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WO2016140459A1 - Composé époxy à base de phosphore, son procédé de préparation, et composition époxy le contenant - Google Patents

Composé époxy à base de phosphore, son procédé de préparation, et composition époxy le contenant Download PDF

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Publication number
WO2016140459A1
WO2016140459A1 PCT/KR2016/001813 KR2016001813W WO2016140459A1 WO 2016140459 A1 WO2016140459 A1 WO 2016140459A1 KR 2016001813 W KR2016001813 W KR 2016001813W WO 2016140459 A1 WO2016140459 A1 WO 2016140459A1
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Prior art keywords
phosphorus
hydrocarbon group
epoxy compound
formula
weight
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English (en)
Korean (ko)
Inventor
이은용
이지애
정병수
정용수
황재석
이귀항
백미정
정원호
최봉구
최호경
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SHIN-A T&C
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SHIN-A T&C
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Priority to CN201680000419.4A priority Critical patent/CN106132974B/zh
Publication of WO2016140459A1 publication Critical patent/WO2016140459A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the present invention relates to a phosphorus-based epoxy compound and a preparation method thereof, and a phosphorus-based epoxy composition comprising the same. More specifically, the present invention relates to a phosphorus-based epoxy compound having a high phosphorus (P) content, having high heat resistance and low dielectric properties, a method for preparing the same, and an epoxy composition comprising the same.
  • P phosphorus
  • a printed circuit board In general, a printed circuit board (PCB) is used to drive electronic products such as computers, cameras, and televisions.
  • a printed circuit board is a circuit connecting part that attaches a thin thin film such as copper to an insulating base film such as phenol or epoxy, and then patterns it in a desired shape to electrically connect and support the part.
  • Copper Clad Laminate is a raw material of a printed circuit board.
  • the insulating plate obtained by heat-pressing several layers of a sheet in which a compound is bonded to an insulating material such as paper or glass is called a laminate, and a copper foil is attached to one or both sides of the laminate.
  • the requirements for insulating materials used here have to be lead-free in accordance with recent environmental regulations. Accordingly, copper-clad laminates requiring an insulating material having high glass transition temperature characteristics have been increased. The demand for CCL is increasing considerably in recent years.
  • the type of copper clad laminate is a composite made by combining two or more kinds of reinforcement materials, such as a reinforcing material penetrating an epoxy compound into glass fiber, a glass epoxy copper clad laminate made of copper foil, and a paper phenolic copper clad laminate mainly used for manufacturing single-sided PCB.
  • reinforcement materials such as a reinforcing material penetrating an epoxy compound into glass fiber, a glass epoxy copper clad laminate made of copper foil, and a paper phenolic copper clad laminate mainly used for manufacturing single-sided PCB.
  • Epoxy compositions are widely used in electrical and electronic device parts due to their excellent properties, but in many cases flame retardancy is imparted to ensure safety against fire.
  • Flame retardance of epoxy compositions has conventionally used halogenated epoxy compounds such as brominated epoxy.
  • Halogenated epoxy compounds have excellent flame retardancy, but environmental problems have been pointed out by pyrolysis to produce harmful halogen compounds such as hydrogen halides and polybrominated dibenzodioxin and furan. For this reason, phosphorus (P) compounds have been studied as flame retardants to replace bromine-containing flame retardants.
  • the conventional phosphorus (P) -based epoxy has a low crosslinking density, low heat resistance that can be evaluated by the glass transition temperature (Tg), and the secondary structure (secondary alcohol) is added to the epoxy structure, the electrical properties (dielectric constant)
  • Tg glass transition temperature
  • secondary alcohol secondary structure
  • DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide) or DOPO- in a di-functional or multi-functional epoxy to provide a phosphorus-based epoxy compound.
  • Phosphorous compounds such as HQ (10- (2,5-dihydroxyphenyl) -10H-9 -oxa-10-phospha-phenantbrene-10-oxide) were prepared and used by modifying by indirect method, (P) content is limited to the latter 2wt% to ⁇ 3wt%, and there is a problem such that gelation occurs during the reaction when the phosphorus-based compound is introduced in excess for the phosphorus content, and more than 5wt%
  • the present invention provides a novel structure of a phosphorus-based epoxy compound having a high heat resistance, low dielectric properties, a high phosphorus (P) content, a manufacturing method, and an epoxy composition comprising the same.
  • the present invention provides a phosphorus epoxy composition
  • a phosphorus epoxy compound comprising a phosphorus epoxy compound and a curing agent, wherein the phosphorus epoxy compound is a phosphorus epoxy compound represented by the following formula (1).
  • R 1 , R 2 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof Or a hetero element (O, S, or N) in the structure
  • R 3 , R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 Are combinations thereof, and hetero elements (O, S, or N) may be present in the structure
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Or a combination thereof, and hetero elements (O, S, or N) may be present in the structure
  • each R 7 is independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Group or a combination thereof, and heteroatoms (O, S, or N) may be present in the structure
  • the present invention provides a phosphorus-based epoxy composition is a phosphorus-based epoxy compound represented by the formula (2).
  • the present invention provides a phosphorus-based epoxy composition of the content of the phosphorus-based epoxy compound of n is 0 to 99wt% of the phosphorus-based epoxy compound.
  • the present invention provides a phosphorus-based epoxy composition
  • a phosphorus-based epoxy composition comprising the equivalent ratio of the phosphorus-based epoxy compound and the curing agent is 1: 0.6 to 1.5.
  • the curing agent is at least one phosphorus epoxy composition selected from the group consisting of amide curing agent, polyamine curing agent, acid anhydride curing agent, phenol novolak-type curing agent, polycapcaptan curing agent, tertiary amine curing agent or imidazole curing agent To provide.
  • the phosphorus-based epoxy composition further comprises a curing accelerator
  • the curing accelerator is 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • Imidazole compounds containing more than one species Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It provides a phosphorus-based epoxy composition comprising one or more selected from.
  • EPPI Ethyl Triphenyl Phosphonium Iodide
  • the present invention provides a phosphorus-based epoxy composition is 2 to 7% by weight relative to the total weight of the phosphorus-based epoxy composition.
  • the present invention also provides a phosphorus-based epoxy composition, wherein the glass transition temperature (Tg) of the cured product obtained from the phosphorus-based epoxy composition is 150 to 230.
  • Tg glass transition temperature
  • the present invention also provides a phosphorus-based epoxy composition, characterized in that the dielectric constant (D k ) of the cured product obtained from the phosphorus-based epoxy composition is 4.2 or less.
  • the present invention also provides a phosphorus-based epoxy composition, characterized in that the loss factor (D f ) of the cured product obtained from the phosphorus-based epoxy composition is 0.020 or less.
  • the phosphorus-based epoxy compound provides a phosphorus-based epoxy composition which is a phosphorus-based epoxy compound represented by the following formula (5).
  • the present invention provides a phosphorous epoxy compound represented by the formula (1).
  • the present invention provides a phosphorus-based epoxy compound represented by the formula (2) or (5).
  • the present invention provides a phosphorus-based epoxy compound of 6 to 8% by weight relative to the total weight of the phosphorus-based epoxy compound.
  • the present invention provides a phosphorus-based epoxy compound, characterized in that the phosphorus-based hydroxy compound and the epoxy compound is prepared by reacting under an alkali catalyst.
  • the present invention provides a reaction material comprising a phosphorus-based hydroxy compound represented by the following formula (3), at least one epoxy compound selected from the epoxy compounds represented by the following formula (4-1) and the formula (4-2), and a first solvent Preparing a reaction mixture to be added to a reactor to obtain a reaction mixture; And reacting the reaction mixture to obtain an epoxy compound containing phosphorus.
  • R 1 , R 2 are each independently, absent or a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and heteroatoms (O, S, or N in the structure) ) May be present, and R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, Or N), R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, or N) may be present and X is a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).)
  • the reaction mixture preparation step 100 to 180 parts by weight of the phosphorus-based hydroxy compound represented by the formula (3) with respect to 100 parts by weight of the first solvent, to the formula 4-1 and the formula 4-2
  • a method for producing a phosphorus-based epoxy compound characterized in that the epoxy compound is mixed in 210 to 290 parts by weight.
  • the present invention provides a laminate comprising the phosphorous epoxy composition.
  • the present invention is a high phosphorus (P) content phosphorus epoxy compound having a high heat resistance, low dielectric properties, and does not contain halogen, flame-retardant UL-94 grade V-0 can be achieved, further flame retardant in industrial use Since there is no need to use an additive, it is possible to provide a phosphorus-based epoxy compound having excellent reliability, a manufacturing method thereof, and a phosphorus-based epoxy composition including the same without reducing physical, mechanical, and electrical properties.
  • P phosphorus
  • C 1", C 2 ", etc. are as meaning the number of carbon atoms, for example," C 1 -C 10 alkylene group "means an alkylene group having a carbon number of 1-10.
  • the present invention is to provide a phosphorus-based epoxy compound represented by the following formula (1) as a high phosphorus (P) content phosphorus-based epoxy compound (Phosphorus Epoxy Compound) having a high heat resistance, low dielectric properties.
  • P phosphorus
  • R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present.
  • R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure.
  • a hetero element O, S, or N
  • an aliphatic hydrocarbon group of C 1 -C 20 More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a.
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
  • R 7 is each independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 , or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. . Preferably it is hydrogen.
  • R 8 is each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, or a polymer (or prepolymer) having a weight average molecular weight of 500 to 5000, and a hetero element ( O, S, or N) may be present.
  • Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (2).
  • the phosphorus (P) content of the phosphorus epoxy compound according to the present invention is included in 5 to 10% by weight, more preferably 6 to 8% by weight relative to the total weight of the compound. If phosphorus (P) is present in less than 5% by weight, this is a major barrier to achieving flame retardant UL-94 grade V-0 in halogen-free formulations, preventing the use of additional flame retardant additives or phosphorus curing agents in industrial use.
  • the dielectric loss of high heat resistance has a very low characteristic.
  • Phosphorus-based epoxy compounds according to the present invention have a phosphorus (P) content of 5 to 10 wt%, which eliminates the need for the use of additional flame retardant additives or phosphorus curing agents to achieve flame retardant UL-94 grade V-0. ) It can give reliability for mechanical, electrical and electrical properties, and enables free formulation, increasing the possibility of blending compositions that give the required properties using other epoxy resins and hardeners.
  • the structure has high heat resistance, low dielectric properties and low softening point due to high phosphorus (P) content and functional groups in the structure, and is particularly suitable for being used as a material for laminated plates used in printed circuit boards. It is also useful as a material.
  • P phosphorus
  • Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (5).
  • the phosphorus-based epoxy compound according to one embodiment of the present invention is selected from a phosphorus-hydroxy compound represented by the following Formula 3 in the first solvent, and an epoxy compound represented by the following Formula 4-1 and the following Formula 4-2 Phosphorus Epoxy Compound having high heat resistance and low dielectric properties prepared by reacting a reaction mixture in which at least one epoxy compound is dissolved.
  • R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present.
  • hetero elements O, S, or N
  • ethylene (ethylene) group (-CH 2 CH 2- ) More preferably, it does not exist.
  • R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure.
  • a hetero element O, S, or N
  • an aliphatic hydrocarbon group of C 1 -C 20 More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a.
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
  • X may be a kind of good leaving group, for example, a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).
  • a halogen group for example, a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).
  • -OTs O-Tosyl
  • -OMs O-Mesyl
  • it is a chlorine group (-Cl), bromine group (-Br).
  • More specific method for producing a phosphorus-based epoxy compound according to the present invention at least one epoxy compound selected from the epoxy compound represented by the formula (4-1) and the formula (4-2) to the phosphorus-hydroxy compound represented by the formula (3)
  • the epoxy compound is reacted with a hydroxy group (-OH) of the phosphorus hydroxy compound to form a phosphorus epoxy compound represented by Chemical Formula 1.
  • the reaction mixture is 80 to 250 parts by weight of the phosphorus hydroxy compound represented by the formula (3) relative to 100 parts by weight of the first solvent, at least one or more of the epoxy compounds represented by the formula (4-1) and (4-2)
  • the epoxy compound is mixed at 210 to 290 parts by weight. More preferably, the phosphorus hydroxy compound represented by Chemical Formula 3 is mixed in an amount of 100 to 220 parts by weight based on 100 parts by weight of the first solvent, and at least one of the epoxy compounds represented by Chemical Formulas 4-1 and 4-2. It is preferable that the above epoxy compound is mixed at 230 to 270 parts by weight.
  • a method of reacting using an alkali catalyst may be used.
  • the alkali catalyst for example, sodium hydroxide, lithium hydroxide, Alkali metal hydroxides such as potassium hydroxide; Alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; Alkali metal hydrides such as phenoxide, sodium hydride, and lithium hydride of alkali metals; Alkali metal salts of organic acids, such as sodium acetate and sodium stearate, etc. can be used.
  • the first solvent may not be used, but when the solvent is used, the solvent gives an effect of improving the reactivity to reduce the amount of the intermediate product during the reaction, thus 10% in the product yield compared to the case where the solvent is not used.
  • the above results are improved, and excellent results can be obtained also in the color of the final product compound.
  • Aromatic solvent containing benzene, toluene, xylene, etc . Acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) cyclohexanone, acetylacetone, dioxane ( ketone solvents such as dioxane); Formamide, N-methylformamide, N, N-dimethylformamide (N, N-dimethylformamide, DMF), acetamide, N-methylacetamide Amide solvents such as N, N-dimethylacetamide, 2-pyrrolidone, and N-methylpyrrolidone (NMP); Ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, 1,4-dioxane, propylene glycol methyl ether, propylene Glycol ether solvents including
  • IPA isopropyl alcohol
  • the synthesis reaction takes place at a temperature of 30 to 200 ° C. More preferably, the reaction is carried out at a temperature of 45 to 170 ° C. In addition, the synthesis reaction takes place for 3 to 7 hours. More preferably, the reaction is carried out for 4 to 6 hours.
  • the catalyst is added in 50 to 120 parts by weight based on 100 parts by weight of the first solvent.
  • the method may further include a refining process (second purification) using an alkali catalyst.
  • the kind of solvent that can be used as the second solvent is the same as the kind of solvent that can be used as the first solvent described above.
  • methyl isobutyl ketone (MIBK) may be used.
  • the first purification step is a step of removing the remaining monomers by heating to 140 to 160 ° C after washing with water using water, and the second purification step is performed at 140 to 160 ° C after the first purification. After slowly adding the solvent to dissolve, it is a refining process of removing the salt generated during the reaction for 1 hour to 1 hour 30 minutes using an alkali catalyst at 70 to 90 ° C.
  • the first purification step is washed with water using 80 to 250 parts by weight of water based on 100 parts by weight of the first solvent
  • the second purification step is 300 to 700 parts by weight of a second solvent relative to 100 parts by weight of the first solvent
  • dissolving by adding to dissolve 10 to 30 parts by weight of catalyst based on 100 parts by weight of the first solvent.
  • the vacuum degassing is carried out to 140 to 160 °C to remove the remaining water and solvent to obtain a yellow phosphorous epoxy compound flake.
  • the method may further include modifying all or part of the obtained epoxy compound into a polyfunctional isocyanate compound. Upon modification, a compound having m of 1 to 3 may be obtained.
  • a catalyst for the modification reaction, a catalyst can be used, and specifically, a catalyst such as imidazole can be used.
  • the polyfunctional isocyanate compound may be a compound having 2 to 5 isocyanate groups per molecule, and may be an aromatic, aliphatic or alicyclic isocyanate compound, and may be used alone or in combination of two or more thereof. Specifically, hexamethylene diisocyanate, isophorone diisocyanate, methylene dicyclohexyl diisocyanate and cyclohexane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, tolidine diisocyanate, Methylene diphenyl diisocyanate (MDI), a polyisocyanate compound in the form of a polymer (or prepolymer).
  • MDI Methylene diphenyl diisocyanate
  • Polyisocyanates may include, in particular, isomeric mixtures of 4,4'-MDI and 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, which are known in the art and are pure. Bayn Suprasec R MPR and 1306.
  • Carbodiimide and / or urethane modified modifications of the polyisocyanates are also possible and include those known in the art and commercially available, such as Huntsman's Suprasec R 2020.
  • polyisocyanates in the form of polymers (or prepolymers) produced by reacting with polyols having a weight average molecular weight of approximately 500 to 5000.
  • Polymer MDIs can also be used, examples include Huntsman's Suprasec R 2185, Suprasec R 5025 and Suprasec R DNR, and the prepolymer polyisocyanate is Huntsman's. Suprasec R 2054, Suprasec R 2061, and the like.
  • the phosphorus epoxy composition which concerns on another form of this invention contains the phosphorus epoxy compound represented by the said Formula (1), and a hardening
  • Phosphorus-based epoxy composition according to the present invention provides a cured product that is excellent in heat resistance and dielectric properties and meets the required physical properties according to the use.
  • the curing agent is a substance that contributes to the crosslinking reaction upon curing of the epoxy composition, and may be regarded as a curing agent as long as it is a substance that contributes to the crosslinking reaction, even if called a curing accelerator.
  • the equivalent ratio of the phosphorus epoxy compound and the curing agent is 1: 0.6 to 1.5.
  • the curing agent is contained in less than 0.6 equivalents to 1 equivalent of the phosphorus-based epoxy compound may cause uncured or very slow curing rate, and when included in excess of 1.5 equivalents, due to the remaining curing agent due to the excessive amount of the curing agent There are problems with tacky and rheological control.
  • the curing agent may be at least one selected from the group consisting of an amide curing agent, a polyamine curing agent, an acid anhydride curing agent, a phenol novolak-type curing agent, a polymercaptan curing agent, a third amine curing agent or an imidazole curing agent.
  • the phenol novolak-type curing agent is a phenol, such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol AD, biphenol, and / or ⁇ -naphthol, ⁇ -Condensation or co-condensation of naphthols such as naphthol and dihydroxynaphthalene, anthracene terpenes and dicyclopentadienes, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, prionaldehyde, benzaldehyde, salicylicaldehyde and the like under an acidic catalyst Novolak resin etc. obtained by making it cure are included.
  • phenol such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol
  • the phosphorus-based epoxy composition further comprises a curing accelerator, suitable curing accelerators to be used 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • a curing accelerator suitable curing accelerators to be used 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • Imidazole compounds containing more than one species Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It is good to use including 1 or more types selected from.
  • EPPI Ethyl Triphenyl Phosphonium Iodide
  • the phosphorus epoxy composition may further include an inorganic filler, and suitable inorganic fillers to be used include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxides.
  • suitable inorganic fillers to be used include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxides.
  • Phosphorus (P) content relative to the total weight of the phosphorus-based epoxy composition according to an embodiment of the present invention is 2 to 7 wt%. If it is less than 2wt% there is a problem that the flame retardant properties are not reduced or not implemented at all, if it is more than 7wt% there is a problem that the heat resistance is lowered and the cured product is brittle (brittle) to collapse.
  • the phosphorus-based epoxy composition according to the present invention As a result of evaluating the properties of the cured product by the phosphorus-based epoxy composition according to the present invention, it has excellent heat resistance and has a low dielectric property, and thus, an encapsulant, a molding material, a mold used in the compound composition for manufacturing a copper clad laminated board used in an electronic circuit board or an electronic part. It is useful as an ash, an adhesive agent, a film material, a material for electrically insulating paints, etc.
  • a prepreg for producing a laminate containing 30 to 70% by weight of the phosphorus-based epoxy composition of the present invention and 30 to 70% by weight of glass fibers is prepared, which is then used as one or more laminates, and copper foil located outside of the laminate.
  • the outer layer may be integrated by heat and pressure to manufacture a laminate for a printed circuit board.
  • 750 parts by weight of (2,5-Dihydroxyphenyl) diphenyl phosphine oxide, 750 parts by weight of Epichlorohydrin and 300 parts by weight of Isopropyl Alcohol (IPA) were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser and purged with nitrogen for 30 minutes.
  • IPA Isopropyl Alcohol
  • Example 1 900 parts by weight of the flakes obtained in Example 1 were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, and the reaction temperature was raised to 120 ° C.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 1, 50 parts by weight of a phenol novolak-type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 2, 45 parts by weight of a phenol novolak type curing agent, and 3 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 3, 40 parts by weight of a phenol novolak type curing agent, and 1 part by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 4, 30 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Comparative Example 1, 50 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • Phosphorus content of the phosphorus-based epoxy compounds of Examples 1 to 3 is 7 wt%
  • phosphorus content of the modified phosphorus-based epoxy compound of Example 4 is 6.57 wt%
  • the phosphorus content of the phosphorus-based epoxy composition of Examples 5 to 8 is 5 wt%, it can be seen that it has a high phosphorus (P) content compared to Comparative Example 2.
  • Tg, Td, Dk, and Df were measured for the phosphorus-based epoxy cured product prepared in Examples 9 to 12 and Comparative Example 3, and the results are shown in Table 2 below.
  • Tg was used by differential scanning calorimetry (DSC, TA instrument), and dielectric constant (Dk) and loss factor (Ds) were Agilent E4991A RF Impedance / by the JIS-C-6481 method. Measurement was made using a material analyzer.
  • glass transition temperature (Tg) is 170 to 180 °C excellent thermal stability It can be seen that.

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Abstract

La présente invention concerne : une nouvelle structure d'un composé époxy à base de phosphore ayant une teneur élevée en phosphore (P) et ayant une résistance à la chaleur élevée et des caractéristiques diélectriques faibles ; un procédé de préparation d'un composé époxy à base de phosphore ayant une teneur élevée en phosphore et ayant une résistance à la chaleur élevée et des caractéristiques diélectriques faibles par le biais d'un procédé de préparation dans lequel un groupe époxy est introduit dans un composé hydroxy à base de phosphore à l'aide d'un composé époxy ; et une composition époxy à base de phosphore contenant celui-ci.
PCT/KR2016/001813 2015-03-05 2016-02-24 Composé époxy à base de phosphore, son procédé de préparation, et composition époxy le contenant Ceased WO2016140459A1 (fr)

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CN112409572A (zh) * 2019-08-22 2021-02-26 苏州巨峰新材料科技有限公司 含磷阻燃低热膨胀系数环氧树脂及其制备方法和所涉及的中间产物以及应用
KR102600976B1 (ko) 2020-10-14 2023-11-10 주식회사 신아티앤씨 인계 화합물
KR102835565B1 (ko) 2023-11-10 2025-07-18 주식회사 신아티앤씨 실세스퀴옥산계 수지 및 이를 포함하는 조성물
KR102722932B1 (ko) 2023-11-14 2024-10-28 주식회사 신아티앤씨 반응형 인계 올리고머 및 인계 난연성 조성물

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