the photosensitive composition. 0.1 mass% to 20 mass% is more preferable, and 0.2 mass% to 10 mass% is particularly preferable. When the content of the sensitizer is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease, exceeding 30% by mass. In some cases, the sensitizer may precipitate from the photosensitive layer during storage.
  • the said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • Particularly preferred examples of the photopolymerization initiator include phosphine oxides, ⁇ -aminoalkyl ketones, halogenated hydrocarbon compounds having a triazine skeleton, which are compatible with laser light having a wavelength of 405 nm in the later-described exposure.
  • Examples thereof include a composite photoinitiator combined with an amine compound as a sensitizer, a hexaarylbiimidazole compound, and titanocene.
  • -Content of photopolymerization initiator- There is no restriction
  • 0.5 mass% with respect to solid content of the said photosensitive composition Is preferably 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.
  • the content of the photopolymerization initiator is less than 0.5% by mass, the exposed area tends to be eluted during development, and when it exceeds 20% by mass, the heat resistance may be lowered.
  • the content of the photopolymerization initiator is within the particularly preferable range, it is advantageous in that a good pattern can be formed and heat resistance is also improved.
  • the thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but has at least one functional group selected from a cyclic ether group, a blocked isocyanate group, an oxazolyl group, and an ethylene carbonate group. Compounds are preferred.
  • thermal crosslinking agent examples include a compound having a cyclic ether group, a compound having a blocked isocyanate group, a compound having an oxazolyl group, and a compound having an ethylene carbonate group.
  • Examples of the compound having a cyclic ether group include a compound having an oxirane group and a compound having an oxetanyl group.
  • Examples of the compound having an oxirane group include an epoxy compound having at least two oxirane groups in one molecule.
  • Examples of the compound having an oxetanyl group include an oxetane compound having at least two oxetanyl groups in one molecule.
  • epoxy compound there is no restriction
  • the oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polyfunctional oxetane compound described in paragraph “0096” of JP-A-2007-2030.
  • the compound having a blocked isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds obtained by reacting an isocyanate group of polyisocyanate and its derivatives with a blocking agent. Examples of such a compound include blocked polyisocyanate described in paragraph “0023” of JP-A-5-9407.
  • the compound having an oxazolyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is obtained by polymerizing an unsaturated monomer having an oxazolyl group with another unsaturated monomer as necessary. Resin etc. are mentioned.
  • the unsaturated monomer having an oxazolyl group include vinyl oxazoline compounds such as 2-isopropenyl-2-oxazoline.
  • a commercial item can be used as a compound which has the said oxazolyl group.
  • Examples of the commercially available product include EPOCROS RPS-1005 manufactured by Nippon Shokubai Co., Ltd.
  • the compound having an ethylene carbonate group is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include an acrylic resin having an ethylene carbonate group.
  • examples of the acrylic resin having an ethylene carbonate group include carbonate group-containing copolymers described in JP-A-1-146968.
  • a compound having an oxirane group is preferable in terms of the smoothness of the pattern side surface and the insulating property.
  • the content of the thermal crosslinking agent in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1% by mass to 50% with respect to the solid content of the photosensitive composition. % By mass is preferable, 2% by mass to 40% by mass is more preferable, and 3% by mass to 30% by mass is particularly preferable.
  • the content of the thermal crosslinking agent is less than 1% by mass, heat resistance may be deteriorated, and when it exceeds 50% by mass, developability and crack resistance may be deteriorated.
  • the content is within the particularly preferable range, a cured film can be produced with good sensitivity, and the formed cured film is advantageous in that both heat resistance and crack resistance can be achieved.
  • the carboxyl group-containing polymer compound is not particularly limited as long as it is a polymer compound having a carboxyl group, and can be appropriately selected according to the purpose.
  • an acid-modified ethylenically unsaturated group-containing polyurethane resin examples thereof include an acid-modified ethylenically unsaturated group-containing epoxy resin, an acrylic resin containing an ethylenically unsaturated group and a carboxyl group, and a polyimide precursor.
  • an acid-modified ethylenically unsaturated group-containing polyurethane resin is preferable in terms of excellent crack resistance.
  • the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited as long as it is a polyurethane resin having an acid group carboxyl group and an ethylenically unsaturated group, and can be appropriately selected according to the purpose.
  • a polyurethane resin having an ethylenically unsaturated group in the side chain (ii) a polyurethane obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule Resin etc. are mentioned.
  • polyurethane resin having an ethylenically unsaturated group in the side chain-- is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the side chain may be represented by the following general formulas (1) to (3). What has at least 1 among the functional groups represented is mentioned.
  • R 1 to R 3 each independently represents a hydrogen atom or a monovalent group.
  • R 1 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
  • the R 2 and R 3 are not particularly limited and may be appropriately selected depending on the purpose. For example, each of R 2 and R 3 is independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group.
  • a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • X represents an oxygen atom, a sulfur atom, or —N (R 12 ) —
  • R 12 represents a hydrogen atom or a monovalent organic group.
  • R 12 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
  • the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom.
  • R 4 to R 8 each independently represents a hydrogen atom or a monovalent group.
  • R 4 to R 8 are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbony
  • substituents that can be introduced include those similar to those of the general formula (1).
  • Y represents an oxygen atom, a sulfur atom, or —N (R 12 ) —.
  • R 12 has the same meaning as R 12 in the general formula (1), and preferred examples are also the same.
  • R 9 to R 11 each independently represents a hydrogen atom or a monovalent group.
  • R 9, is not particularly limited and may be appropriately selected depending on the purpose, for example, an alkyl group which may have a hydrogen atom or a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
  • R 10 and R 11 are not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent
  • An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned.
  • a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • Z represents an oxygen atom, a sulfur atom, —N (R 13 ) —, or an optionally substituted phenylene group.
  • R 13 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain includes at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5):
  • At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If at least one of them is present, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain as a reaction product of the diisocyanate compound and the diol compound is provided. Generated. According to the method, the polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain rather than replacing and / or introducing the desired side chain after the reaction of the polyurethane resin is produced. Can be easily manufactured.
  • the diisocyanate compound represented by the general formula (4) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a monofunctional alcohol or a monofunctional alcohol having a triisocyanate compound and an ethylenically unsaturated group may be used.
  • examples thereof include diisocyanate compounds that can be obtained by addition reaction with 1 equivalent of a functional amine compound.
  • the triisocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438. Is mentioned.
  • the monofunctional alcohol having an ethylenically unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the method for introducing an ethylenically unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a method using a diisocyanate compound containing a polymerizable unsaturated group is preferred.
  • limiting in particular as said diisocyanate compound According to the objective, it can select suitably, A triisocyanate compound and the monofunctional alcohol which has an ethylenically unsaturated group, or 1 equivalent of monofunctional amine compounds are made to react.
  • the diisocyanate compound that can be obtained by the method include compounds having an ethylenically unsaturated group in the side chain described in paragraphs “0042” to “0049” of JP-A-2005-250438.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain contains the ethylenically unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. It is also possible to copolymerize diisocyanate compounds other than the diisocyanate compound.
  • the diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include a diisocyanate compound represented by the following general formula (6).
  • OCN-L 1 -NCO General formula (6) L 1 is a divalent aliphatic which may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Or represents an aromatic hydrocarbon group. If necessary, L 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.
  • the diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Aromatic diisocyanate compounds such as' -diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4 -Alicyclic diisocyanate compounds such as methylenebis (cyclohexyl
  • diol compound represented by the said General formula (5) there is no restriction
  • high molecular diols such as a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound
  • Low molecular diol compounds such as ethylene glycol and neopentyl glycol
  • diol compounds having an ethylenically unsaturated group diol compounds having a carboxylic acid group.
  • a diol compound containing an ethylenically unsaturated group in the side chain is used as a raw material for producing the polyurethane resin.
  • a method is also preferred.
  • the diol compound containing an ethylenically unsaturated group in the side chain may be a commercially available compound such as trimethylolpropane monoallyl ether, or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound.
  • the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose.
  • paragraphs “0057” to “0060” of JP-A-2005-250438 can be used.
  • R 1 to R 3 each independently represents a hydrogen atom or a monovalent group
  • A represents a divalent organic residue
  • X represents an oxygen atom, a sulfur atom, or — N (R 12 ) —
  • R 12 represents a hydrogen atom or a monovalent organic group.
  • R 1 ⁇ R 3 and X in the general formula (G) said a general formula (1) the same meaning as R 1 ⁇ R 3 and X in preferred embodiments versa.
  • the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain is, for example, ethylenic in the side chain from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability.
  • a diol compound other than a diol compound containing an unsaturated group can be copolymerized.
  • the diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol Compound etc. are mentioned.
  • the polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0068” to “0076” of JP-A-2005-250438. It is done.
  • the polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs “0077” to “0079” and paragraphs “0083” to “0085” of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like.
  • the polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs “0080” to “0081” and paragraph “0084” of JP-A-2005-250438, No. 9-No. 12 listed compounds.
  • the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
  • the diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.
  • a diol compound having a carboxyl group can be used in combination with the diol compound described above.
  • the diol compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by the following general formulas (8) to (10).
  • R 15 is a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , —COOR 16 , —OR 16 , —NHCONHR 16 , —NHCOOR 16 , —NHCOR 16 , —OCONHR 16 (wherein R 16 is an alkyl group having 1 to 10 carbon atoms, or 7 to 15 carbon atoms) Represents an aralkyl group.) Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group which may have a group.
  • a substituent for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , —COOR 16 ,
  • L 9 , L 10 and L 11 may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group).
  • a divalent aliphatic or aromatic hydrocarbon group optionally having a group, an alkoxy group, or a halogeno group).
  • an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable.
  • the above L 9 to L 11 may have another functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. .
  • Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose.
  • An aromatic group having 6 to 15 carbon atoms is preferable.
  • the diol compound having a carboxyl group represented by the general formulas (8) to (10) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • 3,5-dihydroxybenzoic acid, 2 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4- Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) ) -3-carboxy-propionamide and the like.
  • the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. More specifically, the polyurethane resin having an ethylenically unsaturated group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the ethylenically unsaturated group in the side chain is 0. 0.05 mmol / g to 3.0 mmol / g is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
  • the side chain has a carboxyl group
  • the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mg KOH / g is particularly preferred.
  • the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity depending on the reactivity and heating. Is done.
  • the molar ratio (M a : M b ) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, and is preferably 1: 1 to 1.2: 1.
  • a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain those having an ethylenically unsaturated group in the polymer terminal and main chain are also preferably used.
  • By having an ethylenically unsaturated group at the polymer terminal and main chain it further has an ethylenically unsaturated group between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated group in the side chain, or in the side chain.
  • Crosslinking reactivity is improved between polyurethane resins, and the strength of the photocured product is increased.
  • a material having excellent toughness can be provided.
  • Examples of the method for introducing an ethylenically unsaturated group at the polymer terminal include the following methods. That is, in the step of synthesizing a polyurethane resin having an ethylenically unsaturated group in the side chain as described above, in the step of treating with a residual isocyanate group at the polymer end and an alcohol or an amine, it has an ethylenically unsaturated group. Alcohols or amines may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an ethylenically unsaturated group.
  • the ethylenically unsaturated group is preferably introduced into the polymer side chain rather than the polymer end from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and the crosslinking reaction efficiency is improved. .
  • the ethylenically unsaturated group to be introduced is not particularly limited and may be appropriately selected according to the purpose.
  • an allyl group, a methacryloyl group, an acryloyl group, and a vinylphenyl group are preferable.
  • a methacryloyl group and an acryloyl group are more preferable, and a methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
  • the amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
  • a method of introducing an ethylenically unsaturated group into the main chain there is a method of using a diol compound having an ethylenically unsaturated group in the main chain direction for the synthesis of a polyurethane resin.
  • the diol compound having an ethylenically unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose, such as cis-2-butene-1,4-diol, trans-2-butene 1,4-diol, polybutadiene diol and the like.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin.
  • the polyurethane resin having an ethylenically unsaturated group in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
  • polyurethane resin having an ethylenically unsaturated group in the side chain examples include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. And 31 polymers. Among these, polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.
  • a polyurethane resin obtained by reacting the carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule includes a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components;
  • a low molecular diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a diol component as a copolymer component.
  • the polyurethane resin it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are improved.
  • the polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom.
  • a reaction product comprising a carboxylic acid-containing diol as an essential component, and reacting the obtained reaction product with a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a —COO— bond. It may be obtained.
  • the polyurethane resin includes at least one selected from diisocyanates represented by the following general formula (11) and carboxylic acid group-containing diols represented by the following general formulas (12-1) to (12-3): Is obtained by reacting a product having an essential component with a compound having an epoxy group and an ethylenically unsaturated group in the molecule represented by the following general formulas (13-1) to (13-16). May be.
  • R 1 may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aromatic or aromatic hydrocarbon.
  • R 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.
  • R 2 represents a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , — COOR 6 , —OR 6 , —NHCONHR 6 , —NHCOOR 6 , —NHCOR 6 , —OCONHR 6 , —CONHR 6 (where R 6 is an alkyl group having 1 to 10 carbon atoms and aralkyl having 7 to 15 carbon atoms) Each group is included), which may have an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group.
  • R 3 , R 4 and R 5 may be the same or different from each other, and may be a single bond, a substituent (for example, , An alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group are preferable), and may represent a divalent aliphatic or aromatic hydrocarbon.
  • an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable.
  • any other functional group that does not react with an isocyanate group for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of said R ⁇ 2 >, R ⁇ 3 >, R ⁇ 4 > and R ⁇ 5 >.
  • Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms.
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 represents an alkylene group having 1 to 10 carbon atoms
  • R 16 represents a carbon atom. This represents a hydrocarbon group having a number of 1 to 10.
  • p represents 0 or an integer of 1 to 10.
  • polyurethane resin examples include at least one selected from diisocyanates represented by the general formula (11) and carboxylic acid group-containing diols represented by the general formulas (12-1) to (12-3).
  • the reaction product is further reacted with a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any one of the general formulas (13-1) to (13-16).
  • An alkali-soluble photo-crosslinkable polyurethane resin having an acid value of 20 mgKOH / g to 120 mgKOH / g is preferred.
  • These polymer compounds may be used alone or in combination of two or more.
  • the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating.
  • the molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. If an isocyanate group remains at the end of the polymer, the molar ratio can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.
  • the diisocyanate compound represented by the general formula (11) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, compounds described in paragraph “0021” of JP-A-2007-2030, etc. Is mentioned.
  • the diol compound having a carboxyl group represented by the general formulas (12-1) to (12-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph “0047” of the publication No. 2030.
  • the carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0048” of JP-A-2007-2030. It is done.
  • the copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80 mol% or less, and particularly preferably 50 mol% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.
  • polyurethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule include, for example, paragraph “Japanese Patent Application Laid-Open No. 2007-2030”.
  • Glycidyl acrylate as an epoxy group and ethylenically unsaturated group-containing compound in the polymers of U1 to U13, U1 to U4 and U6 to U11 shown in "0314" to "0315” is converted into glycidyl methacrylate, 3,4-epoxycyclohexylmethyl.
  • Examples thereof include polymers in place of acrylate (trade name: Cyclomer A400 (manufactured by Daicel Chemical Industries)) and 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical Industries)).
  • the weight average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 60,000, and preferably 3,000 to 50 3,000 is more preferable, and 3,000 to 30,000 is particularly preferable.
  • the weight average molecular weight is less than 2,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may deteriorate. is there.
  • the photosensitive composition when used as a photosensitive solder resist when the weight average molecular weight is 2,000 to 60,000, it is excellent in crack resistance and heat resistance, and is non-image area by an alkaline developer. Excellent developability.
  • the weight average molecular weight is determined by using, for example, a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Kogyo Co., Ltd.) and using a 0.5 mass% tetrahydrofuran (THF) solution as a sample solution, and the column is TSKgel HZM- Using one M, 200 ⁇ L of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm).
  • the acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g, preferably 30 mgKOH / g to 110 mgKOH / g is more preferable, and 35 mgKOH / g to 100 mgKOH / g is particularly preferable.
  • the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.
  • the ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.05 mmol / g to 3.0 mmol / g. Preferably, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
  • the heat resistance of the cured film may be inferior, and when it exceeds 3.0 mmol / g, the brittleness of the cured film may increase.
  • the said ethylenically unsaturated group equivalent can be calculated
  • the bromine number can be measured according to, for example, JIS K2605.
  • the acid-modified ethylenically unsaturated group-containing epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least two or more per molecule described in Japanese Patent No.
  • Acid-modified ethylenically unsaturated group-containing epoxy resin which is a reaction product of acid (c) product (I) and polybasic acid anhydride (d), epoxy having at least two epoxy groups in one molecule
  • Compound (a) compound (b) having one reactive group other than a hydroxyl group that reacts with at least two hydroxyl groups and an epoxy group in one molecule, and an ethylenically unsaturated group-containing monomer
  • An acid-modified ethylenically unsaturated group-containing epoxy resin which is a product of a product (I) of a boric acid (c), a polybasic acid anhydride (d), and an ethylenically unsaturated
  • acid-modified ethylenically unsaturated group-containing epoxy resin examples include ZFR series, CCR series, and PCR series (manufactured by Nippon Kayaku Co., Ltd.).
  • -Acrylic resin containing ethylenically unsaturated groups and carboxyl groups There is no restriction
  • an acrylic resin for example, it is obtained from (meth) acrylic acid ester and a compound containing an ethylenically unsaturated group and having at least one acid group described in JP-A-2009-86376.
  • examples thereof include a modified copolymer obtained by adding glycidyl (meth) acrylate to a part of acid groups of the obtained copolymer.
  • a commercial item can be used for the acrylic resin containing the said ethylenically unsaturated group and a carboxyl group.
  • CyclomerP 200HM made by Daicel Chemical Industries
  • thermoplastic elastomers examples include thermoplastic elastomers, thermosetting accelerators, adhesion promoters, thermal polymerization inhibitors, inorganic fillers, colorants, organic solvents, thixotropic agents, antifoaming agents, and leveling agents.
  • thermosetting accelerators thermosetting accelerators
  • adhesion promoters thermal polymerization inhibitors
  • inorganic fillers colorants
  • organic solvents organic solvents
  • thixotropic agents antifoaming agents
  • leveling agents leveling agents.
  • thermoplastic elastomer By adding the thermoplastic elastomer to the photosensitive composition, heat resistance, flexibility and toughness can be imparted to the photosensitive composition.
  • thermoplastic elastomer There is no restriction
  • thermoplastic elastomers are composed of a hard segment component and a soft segment component.
  • the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.
  • styrene elastomer examples include, for example, paragraph “ And the like described in “0087” to “0095”.
  • thermoplastic elastomer The content of the thermoplastic elastomer in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. It is 1% by mass to 50% with respect to the solid content of the photosensitive composition. % By mass is preferable, 2% by mass to 20% by mass is more preferable, and 3% by mass to 10% by mass is particularly preferable. If the content is less than 1% by mass, the crack resistance may be inferior, and if it exceeds 50% by mass, the unexposed part may not be eluted with the developer. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of improving developability and crack resistance.
  • thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0101” of JP-A-2007-2030.
  • thermosetting accelerator- There is no restriction
  • the content of the thermosetting accelerator is less than 0.01% by mass, the toughness of the cured film may not be expressed.
  • the storage stability of the photosensitive composition may be reduced. May get worse.
  • the content of the thermosetting accelerator is within the particularly preferable range, it is advantageous in that the storage stability of the photosensitive composition and the physical properties of the cured film are improved.
  • the adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0108” of JP-A-2007-2030.
  • the thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0113” of JP-A-2007-2030.
  • the inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably contains silica particles having an average particle diameter (d50) of 0.05 ⁇ m to 3.0 ⁇ m.
  • d50 average particle diameter
  • the inorganic filler contains silica particles, the heat resistance of the cured film is improved, the dispersibility with the carboxyl group-containing polymer compound is improved, and the viscosity of the photosensitive composition is maintained in a suitable range. And suitable coating aptitude is obtained.
  • silica in the said silica particle there is no restriction
  • the average particle diameter (d50) of the silica particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 ⁇ m to 3.0 ⁇ m, more preferably 0.1 ⁇ m to 2.5 ⁇ m. 0.1 ⁇ m to 2.0 ⁇ m is particularly preferable.
  • the coating viscosity may increase, and when it exceeds 3.0 ⁇ m, smoothness may not be maintained.
  • the average particle diameter (d50) of the silica particles is within the particularly preferable range, it is advantageous in view of coating viscosity, smoothness of a cured film and heat resistance.
  • the average particle diameter of the silica particles (d50) is integrated intended to be defined by the integrated value of 50% particle size when expressed in (cumulative) weight percent, intended to be defined as such d50 (D 50) Yes, for example, using a dynamic light scattering photometer (trade name DLS7000, manufactured by Otsuka Electronics Co., Ltd.), the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method. be able to.
  • the content of the inorganic filler in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1% by mass to the solid content of the photosensitive composition. 60% by mass is preferable, 10% by mass to 60% by mass is more preferable, and 15% by mass to 60% by mass is particularly preferable.
  • content of the said inorganic filler is less than 1 mass%, heat resistance may be inferior, and when it exceeds 60 mass%, pattern formability may be inferior.
  • the content is within the particularly preferable range, it is advantageous in that the pattern formability and heat resistance are improved.
  • a coloring pigment and the dye suitably selected from well-known dye can be used.
  • the color pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0106” of JP-A-2007-2030.
  • Organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in “0121”.
  • the content of the organic solvent in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. It is 1% by mass to 80% by mass with respect to the solid content of the photosensitive composition. %, Preferably 2% to 70% by weight, more preferably 3% to 60% by weight.
  • the content of the organic solvent is less than 1% by mass, the viscosity of the composition may be high and it may be difficult to form a coating film.
  • the content exceeds 80% by mass, it is difficult to control the desired film thickness. May be.
  • the content of the organic solvent is within the particularly preferable range, it is advantageous from the viewpoint of coating film production suitability.
  • the photosensitive solder resist composition of the present invention contains the photosensitive composition of the present invention. According to the photosensitive solder resist composition of the present invention, it is possible to obtain a solder resist excellent in insulation, smoothness of the pattern side surface, and plating resistance.
  • the photosensitive solder resist composition of the present invention can be used as a liquid resist by coating and drying on a substrate on which a conductor wiring is formed, but is particularly useful for the production of a photosensitive solder resist film.
  • the photosensitive solder resist film of the present invention comprises at least a support and a photosensitive layer, preferably a protective film, and further comprises a cushion layer, an oxygen barrier layer (hereinafter referred to as “PC”) as necessary. It may be abbreviated as “layer”).
  • PC oxygen barrier layer
  • Form Form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film on the support.
  • the photosensitive layer may be a single layer or a plurality of layers.
  • the support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and further the surface smoothness Is more preferable.
  • a transparent synthetic resin film is mentioned.
  • the transparent synthetic resin film is not particularly limited and may be appropriately selected depending on the intended purpose.
  • plastic films such as polytetrafluoroethylene, polytrifluoroethylene, cellulose-based film, and nylon film.
  • the transparent synthetic resin film is preferably polyethylene terephthalate.
  • the support is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the thickness of the support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 4 ⁇ m to 300 ⁇ m, and more preferably 5 ⁇ m to 175 ⁇ m.
  • the length of the long support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 m to 20,000 m.
  • the photosensitive layer is formed by the photosensitive solder resist composition of the present invention.
  • the photosensitive layer is formed by the photosensitive solder resist composition of the present invention.
  • the thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 70 ⁇ m.
  • a photosensitive solder resist composition solution is prepared by dissolving, emulsifying, or dispersing the photosensitive solder resist composition of the present invention in water or a solvent on the support, The method of laminating
  • the solvent for the photosensitive solder resist composition solution is not particularly limited and may be appropriately selected depending on the intended purpose.
  • alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and the like.
  • esters examples include ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate.
  • aromatic hydrocarbons include toluene, xylene, benzene, ethylbenzene and the like.
  • halogenated hydrocarbons include carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene.
  • ethers examples include tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, and the like. These may be used individually by 1 type and may use 2 or more types together.
  • the solid content concentration of the photosensitive solder resist composition solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass to 90% by mass, and more preferably 15% by mass to 50% by mass. More preferred.
  • the application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc.
  • coating is mentioned.
  • the drying conditions are not particularly limited and may be appropriately selected depending on the purpose. The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 110 ° C. for 30 seconds. About 15 minutes.
  • the protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
  • the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin sheets, polytetrafluoroethylene sheets, and the like.
  • the thickness of the protective film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m to 100 ⁇ m, and more preferably 8 ⁇ m to 30 ⁇ m.
  • the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
  • the combination of the support and the protective film include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. It is done.
  • the above-mentioned relationship of adhesive force can be satisfy
  • the surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • coating of a primer layer corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.
  • the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll.
  • the method for storing the photosensitive solder resist film is not particularly limited and can be appropriately selected according to the purpose.
  • the photosensitive solder resist film is wound around a cylindrical core and wound into a long roll.
  • the length of the long photosensitive solder resist film is not particularly limited, and can be appropriately selected from a range of 10 m to 20,000 m, for example.
  • slitting may be performed so that the user can use it easily, and a long body in the range of 100 m to 1,000 m may be rolled.
  • the support is wound up so as to be the outermost side.
  • a separator especially moisture-proof and desiccant-containing
  • a separator especially moisture-proof and desiccant-containing
  • the protective film may be surface-treated to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane or fluorinated polyolefin such as polyfluoroethylene or polyvinyl alcohol is formed on the surface of the protective film.
  • the undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 ° C. to 150 ° C. (especially 50 ° C. to 120 ° C.) for 1 minute to 30 minutes. be able to.
  • a cushion layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • the cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
  • the PC layer is usually a film having a thickness of about 1.5 ⁇ m formed mainly of polyvinyl alcohol.
  • the photosensitive solder resist film has a small surface tackiness, good laminating property and handleability, and is a photosensitive layered with a photosensitive solder resist composition excellent in insulation, plating resistance and pattern side smoothness. Having a layer. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls and other display members, holograms, micromachines, proofs, etc. It can be suitably used for the forming method. In particular, since the photosensitive solder resist film of the present invention has a uniform thickness, it is more accurately laminated on a substrate when a permanent pattern is formed.
  • the permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
  • the permanent pattern is preferably at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the dynamic elastic modulus at 220 ° C. is preferably 20 to 100 MPa, more preferably 25 to 80 MPa, and particularly preferably 30 to 50 MPa. If the dynamic elastic modulus is less than 20 MPa, the heat resistance may be inferior, and if it exceeds 100 MPa, the thermal shock resistance may be inferior and cracks may occur in the cured film.
  • the photosensitive solder resist composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed (exposure process).
  • Develop development process
  • the photosensitive solder resist film of the present invention is laminated on the surface of the substrate under at least one of heating and pressurization, and then exposed (exposure). Process) and development (development process).
  • the substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a printed wiring board forming substrate such as a copper-clad laminate, a glass plate such as a soda glass plate, or a synthetic resin film , Paper, metal plate and the like.
  • a printed wiring board forming substrate on which wiring is already formed is preferable in that high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board is possible.
  • the substrate is a laminate in which a photosensitive layer made of the photosensitive solder resist composition is formed on the substrate as the first aspect, or the photosensitive solder resist film as the second aspect. It is possible to use by forming a laminate in which the photosensitive layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed region can be cured, and a permanent pattern can be formed by development to be described later.
  • the said photosensitive soldering resist composition is apply
  • the method for coating and drying is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the photosensitive solder resist composition solution is spin coater, slit spin coater, roll coater, die coater, curtain. The method of apply
  • the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 70 ° C to 130 ° C, and more preferably 80 ° C to 110 ° C.
  • the pressurizing pressure is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 MPa to 1.0 MPa, more preferably 0.05 MPa to 1.0 MPa.
  • An apparatus for performing at least one of the heating and pressurization is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a heat press for example, VP-manufactured by Taisei Laminator Co., Ltd.) II
  • a vacuum laminator for example, MVLP500 manufactured by Meiki Seisakusho Co., Ltd.
  • suitable devices for example, a heat press, a heat roll laminator (for example, VP-manufactured by Taisei Laminator Co., Ltd.) II), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho Co., Ltd.) and the like can be mentioned as suitable devices.
  • the exposure step is a step of performing pattern exposure on the photosensitive layer.
  • the subject of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected according to the purpose.
  • the photosensitive solder resist composition or the photosensitive solder resist is formed on a substrate. It is preferable to be performed on the laminate formed with a film.
  • the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling the support and cushion layer, the photosensitive layer is exposed through the PC layer. Alternatively, the photosensitive layer may be exposed after the support, the cushion layer and the PC layer are peeled off.
  • the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure. Among these, digital exposure is preferable.
  • the digital exposure is not particularly limited and can be appropriately selected depending on the purpose.
  • a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.
  • the digital exposure means is not particularly limited and may be appropriately selected depending on the purpose.
  • light irradiation means for irradiating light light emitted from the light irradiation means based on pattern information to be formed
  • a light modulation means for modulating the light intensity for example, light irradiation means for irradiating light, light emitted from the light irradiation means based on pattern information to be formed
  • a light modulation means for modulating the light intensity.
  • the light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose, but preferably has n pixel portions.
  • the light modulation means having the n picture elements is not particularly limited and may be appropriately selected according to the purpose, but a spatial light modulation element is preferable.
  • the spatial light modulation element is not particularly limited and may be appropriately selected depending on the purpose.
  • a spatial light modulation element of a digital micromirror device (DMD) or MEMS (Micro Electro Mechanical Systems) type examples thereof include SLM (Special Light Modulator), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, and a liquid crystal light shutter (FLC).
  • SLM Specific Light Modulator
  • PZT element optical element
  • FLC liquid crystal light shutter
  • a digital micromirror device is preferable.
  • the light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
  • the control signal generated by the pattern signal generation unit.
  • the developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.
  • the method for removing the uncured region is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method using a developer.
  • the developer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of Among these, an aqueous sodium carbonate solution is preferable.
  • the developer may be used in combination with a surfactant, an antifoaming agent, an organic base, an organic solvent or the like for accelerating development.
  • the organic base is not particularly limited and may be appropriately selected depending on the intended purpose.
  • benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanol An amine etc. are mentioned.
  • the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, ketones, esters, ethers, amides, and lactones.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
  • the permanent pattern forming method of the present invention preferably further includes a curing treatment step.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.
  • the curing treatment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include full exposure processing and full heat treatment.
  • the method for the entire surface exposure treatment is not particularly limited and may be appropriately selected depending on the purpose.
  • the entire surface exposure accelerates the curing of the resin in the photosensitive solder resist composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
  • an apparatus which performs the said whole surface exposure According to the objective, it can select suitably, For example, UV exposure machines, such as a super-high pressure mercury lamp, etc. are mentioned.
  • the method for the entire surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, a method for heating the entire surface of the laminate on which the permanent pattern is formed after the development step. Etc.
  • the entire surface heating increases the film strength of the surface of the permanent pattern.
  • the heating temperature for the entire surface heating is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 120 ° C. to 250 ° C., more preferably 120 ° C. to 200 ° C. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive solder resist composition is decomposed and the film quality is weak. May become brittle.
  • the heating time in the entire surface heating is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
  • an apparatus which performs the said whole surface heating According to the objective, it can select suitably, For example, a dry oven, a hot plate, IR heater etc. are mentioned.
  • the permanent pattern of the present invention can be formed on the printed wiring board, and soldering can be performed as follows. That is, the hardened layer which is the permanent pattern is formed by the developing process, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.
  • soldering can be performed as follows. That is, the hardened layer which is the permanent pattern is formed by the developing process, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time,
  • the permanent pattern forming method of the present invention it is preferable to form at least one of a protective film and an interlayer insulating film.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film
  • the wiring can be protected from external impact and bending, particularly when the interlayer insulating film is the interlayer insulating film. Is useful for high-density mounting of semiconductors and components on, for example, multilayer wiring boards and build-up wiring boards.
  • the permanent pattern forming method of the present invention can be widely used for forming various patterns because the pattern can be formed at a high speed, and can be particularly suitably used for forming a wiring pattern.
  • the permanent pattern formed by the permanent pattern forming method of the present invention has excellent insulating properties, plating resistance, smoothness of the pattern side surface, etc., and is suitable as a protective film, interlayer insulating film, solder resist pattern, etc. Can be used.
  • the printed circuit board of the present invention comprises at least a base material and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
  • the printed circuit board of the present invention can select suitably, For example, the buildup board
  • reaction solution was poured into 1.2 L of ion-exchanged water with strong stirring to crystallize the desired product. Washing with isopropanol / hexane (2/8 (mass ratio)), filtration and drying gave 121.1 g of compound T-3 having the following structure.
  • the obtained carboxyl group-containing polymer compound B-4 solution had a solid content acid value of 68 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 6,500. Yes, the ethylenically unsaturated group equivalent was 1.83 mmol / g.
  • the acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
  • the weight average molecular weight is determined by using a high-speed GPC device (HLC-802A manufactured by Toyo Soda Industry Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column using one TSKgel HZM-M.
  • a 200 ⁇ L sample was injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm).
  • the said ethylenically unsaturated group equivalent was calculated
  • carboxyl group-containing polymer compound B-5 solution After cooling to room temperature, 214 g of a carboxyl group-containing polymer compound B-5 solution was obtained.
  • the obtained carboxyl group-containing polymer compound B-5 solution had a solid content acid value of 75 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 12,000. Yes, the ethylenically unsaturated group equivalent was 1.3 mmol / g.
  • Example 1 ⁇ Preparation of photosensitive composition coating solution 1> The following components were mixed to prepare photosensitive composition coating solution 1 (photosensitive solder resist composition coating solution).
  • photosensitive composition coating solution 1 photosensitive solder resist composition coating solution
  • ⁇ ZFR-1776 Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing epoxy resin: 65% by mass methoxypropyl acetate solution
  • B-1 32.3 parts by mass Compound T-1 0.8 parts by mass Coloring pigment: HELIOGEN BLUE D7086 (manufactured by BASF) 0.021 parts by mass Coloring pigment: Pariotol Yellow D0960 (BASF) 0.006 parts by mass Dispersant: Solsperse 24000GR (manufactured by Loop Resor) 0.22 parts by mass Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Initiator: Irgacure 907 (BASF)
  • ⁇ Preparation of photosensitive solder resist film 1> Using a polyethylene terephthalate film (PET) having a thickness of 25 ⁇ m as a support, the photosensitive composition coating solution 1 was applied onto the support with a bar coater so that the thickness of the photosensitive layer after drying was about 30 ⁇ m.
  • the photosensitive solder resist film 1 was produced by drying in a hot air circulating dryer at 80 ° C. for 30 minutes.
  • a copper-clad laminate (with no through holes and a printed wiring board with a copper thickness of 12 ⁇ m) on which a surface was chemically polished was used.
  • the copper-clad laminate is laminated using a vacuum laminator (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) so that the photosensitive layer of the photosensitive solder resist film 1 is in contact with the copper-clad laminate.
  • MVLP500 vacuum laminator
  • the pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.
  • the resist pattern was formed with the evaluation method shown below.
  • a predetermined pattern can be obtained with a laser beam of 405 nm from the polyethylene terephthalate film (support) side using the pattern forming apparatus by blue-violet laser exposure having a predetermined pattern with respect to the photosensitive layer in the prepared laminate. In this way, an energy amount of 40 mJ / cm 2 was irradiated for exposure, and a partial region of the photosensitive layer was cured.
  • the copper foil of the printed circuit board obtained by laminating a copper foil having a thickness of 12 ⁇ m on a glass epoxy substrate is etched, the line width / space width is 50 ⁇ m / 50 ⁇ m, the lines are not in contact with each other, and the same facing each other A comb electrode on the surface was obtained.
  • the photosensitive solder resist film 1 was laminated on the comb-shaped electrode of the substrate in the same manner as described in the method for preparing the laminate, and the exposure was performed at the optimum exposure amount (300 mJ / cm 2 to 1 J / cm 2 ). .
  • a photosensitive solder resist film 1 is laminated on a printed circuit board obtained by laminating a copper foil having a thickness of 12 ⁇ m on a glass epoxy substrate in the same manner as described in the method for preparing the laminate, and through a 2 mm square photomask, Oak Manufacturing Co., Ltd.
  • Using an HMW-201GX type exposure machine manufactured by the company exposure was performed with an optimum exposure amount (300 mJ / cm 2 to 1 J / cm 2 ) that can form a 2 mm square pattern.
  • spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C.
  • the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm 2 using an ultraviolet irradiation device manufactured by Oak Manufacturing. Further, the photosensitive layer was subjected to a heat treatment at 150 ° C. for 60 minutes to obtain a substrate for evaluation on which a 25 ⁇ m thick solder resist having a rectangular opening of 2 mm square was formed. The obtained substrate was exposed to an atmosphere of ⁇ 65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then exposed to the air of ⁇ 65 ° C. again for 1,000 times.
  • Example 2 In Example 1, ZFR-1176 (produced by Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing epoxy resin) (B-1) was added to CyclerP 200HM (produced by Daicel Chemical Industries, Ltd., containing ethylenically unsaturated groups and carboxyl groups). A photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1, except that the acrylic resin was changed to (B-2) (the content in the solid content was the same). . The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 In Example 1, ZFR-1176 (Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing epoxy resin) (B-1) was added to UXE-3024 (Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing product). A photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the polyurethane resin (B-3) was replaced (the content in the solid content was the same). The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 In Example 1, a carboxyl group-containing polymer compound (acid-modified ethylenically unsaturated polymer) obtained by synthesizing ZFR-1176 (manufactured by Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing epoxy resin) (B-1) in Synthesis Example 5 was used. A photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the saturated group-containing polyurethane resin (B-4) was replaced (the content in the solid content was the same). Produced. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 a photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 4 except that the compound T-1 was replaced with the compound T-2.
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 a photosensitive composition coating solution and a photosensitive solder resist film were produced in the same manner as in Example 4 except that the compound T-1 was replaced with the compound T-3.
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 a photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 4 except that Compound T-1 was replaced with Compound T-4.
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 8 In Example 5, except that the blending amount of Compound T-2 was changed from 1.7% by mass to 3.0% by mass with respect to the solid content of the photosensitive composition coating solution, A photosensitive composition coating solution and a photosensitive solder resist film were prepared. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 9 In Example 5, Epototo YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd., a compound having an oxirane group (bisphenol F type epoxy resin)) as an thermal crosslinking agent was used as ETERNACOLL OXBP (manufactured by Ube Industries, Ltd., a compound having an oxetanyl group) A photosensitive composition coating solution and a photosensitive solder resist film were produced in the same manner as in Example 5 except that the above was replaced. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 10 Epototo YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd., a compound having an oxirane group (bisphenol F type epoxy resin)) as a thermal crosslinking agent was added to Sumidur BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd., blocked isocyanate group).
  • a photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 5 except that the compound was changed to (Compound with a).
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 11 In Example 5, Epototo YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd., a compound having an oxirane group (bisphenol F type epoxy resin)) as a thermal crosslinking agent was converted into YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd., oxirane group A photosensitive composition coating solution and a photosensitive solder resist film were produced in the same manner as in Example 5 except that the compound was changed to (Compounds). The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 12 the carboxyl group-containing polymer compound (acid-modified ethylenically unsaturated polymer) synthesized in Synthesis Example 6 was prepared by synthesizing ZFR-1176 (manufactured by Nippon Kayaku Co., Ltd., acid-modified ethylenically unsaturated group-containing epoxy resin) (B-1).
  • a photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the saturated group-containing polyurethane resin (B-5) was replaced (the content in the solid content was the same). Produced.
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 A photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the T-1 compound and the thermal crosslinking agent were not blended in Example 1. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 2 In Example 1, a photosensitive composition coating liquid and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the T-1 compound was not blended. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A photosensitive composition coating solution and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that the T-1 compound was replaced with IXE6107 (inorganic ion exchanger manufactured by Toagosei Co., Ltd.) in Example 1. Produced. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 (Comparative Example 4) In Example 1, except that the T-1 compound was replaced with the compound TZ (1,2,4-triazole) having the following structure, the photosensitive composition coating liquid and the photosensitive composition were the same as in Example 1. A solder resist film was prepared. The obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 (Comparative Example 5)
  • a photosensitive composition coating liquid and a photosensitive solder resist film were prepared in the same manner as in Example 1 except that no thermal crosslinking agent was added.
  • the obtained photosensitive composition coating liquid and photosensitive solder resist film were evaluated in the same manner as in Example 1. The results are shown in Table 1. However, in Table 1, the content (mass%) of the triazole compound is the content with respect to the solid content of the photosensitive composition coating solution.
  • Examples 1 to 12 were excellent in insulation, plating resistance, smoothness of the pattern side surface, and crack resistance.
  • compound T-2 was used as the triazole compound, the insulation was very excellent.
  • B-4 that is, an acid-modified ethylenically unsaturated group-containing polyurethane resin was used as the carboxyl group-containing polymer compound, the crack resistance was excellent.
  • a compound having an oxirane group was used as the thermal crosslinking agent, the smoothness of the pattern side surface was excellent.
  • Comparative Example 1 all of insulating properties, plating resistance, pattern side surface smoothness, and crack resistance were much inferior to those of the Examples.
  • the comparative example 2 which does not contain a triazole compound, compared with the Example, insulation, the smoothness of the pattern side surface, and crack resistance were inferior.
  • Comparative Example 3 using an inorganic ion trapping agent, although the plating resistance was equal to that of the Example, the smoothness of the pattern side surface was inferior and the crack resistance was very inferior.
  • Comparative Example 4 using 1,2,4-triazole as the triazole compound, the smoothness of the pattern side surface and the plating resistance were inferior to those of the Examples.
  • the comparative example 5 which does not contain a thermal crosslinking agent, it resulted in inferior insulation, crack resistance, and plating resistance.
  • the improvement in the smoothness of the pattern side surface in Examples 1 to 12 is an effect that is not obtained in Comparative Examples 1 to 4, and an effect that is not known in the prior art using a triazole compound in the photosensitive composition. It is.
  • ⁇ 1> containing a compound having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent and a triazole ring, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. It is the photosensitive composition characterized.
  • ⁇ 2> The photosensitive composition according to ⁇ 1>, further including a carboxyl group-containing polymer compound.
  • ⁇ 3> The photosensitive composition according to ⁇ 2>, wherein the carboxyl group-containing polymer compound is an acid-modified ethylenically unsaturated group-containing polyurethane resin.
  • thermo crosslinking agent according to any one of ⁇ 1> to ⁇ 3>, wherein the thermal crosslinking agent is a compound having at least one functional group selected from a cyclic ether group, a blocked isocyanate group, an oxazolyl group, and an ethylene carbonate group.
  • the compound having a triazole ring and at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent is a compound represented by the following general formula (I): > The photosensitive composition according to any one of the above. However, in said general formula (I), X represents a triazole ring.
  • Y represents an organic group having at least one of a group capable of reacting with a radical and a group capable of reacting with a thermal crosslinking agent.
  • n represents an integer of 1 to 3. When n is 2 to 3, Y may be the same or different.
  • Y in the general formula (I) is a group represented by the following general formula (II).
  • Y 1 represents an m + 1 valent organic group having 2 to 25 carbon atoms.
  • Z 1 represents any of a carboxyl group, an acryloyloxy group, and a methacryloyloxy group.
  • m represents an integer of 1 to 2. When m is 2, Z 1 may be the same or different.
  • ⁇ 7> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, wherein the thermal crosslinking agent is a compound having an oxirane group.
  • a photosensitive solder resist composition comprising the photosensitive composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> A photosensitive solder resist film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive solder resist composition according to ⁇ 8> on the support.
  • the photosensitive solder resist composition according to ⁇ 8> is applied to the surface of a substrate, dried to form a laminate by forming a photosensitive layer, and then exposed and developed. This is a permanent pattern forming method.
  • ⁇ 11> A permanent pattern formed by the method for forming a permanent pattern according to ⁇ 10>.
  • ⁇ 12> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to ⁇ 10>.
  • the photosensitive solder resist film of the present invention is a protective film, interlayer insulating film, various pattern formation such as a permanent pattern such as a solder resist pattern, manufacture of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, It can be suitably used for the production of holograms, micromachines, proofs, etc., and can be particularly suitably used for forming a permanent pattern on a printed circuit board.
  • the pattern forming method of the present invention uses the photosensitive composition, it is for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, a partition wall. It can be suitably used for the production of liquid crystal structural members such as holograms, micromachines, and proofs, and can be suitably used for the formation of permanent patterns on printed boards.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne une composition photosensible qui comprend : un composé qui possède un cycle triazole, et un groupe capable de réagir avec un radical et/ou un groupe capable de réagir avec un agent de réticulation thermique; un composé polymérisable; un initiateur de photopolymérisation; et un agent de réticulation. De préférence, la composition photosensible de l'invention comprend également un composé polymère ayant un groupe carboxyle. De préférence, le composé polymère ayant un groupe carboxyle consiste en une résine de polyuréthane ayant un groupe éthyléniquement insaturé.
PCT/JP2012/051878 2011-02-28 2012-01-27 Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé Ceased WO2012117786A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011042953 2011-02-28
JP2011-042953 2011-02-28

Publications (1)

Publication Number Publication Date
WO2012117786A1 true WO2012117786A1 (fr) 2012-09-07

Family

ID=46757728

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/051878 Ceased WO2012117786A1 (fr) 2011-02-28 2012-01-27 Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé

Country Status (3)

Country Link
JP (1) JP2012194534A (fr)
TW (1) TW201235781A (fr)
WO (1) WO2012117786A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019066510A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 感光性樹脂組成物、並びに、これを用いた感光性エレメント、レジストパターンの形成方法、ソルダーレジスト、層間絶縁膜、層間絶縁膜の形成方法、プリント配線板の製造方法及びプリント配線板
CN111909409A (zh) * 2020-08-11 2020-11-10 河北工业大学 一种含唑环的低聚硅氧烷复合质子交换膜的制备方法
EP4368612A4 (fr) * 2021-06-30 2025-11-05 Samsung Display Co Ltd Nouveau composé pour couche de recouvrement, et dispositif électroluminescent organique le comprenant

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101908469B1 (ko) 2013-02-19 2018-10-16 후지필름 가부시키가이샤 근적외선 흡수성 조성물, 근적외선 차단 필터와 그 제조 방법, 및 카메라 모듈과 그 제조 방법
JP6247014B2 (ja) * 2013-04-04 2017-12-13 東京応化工業株式会社 感光性樹脂組成物
WO2014168221A1 (fr) 2013-04-11 2014-10-16 富士フイルム株式会社 Composition absorbant les rayons proche infrarouge, filtre de coupure de rayon proche infrarouge l'utilisant, procédé de fabrication de celui-ci, module de caméra, et procédé de fabrication de celui-ci
JP6159291B2 (ja) 2013-05-23 2017-07-05 富士フイルム株式会社 近赤外線吸収性組成物、これを用いた近赤外線カットフィルタおよびその製造方法、並びに、カメラモジュール
JP2015017244A (ja) 2013-06-12 2015-01-29 富士フイルム株式会社 硬化性組成物、硬化膜、近赤外線カットフィルタ、カメラモジュールおよびカメラモジュールの製造方法
JP6612970B2 (ja) 2016-03-23 2019-11-27 富士フイルム株式会社 積層体、パターン状被めっき層付き基板の製造方法、金属層含有積層体の製造方法、タッチパネルセンサー、及びタッチパネル
CN107382719B (zh) * 2017-06-23 2020-07-14 武汉长盈鑫科技有限公司 一种酸酐改性联苯氧杂环丁烷丙烯酸酯预聚物的制备方法
KR102230622B1 (ko) * 2017-11-24 2021-03-22 주식회사 엘지화학 포토레지스트 조성물 및 이를 이용한 포토레지스트 필름
KR102763590B1 (ko) * 2019-07-10 2025-02-07 가부시끼가이샤 레조낙 감광성 수지 조성물, 감광성 수지 필름, 경화물의 제조 방법, 적층체, 및 전자 부품
JPWO2021117586A1 (fr) * 2019-12-11 2021-06-17
JP7493957B2 (ja) 2020-02-25 2024-06-03 キヤノン株式会社 膜形成装置、膜形成方法、および物品の製造方法
JP7229304B2 (ja) * 2020-08-06 2023-02-27 株式会社タムラ製作所 感光性樹脂組成物及び感光性樹脂組成物を塗布したプリント配線板
JP2022119326A (ja) * 2021-02-04 2022-08-17 旭化成株式会社 複素環化合物
CN114524807B (zh) * 2022-03-03 2023-03-24 波米科技有限公司 一种三氮唑基交联剂及其制备方法、应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0643638A (ja) * 1992-03-17 1994-02-18 Fuji Photo Film Co Ltd 光重合性組成物
JPH1020493A (ja) * 1996-06-28 1998-01-23 Nippon Chibagaigii Kk 光重合性熱硬化性樹脂組成物
JPH10115921A (ja) * 1996-08-20 1998-05-06 Fujitsu Ltd 可視光硬化型ソルダーレジスト組成物及びソルダーレジストパターンの形成方法
JPH10115919A (ja) * 1996-08-02 1998-05-06 E I Du Pont De Nemours & Co プリント回路を被覆する可撓性、難燃性、および光画像形成性組成物
WO2009151012A1 (fr) * 2008-06-09 2009-12-17 旭化成イーマテリアルズ株式会社 Résine polyamide, composition de résine photosensible, procédé de formation de motif en relief durci, et dispositif semi-conducteur
JP2010117452A (ja) * 2008-11-12 2010-05-27 Toyo Ink Mfg Co Ltd 感光性難燃樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0643638A (ja) * 1992-03-17 1994-02-18 Fuji Photo Film Co Ltd 光重合性組成物
JPH1020493A (ja) * 1996-06-28 1998-01-23 Nippon Chibagaigii Kk 光重合性熱硬化性樹脂組成物
JPH10115919A (ja) * 1996-08-02 1998-05-06 E I Du Pont De Nemours & Co プリント回路を被覆する可撓性、難燃性、および光画像形成性組成物
JPH10115921A (ja) * 1996-08-20 1998-05-06 Fujitsu Ltd 可視光硬化型ソルダーレジスト組成物及びソルダーレジストパターンの形成方法
WO2009151012A1 (fr) * 2008-06-09 2009-12-17 旭化成イーマテリアルズ株式会社 Résine polyamide, composition de résine photosensible, procédé de formation de motif en relief durci, et dispositif semi-conducteur
JP2010117452A (ja) * 2008-11-12 2010-05-27 Toyo Ink Mfg Co Ltd 感光性難燃樹脂組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019066510A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 感光性樹脂組成物、並びに、これを用いた感光性エレメント、レジストパターンの形成方法、ソルダーレジスト、層間絶縁膜、層間絶縁膜の形成方法、プリント配線板の製造方法及びプリント配線板
CN111909409A (zh) * 2020-08-11 2020-11-10 河北工业大学 一种含唑环的低聚硅氧烷复合质子交换膜的制备方法
CN111909409B (zh) * 2020-08-11 2022-07-05 河北工业大学 一种含唑环的低聚硅氧烷复合质子交换膜的制备方法
EP4368612A4 (fr) * 2021-06-30 2025-11-05 Samsung Display Co Ltd Nouveau composé pour couche de recouvrement, et dispositif électroluminescent organique le comprenant

Also Published As

Publication number Publication date
TW201235781A (en) 2012-09-01
JP2012194534A (ja) 2012-10-11

Similar Documents

Publication Publication Date Title
WO2012117786A1 (fr) Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé
JP5593266B2 (ja) 感光性組成物、並びに感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2011095705A (ja) 感光性組成物、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン、その形成方法及びプリント基板
US20120183776A1 (en) Curable composition, curable film, curable laminate, method for forming a permanent pattern, and printed substrate
JP7514058B2 (ja) 感光性フィルム積層体およびその硬化物、並びに電子部品
JP2012073601A (ja) 感光性組成物、並びに、感光性フィルム、永久パターン、永久パターン形成方法、及びプリント基板
JP2012073589A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
WO2012029786A1 (fr) Composition photosensible, film photosensible, motif permanent, procédé de formation d'un motif permanent et substrat imprimé
JP2011164570A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2011175254A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2012198361A (ja) 感光性組成物、感光性フィルム、永久パターン形成方法、永久パターン、及びプリント基板
JP2012185459A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2011215392A (ja) 感光性組成物、並びに、感光性積層体、永久パターン形成方法、及びプリント基板
JP2011197310A (ja) 硬化性組成物、並びに、これを用いた硬化性フィルム、硬化性積層体、永久パターン形成方法、及びプリント基板
JP2012078462A (ja) 感光性樹脂組成物、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン、その形成方法及びプリント基板
JP2012078463A (ja) 感光性樹脂組成物、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン、その形成方法及びプリント基板
JP2012073598A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
TW201308001A (zh) 感光性組成物、感光性乾膜、感光性積層體、可撓性配線基板及其製造方法以及永久圖案形成方法
WO2012117763A1 (fr) Composition de dispersion de silice
JP5734773B2 (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2012203355A (ja) 感光性組成物、感光性積層体、永久パターン形成方法、及びプリント基板
JP2012181371A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
JP2012255112A (ja) 組成物、感光性フイルム、感光性積層体、永久パターン形成方法およびプリント基板
JP2013020094A (ja) 感光性組成物、感光性ドライフィルム、感光性積層体、フレキシブル配線板、及び永久パターン形成方法
JP2012211944A (ja) 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12752512

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12752512

Country of ref document: EP

Kind code of ref document: A1