Classifications

• • 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
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
• • 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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a modified phenoxy resin having excellent dielectric properties and storage stability. Further, the present invention relates to a resin composition containing the modified phenoxy resin and a curing agent, which has excellent storage stability, a cured product having excellent dielectric properties, and a laminated board for an electric / electronic circuit made of the resin composition.
• Epoxy resin is widely used in fields such as paints, civil engineering, adhesives, and electrical materials because it has excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, and electrical characteristics. Then, the film-forming property is imparted by increasing the molecular weight by various methods.
• the high molecular weight epoxy resin is called a phenoxy resin.
• bisphenol A type phenoxy resin is mainly used as a base resin for paint varnish, a base resin for film molding, and added to epoxy resin varnish to adjust fluidity, improve toughness and adhesiveness when made into a cured product. Used for improvement purposes. Further, those having a phosphorus atom or a bromine atom in the skeleton are used as a flame retardant to be blended in an epoxy resin composition or a thermoplastic resin.
• Phenoxy resin which is used as an electrical material such as laminated plates for electrical and electronic circuits, is required to have excellent dielectric properties in order to suppress deterioration of insulating properties and occurrence of defects in electrical and electronic circuits.
• phenoxy resin When phenoxy resin is used as an electric material such as a laminated board for electric / electronic circuits, it is generally used as a mixture with multiple materials such as an epoxy resin and a curing agent. However, it is clear that the phenoxy resin produced by using amines, ammonium salts, and alkaline compounds as catalysts as described in Non-Patent Document 1 below has insufficient storage stability when mixed with other materials. became.
• An object of the present invention is to provide a phenoxy resin having excellent dielectric properties and storage stability. Further, the resin composition containing the same is cured to provide a cured product having excellent dielectric properties.
• the present inventor has diligently studied a phenoxy resin and found that a phenoxy resin having a specific structure is excellent in dielectric properties and storage stability, and further obtained a resin composition containing the same. We have found that the cured product is excellent in dielectric properties, and completed the present invention.
• the present invention is a modified phenoxy resin represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000.
• X is a divalent group.
• Y is an acyl group or a hydrogen atom having 2 to 20 carbon atoms.
• Z is an acyl group or a hydrogen atom having 2 to 20 carbon atoms, and 5 mol% or more is the above acyl group.
• n is an average value of the number of repetitions, which is 15 or more and 500 or less.
• the present invention is a resin composition containing the above-mentioned modified phenoxy resin and a curing agent.
• the resin composition may contain 0.1 to 100 parts by mass of the curing agent as a solid content with respect to 100 parts by mass of the solid content of the modified phenoxy resin.
• the resin composition contains the above-mentioned modified phenoxy resin, an epoxy resin, and a curing agent, and the mass ratio of the solid content of the modified phenoxy resin and the epoxy resin can be 99/1 to 1/99.
• This resin composition may contain 0.1 to 100 parts by mass of the curing agent as a solid content with respect to a total of 100 parts by mass of the solid content of the modified phenoxy resin and the epoxy resin.
• Examples of the curing agent to be blended in the above resin composition include acrylic acid ester resin, melamine resin, urea resin, phenol resin, acid anhydride compound, amine compound, imidazole compound, amide compound, and cationic polymerization initiator. There is at least one selected from the group consisting of organic phosphines, polyisocyanate compounds, blocked isocyanate compounds, and active ester-based curing agents.
• the present invention is a cured product obtained by curing the above resin composition. Further, the present invention is a laminated board for an electric / electronic circuit using the above resin composition.
• the present invention is a method for producing the modified phenoxy resin, which comprises reacting a bifunctional epoxy resin represented by the following formula (2) with a compound represented by the following formula (3).
• X is a divalent group.
• Y 1 is an acyl group having 2 to 20 carbon atoms.
• G is a glycidyl group.
• m is the average value of the number of repetitions, and is 0 or more and 6 or less.
• 1.0 mol or more and 2.0 mol or less of the acid anhydride represented by the following formula (5) is used with respect to 1 mol of the alcoholic hydroxyl group equivalent of the phenoxy resin represented by the following formula (4).
• L is independently a glycidyl group or a hydrogen atom
• X is a divalent group
• Y 1 is an acyl group having 2 to 20 carbon atoms.
• n is an average value of the number of repetitions, which is 15 or more and 500 or less.
• a modified phenoxy resin having excellent dielectric properties and storage stability. Further, a resin composition using this modified phenoxy resin can provide a cured product having excellent dielectric properties.
• the modified phenoxy resin of the present invention is represented by the above formula (1) and has a weight average molecular weight (Mw) of 10,000 to 200,000.
• Mw weight average molecular weight
• the Mw is preferably 15,000 to 160,000, more preferably 20,000 to 120,000, still more preferably 20,000 to 120,000. Mw can be measured by the gel permeation chromatography method (GPC method) described in Examples.
• the terminal group Y is an acyl group or a hydrogen atom, and further has a structure in which a part or all of hydrogen atoms in the hydroxyl group of a normal phenoxy resin is substituted with an acyl group.
• modified phenoxy resin of the present invention can be advantageously obtained by the production method of the present invention.
• modified phenoxy resin obtained by the production method of the present invention may be referred to as "modified phenoxy resin of the present invention”.
• X represents a divalent group.
• X may have a divalent hydrocarbon group or a group such as -O-, -CO-, -S-, -COO-, -SO-, -SO 2- in the hydrocarbon chain. It is a hydrocarbon group.
• the divalent group include an aromatic skeleton representing a residual skeleton obtained by removing two hydroxyl groups from an aromatic diol compound, an aliphatic skeleton representing a residual skeleton obtained by removing two hydroxyl groups from an aliphatic diol compound, and a fat.
• Examples thereof include an alicyclic skeleton representing a residual skeleton obtained by removing two hydroxyl groups from a ring diol compound. These groups are derived from the residual skeleton obtained by removing the two glycidyl groups from the bifunctional epoxy resin, the residual skeleton obtained by removing the two ester structures from the diester compound, and the residual skeleton obtained by removing the two aquatic groups from the bifunctional phenol compound. ..
• the aromatic skeleton having a structure in which two hydroxyl groups are removed from the aromatic diol compound is bisphenol A, bisphenol acetophenone, bisphenol AF, bisphenol AD, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol. G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol trimethylcyclohexane, bisphenolcyclohexane and other unsubstituted or bisphenol type which may have an alkyl group having 1 to 10 carbon atoms as a substituent, hydroquinone, and the like.
• Substituted benzene type such as resorcin, catechol or the like or optionally having an alkyl group having 1 to 10 carbon atoms as a substituent, or an unsubstituted or alkyl group having 1 to 10 carbon atoms is substituted.
• Naphthalene type such as dihydroxynaphthalene which may have as a group
• biphenyl type such as dihydroxybiphenyl which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent
• bisphenol fluorene such as dihydroxynaphthalene which may have as a group
• bisphenol fluorene such as dihydroxynaphthalene which may have as a group
• bisphenol fluorene such as dihydroxynaphthalene which may have as a group
• bisphenol fluorene such as dihydroxynaphthalene which may have as a group
• bisphenol fluorene such as dihydroxynaphthalene which
• bisphenol fluorenes such as bisphenol fluorene or bisphenol fluorene which may have an alkyl group having 1 to 10 carbon atoms as a substituent, fluorene type such as bisnaphthol fluorene, and 10- (2,5-dihydroxy).
• aliphatic skeleton examples include alkylene glycol skeletons such as ethylene glycol, propylene glycol and butylene glycol.
• alicyclic skeleton examples include hydrogenated bisphenol skeletons such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol acetophenone.
• Y is independently an acyl group of 2 to 20 or a hydrogen atom.
• Y is an acyl group
• an ester group is given to the terminal
• Y is a hydrogen atom
• a hydroxyl group is given to the terminal.
• the acyl group is represented by R-CO-, and R is a hydrocarbon group having 1 to 19 carbon atoms.
• the proportion of these terminal groups may be controlled according to the application.
• the hydrocarbon group having 1 to 19 carbon atoms an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms is preferable.
• the alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a sec-butyl group.
• n-butyl group n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n- Examples thereof include an octyl group, a cyclooctyl group, an n-nonyl group, a 3,3,5-trimethylcyclohexyl group, an n-decyl group, a cyclodecyl group, an n-undecyl group, an n-dodecyl group and a cyclododecyl group.
• aryl group having 6 to 12 carbon atoms examples include a phenyl group, a tolyl group, an ethylphenyl group, a xsilyl group, an n-propylphenyl group, an isopropylphenyl group, a mesityl group, a naphthyl group, a methylnaphthyl group and the like.
• Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a phenethyl group, a 2-phenylisopropyl group, a naphthylmethyl group and the like.
• a acyl group when Y is an acyl group an acyl group having a hydrocarbon group having 1 to 7 carbon atoms is more preferable, and an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group, and a methylbenzoyl group are preferable. More preferably, an acetyl group and a benzoyl group are particularly preferable.
• the acetyl group is understood to be an acyl group having 2 carbon atoms.
• Z is an acyl group having 2 to 20 carbon atoms (hereinafter, may be simply referred to as an “acyl group”) or a hydrogen atom. More than 5 mol% of Z is an acyl group and the rest is a hydrogen atom.
• the content rate (mol%) of the acyl group in the total Z in the formula (1) is also referred to as the acylation rate.
• the acylation rate is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more. Further, the upper limit is preferably 100%, but it may be substantially 95%.
• the acyl group having 2 to 20 carbon atoms is the same as that exemplified in Y above, and the preferred acyl group is also the same.
• the modified phenoxy resin of the present invention does not contain a secondary hydroxyl group, and the dielectric properties can be further improved. It can also be expected to improve solubility and moisture resistance.
• the modified phenoxy of the present invention is used. It is also possible to intentionally allow an appropriate amount of secondary hydroxyl groups to be present in the resin.
• n is the number of repetitions and is an average value.
• the range of the value is 15 or more and 500 or less. From the viewpoint of moldability and handleability, it is preferably 17 or more and 400 or less, and more preferably 20 or more and 300 or less.
• the n number can be calculated from the number average molecular weight (Mn) obtained by the GPC method.
• the modified phenoxy resin of the present invention is obtained by acylating a part or all of the secondary hydroxyl group or the terminal hydroxyl group of a normal phenoxy resin, and can be obtained by various methods.
• a preferable manufacturing method for example, there are the following manufacturing methods.
• a manufacturing method (B) The phenoxy resin represented by the above formula (4) and an acid component (acylating agent) such as an acid anhydride of an organic acid, a halide of an organic acid, and an esterified product of an organic acid, preferably an organic acid.
• a production method for reacting with an acid anhydride hereinafter, it may be referred to as a manufacturing method (B).
• the modified phenoxy resin obtained by the production methods (A) and (B) is the modified phenoxy resin of the present invention.
• the production method (A) is a method of reacting a bifunctional epoxy resin represented by the formula (2) with a diester compound represented by the formula (3).
• G is a glycidyl group
• m is the number of repetitions
• the average value thereof is 0 or more and 6 or less, preferably 0 or more and 3 or less.
• Y 1 is an acyl group having 2 to 20 carbon atoms.
• the X in the equations (2) and (3) is selected to give the X in the equation (1).
• the bifunctional epoxy resin used in the production method (A) of the present invention is an epoxy resin represented by the above formula (2), and for example, a bifunctional phenol compound represented by HO-X-OH and epihalohydrin.
• Epoxy resin obtained by reacting in the presence of an alkali metal compound and the like can be mentioned.
• X is the same as X in the above formula (1).
• Examples of epichlorohydrin include epichlorohydrin and epibromohydrin.
• Examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride, and the like.
• Examples thereof include alkali metal alkoxides such as sodium methoxydo and sodium ethoxydo, alkali metal salts of organic acids such as sodium acetate and sodium stearate, alkali metal phenoxide, sodium hydride, lithium hydride and the like.
• the reaction between the bifunctional phenol compound and epihalohydrin to obtain the raw material epoxy resin is 0.80 to 1.20 times mol, preferably 0.85 to 1.05 times the functional group in the bifunctional phenol compound.
• a molar alkali metal compound is used. If it is less than this, the amount of residual hydrolyzable chlorine increases, which is not preferable.
• the alkali metal compound it is used in an aqueous solution, an alcohol solution or a solid state.
• an excess amount of epihalohydrin is used for the bifunctional phenol compound.
• 1.5 to 15 times mol of epihalohydrin is used with respect to 1 mol of the functional group in the bifunctional phenol compound, preferably 2 to 10 times mol, more preferably 5 to 8 times mol. If it is more than this, the production efficiency will decrease, and if it is less than this, the amount of high molecular weight epoxy resin produced will increase, making it unsuitable as a raw material for phenoxy resin.
• the epoxidation reaction is usually carried out at a temperature of 120 ° C. or lower. During the reaction, if the temperature is high, the amount of so-called persistently hydrolyzable chlorine increases, making it difficult to achieve high purity.
• the temperature is preferably 100 ° C. or lower, more preferably 85 ° C. or lower.
• m is usually larger than 0.
• the epoxy resin produced by a known method is highly purified by a method such as distillation or crystallization, or the above bifunctional phenol compound is allylated and then the olefin moiety is oxidized. There is a method of epoxidation with.
• the diester compound used in the production method (A) of the present invention is, for example, an acylation of the above bifunctional phenol compound by a condensation reaction with an acid anhydride of an organic acid, a halide of an organic acid, or an organic acid. can get.
• the modified phenoxy resin of the present invention does not contain a secondary hydroxyl group, and the dielectric properties and moisture resistance can be further improved. Further, for example, when finely adjusting the adhesiveness to a metal, by using an epoxy resin having an appropriate number of m, the modified phenoxy resin can be used as long as it does not significantly affect other physical properties such as moisture resistance. It is also possible to dare to have an appropriate amount of secondary hydroxyl groups.
• the amount of the bifunctional epoxy resin and the diester compound used is preferably 1.0 to 1.2 equivalents, more preferably 1.02 to 1.15 equivalents, relative to 1 equivalent of the epoxy group. This equivalent ratio is preferable because it facilitates the progress of molecular weight increase in the state of having an acyl group at the end of the molecule. It is also possible to replace a part of the diester compound with the above-mentioned bifunctional phenol compound. As a result, the physical properties can be finely adjusted by intentionally allowing an appropriate amount of secondary hydroxyl groups to be present in the modified phenoxy resin. In the production method (A), Mw is increased to form a modified phenoxy resin, and at the same time, a part of the OH groups of the phenoxy resin is esterified.
• a catalyst may be used, and the catalyst may be any compound having a catalytic ability to promote the reaction between the epoxy group and the ester group.
• the catalyst may be any compound having a catalytic ability to promote the reaction between the epoxy group and the ester group.
• tertiary amines, cyclic amines, imidazole compounds, organic phosphorus compounds, quaternary ammonium salts and the like can be mentioned. Further, these catalysts may be used alone or in combination of two or more.
• tertiary amine examples include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and the like. , Not limited to these.
• cyclic amines examples include 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo [ 4,3,0] Nonen-5 (DBN), N-methylmorpholin, pyridine, N, N-dimethylaminopyridine (DMAP) and the like, but are not limited thereto.
• imidazole compound examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2.
• organophosphorus compound examples include tri-n-propylphosphine, tri-n-butylphosphine, diphenylmethylphosphine, triphenylphosphine, tris (p-tril) phosphine, tricyclohexinephosphine, tri (t-butyl) phosphine, and the like.
• Phosphines such as tris (p-methoxyphenyl) phosphine, paramethylphosphine, 1,2-bis (dimethylphosphino) ethane, 1,4-bis (diphenylphosphine) butane, tetramethylphosphonium bromide, tetramethylphosphonium.
• Iodide tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium Examples thereof include, but are not limited to, phosphonium salts such as iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, and triphenylbenzylphosphonium bromide.
• phosphonium salts such as iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide,
• Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, and tetra.
• Examples thereof include propylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride and the like. However, it is not limited to these.
• the amount of the catalyst used is usually 0.001 to 1% by mass in the reaction solid content, but when these compounds are used as a catalyst, these catalysts remain as a residue in the obtained phenoxy resin, and the printed wiring is printed. There is a risk of deteriorating the insulation properties of the board and shortening the pot life of the composition. Therefore, the nitrogen content derived from the catalyst in the phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.
• the catalyst-derived phosphorus content in the phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass.
• a solvent for reaction may be used, and the solvent may be any solvent as long as it dissolves the phenoxy resin.
• the solvent may be any solvent as long as it dissolves the phenoxy resin. Examples thereof include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, ester solvents and the like. Further, these solvents may be used alone or in combination of two or more.
• aromatic solvent examples include benzene, toluene, xylene and the like.
• ketone solvent examples include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone and the like.
• amide solvent examples include formamide, N-methylformamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Will be.
• glycol ether-based solvent examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n.
• ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol mono-n.
• -Diethylene glycol monoalkyl ethers such as butyl ether
• propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol.
• Ethylene glycol dialkyl ethers such as dibutyl ether, polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether, and propylene glycol dimethyl ether.
• Propylene glycol dialkyl ethers such as propylene glycol diethyl ether and propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol.
• Polypropylene glycol dialkyl ethers such as dibutyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl.
• Polyethylene Glycol Monoalkyl Ether Acetates such as Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate, Triethylene Glycol Monomethyl Ether Acetate, Triethylene Glycol Monoethyl Ether Acetate, Triethylene Glycol Monobutyl Ether Acetate, etc.
• Examples thereof include setates and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate.
• ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone and the like.
• solvents examples include dioxane, dimethylsulfoxide, sulfolane, and the like.
• the solid content concentration at the time of reaction is preferably 35 to 95% by mass. It is more preferably 50 to 90% by mass, still more preferably 70 to 90% by mass. Further, when a highly viscous product is generated during the reaction, an additional solvent can be added to continue the reaction. After completion of the reaction, the solvent can be removed or further added, if necessary.
• the reaction temperature should be within the temperature range where the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and the target molecular weight may not be achieved. Therefore, the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C.
• the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low boiling point solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be secured by carrying out the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used by the heat of reaction, the indirect cooling method, or a combination thereof.
• the manufacturing method (B) of the present invention will be described.
• 0.05 mol or more of the acid anhydride represented by the formula (5) is added to 1 mol of the phenoxy resin represented by the formula (4) and the alcoholic hydroxyl group equivalent of the phenoxy resin.
• This phenoxy resin can be obtained by a conventionally known method.
• a method for producing a bifunctional phenol compound by reacting it with epihalohydrin in the presence of an alkali metal compound (hereinafter referred to as “one-step method”), or a bifunctional epoxy resin and a bifunctional phenol compound in the presence of a catalyst. (Hereinafter, referred to as “two-step method”) can be mentioned.
• the phenoxy resin may be obtained by any production method, but it is generally preferable to use the two-step method because the two-step method is easier to obtain the phenoxy resin than the one-step method.
• the molar ratio of epihalohydrin and the bifunctional phenol compound charged in the one-step method is appropriately adjusted, and the charged molar ratio of the bifunctional epoxy resin and the bifunctional phenol compound is appropriately adjusted in the two-step method. This makes it possible to manufacture a product in the desired range.
• Examples of the bifunctional phenol compound used in the production of the one-step method and the two-step method include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol acetophenone, bisphenol fluorene, dihydroxybiphenyl ether and dihydroxy.
• Examples thereof include bisphenols such as biphenylthioether, biphenols such as 4,4'-biphenol and 2,4'-biphenol, 1,1-bi-2-naphthol, catechol, resorcin, hydroquinone and dihydroxynaphthalene.
• a plurality of these bifunctional phenol compounds may be used in combination.
• the one-step method In the case of the one-step method, 0.98 to 1.0 mol of epihalohydrin, preferably 0.985 to 0.997 mol, more preferably 0.99 to 0.995 mol, per 1 mol of the bifunctional phenol compound.
• a phenoxy resin can be obtained by reacting in a non-reactive solvent in the presence of an alkali metal compound so that epihalohydrin is consumed and the weight average molecular weight is 10,000 or more. After the reaction is completed, it is necessary to remove the by-produced salt by filtration or washing with water.
• the alkali metal compound include the same alkali metal compounds used in the production of the bifunctional epoxy resin represented by the above formula (2) used in the production method (A) of the present invention.
• the reaction temperature is usually preferably 20 to 200 ° C., more preferably 30 to 170 ° C., still more preferably 40 to 150 ° C., and particularly preferably 50 to 100 ° C. in the case of a reaction under normal pressure.
• 20 to 100 ° C. is preferable, 30 to 90 ° C. is more preferable, and 35 to 80 ° C. is further preferable. If the reaction temperature is within this range, side reactions are unlikely to occur and the reaction is likely to proceed.
• the reaction pressure is usually normal pressure. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used, the indirect cooling method, or a combination thereof by the heat of reaction.
• alcohols such as ethanol, isopropyl alcohol, and butyl alcohol can be used in addition to the reaction solvent exemplified in the production method (A) of the present invention. Only one type may be used, or two or more types may be used in combination.
• the two-step method As the bifunctional epoxy resin used as the raw material epoxy resin of the two-step method, the same bifunctional epoxy resin represented by the above formula (2) used in the production method (A) of the present invention is used.
• Examples of the bifunctional epoxy resin used as the raw material of the two-step method include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, diphenyl sulfide type epoxy resin, and diphenyl ether type epoxy resin.
• Examples thereof include bisphenol type epoxy resin, biphenol type epoxy resin, diphenyldicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, naphthalene type epoxy resin, benzene type epoxy resin, aliphatic cyclic epoxy resin and the like.
• These epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. A plurality of types of these epoxy resins may be used in combination.
• the amount of the bifunctional epoxy resin used is preferably 0.85 to 1.00 mol, more preferably 0.90 to 1.00 mol, and 0.95 to 1. 00 mol is more preferable, and 0.97 to 0.99 mol is particularly preferable.
• the blending amount of the bifunctional epoxy resin is within this range, the molecular weight of the obtained phenoxy resin is sufficiently extended, which is preferable.
• any compound can be used as long as it can use a catalyst and has a catalytic ability to promote the reaction between the epoxy group and the phenolic hydroxyl group.
• the same as the catalyst exemplified in the production method (A) of the present invention can be mentioned.
• an alkali metal compound used in the production of the bifunctional epoxy resin represented by the above formula (2) can also be used.
• These catalysts may be used alone or in combination of two or more. Further, the amount used is the same as the amount used exemplified in the production method (A) of the present invention.
• a solvent may be used, and the solvent may be any solvent as long as it dissolves a phenoxy resin and does not adversely affect the reaction.
• the same solvent as that exemplified in the production method (A) of the present invention is exemplified. These solvents may be used alone or in combination of two or more.
• the amount of the solvent to be used can be appropriately selected according to the reaction conditions, but for example, in the case of the two-step method, the solid content concentration is preferably 35 to 95% by mass. If a highly viscous product is produced during the reaction, a solvent can be added during the reaction to continue the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or can be further added.
• the reaction temperature should be within the temperature range where the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and the target molecular weight may not be achieved. Therefore, the reaction temperature is preferably 50 to 230 ° C, more preferably 100 to 210 ° C, and even more preferably 120 to 200 ° C.
• the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low boiling point solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be secured by carrying out the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used by the heat of reaction, the indirect cooling method, or a combination thereof.
• the modified phenoxy resin of the present invention can be obtained by acylating the hydroxyl group in the phenoxy resin represented by the above formula (4) thus obtained. Acylation may be performed not only by direct esterification but also by a method such as transesterification.
• Examples of the acid component used for the acylation include acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, octanoic acid, capric acid, lauric acid, stearic acid, oleic acid, benzoic acid, and t-butylbenzoic acid.
• Organic acids such as hexahydrobenzoic acid, phenoxyacetic acid, acrylic acid, and methacrylic acid, acid anhydrides of organic acids, halides of organic acids, esterified products of organic acids, and the like can be used. It is preferably an acid anhydride represented by the formula (5).
• Examples of the acid anhydride of the organic acid include acetic anhydride, benzoic acid anhydride, phenoxyacetic anhydride and the like.
• Examples of the esterified product of the organic acid include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, ethyl benzoate and the like.
• Examples of the halide of the organic acid include acetic acid chloride, benzoic acid chloride, phenoxyacetic acid chloride and the like.
• Examples of the compound used for esterification include halides of organic acids such as chloride, benzoic acid chloride and phenoxyacetic acid chloride, acid halides such as anhydrous acetic acid, benzoic acid anhydride and phenoxyacetic acid anhydride, and acid anhydride of organic acids.
• Acid anhydrides such as anhydrous acetic acid and benzoic acid anhydride are more preferable in the sense that they are preferable, do not require washing with water after esterification, and avoid mixing of halogens that are disliked in electrical material applications.
• the charging ratio when reacting the phenoxy resin with acid components such as the organic acid used for esterifying the hydroxyl group of the phenoxy resin, the acid anhydride of the organic acid, the halide of the organic acid, and the esterified product of the organic acid is determined.
• the charging ratio may be the same as the desired esterification ratio. If the reactivity is low, the above acid component is excessively charged with respect to the hydroxyl group, reacted to the desired esterification rate, and then the unreacted acid component is removed. You may.
• esterifications such as acid catalysts such as p-toluenesulfonic acid and phosphoric acid and metal catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyl tin oxide, dioctyl tin oxide and zinc chloride. It can be carried out while dehydrating using a catalyst. Usually, it is preferably carried out at 100 to 250 ° C. in a nitrogen atmosphere, and more preferably 130 to 230 ° C.
• a method of filtering the salt after neutralization using a basic compound, or washing with water after neutralization using a basic compound Any of the method, the method of washing with water without neutralization, and the method of removing by distillation, adsorption, or the like may be used, or may be used in combination.
• removing an acid having a boiling point lower than that of the reaction solvent it is preferable to remove the acid by distillation.
• the phenoxy resin When the phenoxy resin is esterified by ester exchange, it is usually organic such as dibutyltin oxide, dioctyltin oxide, stanoxane catalyst, tetraisopropyl titanate, tetrabutyltitanate, lead acetate, zinc acetate, antimony trioxide, etc. under a nitrogen atmosphere. It is desirable to carry out the process while dealcoholizing using a known esterification catalyst such as a metal catalyst, an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid or sulfonic acid, or a basic catalyst such as lithium hydroxide or sodium hydroxide.
• a known esterification catalyst such as a metal catalyst, an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid or sulfonic acid, or a basic catalyst such as lithium hydroxide or sodium hydroxide.
• a solvent for reaction may be used, and the solvent may be any solvent as long as it dissolves a phenoxy resin.
• the solvent exemplified in the production method (A) of the present invention can be mentioned. These solvents may be the same as those used in the preparation of the phenoxy resin, or may be different. Further, only one type may be used, or two or more types may be used in combination.
• the resin composition of the present invention is a resin composition containing at least the modified phenoxy resin of the present invention and a curing agent, but preferably contains an epoxy resin.
• various additives such as an inorganic filler, a coupling agent, and an antioxidant can be appropriately added to the resin composition of the present invention, if necessary.
• the resin composition of the present invention provides a cured product that sufficiently satisfies various physical properties required for various uses.
• a curing agent can be blended with the modified phenoxy resin of the present invention to prepare a resin composition.
• the curing agent refers to a substance that contributes to a cross-linking reaction and / or a chain length extension reaction with a modified phenoxy resin.
• a curing accelerator even if it is usually called a "curing accelerator", if it is a substance that contributes to the cross-linking reaction and / or the chain length extension reaction of the modified phenoxy resin, it is regarded as a curing agent.
• the content of the curing agent in the resin composition of the present invention is preferably 0.1 to 100 parts by mass in terms of solid content with respect to 100 parts by mass in solid content of the modified phenoxy resin. Further, it is more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less.
• the weight ratio of the solid content of the modified phenoxy resin and the epoxy resin is 99/1 to 1/99.
• the "solid content” means a component excluding the solvent, and includes not only solid modified phenoxy resin and epoxy resin but also semi-solid and viscous liquid material.
• the "resin component” means the total of the modified phenoxy resin of the present invention and the epoxy resin described later.
• Examples of the curing agent used in the resin composition of the present invention include those having two or more functional groups that react with the residual hydroxyl groups of the modified phenoxy resin.
• an acid anhydride-based curing agent, an isocyanate-based curing agent, a blocked isocyanate-based curing agent, and the like can be mentioned.
• These curable agents may be used alone or in combination of two or more.
• the resin composition of the present invention can contain an epoxy resin and a curing agent.
• the epoxy resin preferably has two or more epoxy groups in the molecule, and more preferably an epoxy resin having three or more epoxy groups. Examples thereof include polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, two or more kinds of epoxy resins of the same system may be used in combination, or epoxy resins of different systems may be used in combination.
• polyglycidyl ether compound examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, bisphenol fluorene type epoxy resin, and diphenyl sulfide type epoxy resin.
• Diphenyl ether type epoxy resin Diphenyl ether type epoxy resin, naphthalene type epoxy resin, hydroquinone type epoxy resin, resorsinol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, styrated phenol novolak type epoxy resin, bisphenol novolak type Epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, biphenyl aralkyl phenol type epoxy resin, biphenyl type epoxy resin, Various epoxy resins such as triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, and aliphatic cyclic epoxy resin can be used.
• polyglycidylamine compound examples include a diaminodiphenylmethane type epoxy resin, a metaxylene diamine type epoxy resin, a 1,3-bisaminomethylcyclohexane type epoxy resin, an isocyanurate type epoxy resin, an aniline type epoxy resin, and a hydridein type epoxy resin.
• Aminophenol type epoxy resin and the like can be mentioned.
• polyglycidyl ester compound examples include a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, and a trimellitic acid type epoxy resin.
• alicyclic epoxy compound examples include aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).
• modified epoxy resins include, for example, urethane-modified epoxy resin, oxazolidone ring-containing epoxy resin, epoxy-modified polybutadiene rubber derivative, carboxyl group-terminated butadiene nitrile rubber (CTBN) -modified epoxy resin, and polyvinyl allene polypeptide (for example, divinylbenzene dioxide). , Trivinylnaphthalene trioxide, etc.), phenoxy resin, etc.
• CBN butadiene nitrile rubber
• the curing agent used in the resin composition of the present invention containing an epoxy resin is not particularly limited, and all generally known as epoxy resin curing agents can be used.
• the curing agent other than the above include a phenol-based curing agent, an amide-based curing agent, an imidazole-based compound, an active ester-based curing agent, an amine-based curing agent, a hydrazide-based curing agent, and the like.
• Phenol-based curing agents, active ester-based curing agents, amide-based curing agents, imidazole-based compounds and the like are preferable from the viewpoint of enhancing heat resistance, and phenol-based curing agents and activities are preferable from the viewpoint of enhancing water resistance.
• ester-based curing agents include ester-based curing agents. These curable agents may be used alone or in combination of two or more.
• phenolic curing agent examples include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, and 1,3-bis ( 4-Hyhydroxyphenoxy) benzene, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10- (2,5-Dihydroxyphenyl) -10H-9-oxa-10-phosphafenanslen-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak , Xylenol novolak, poly-p-hydroxystyrene, hydroquinone, phenol
• amide-based curing agent examples include dicyandiamide and its derivatives, polyamide resins and the like.
• imidazole-based compound examples include 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl.
• Imidazole 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]- Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- Examples thereof include 4,5-dihydroxymethylimidazole, 2-phenyl-4-
• active ester-based curing agent examples include reaction products of polyfunctional phenol compounds and aromatic carboxylic acids as described in Japanese Patent No. 5152445, and commercially available products include Epicron HPC-8000-65T (DIC Corporation). (Made), etc., but not limited to these.
• the blending amount of the epoxy resin is preferably 1 to 99 in all the components of the modified phenoxy resin and the epoxy resin as solids. It is by mass, more preferably 5 to 97% by mass, still more preferably 10 to 95% by mass, still more preferably 10 to 90% by mass.
• the epoxy resin is within the above blending amount, heat resistance and mechanical strength can be improved when a cured product made of the resin composition of the present invention is obtained.
• the resin composition of the present invention may contain a solvent or a reactive diluent in order to appropriately adjust the viscosity of the resin composition at the time of handling at the time of forming the coating film.
• the solvent or the reactive diluent is used to ensure handleability and workability in molding of the resin composition, and the amount used thereof is not particularly limited.
• the word "solvent” and the above-mentioned word “solvent” are used separately according to their usage modes, but the same kind or different ones may be used independently.
• Examples of the solvent that can be contained in the resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, N and N. -Includes amides such as dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.
• the above-mentioned solvents may be used alone or in admixture of two or more in any combination and ratio.
• the reactive diluent examples include monofunctional glycidyl ethers such as allyl glycidyl ether, bifunctional glycidyl ethers such as propylene glycol diglycidyl ether, polyfunctional glycidyl ethers such as trimethylolpropane polyglycidyl ether, and glycidyl esters. , Glycidylamines and the like.
• solvents or reactive diluents are preferably used in an amount of 90% by mass or less as a non-volatile content, and the appropriate type and amount thereof are appropriately selected depending on the intended use.
• a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferable, and the amount used is preferably 40 to 80% by mass in terms of non-volatile content.
• ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the amount used is a non-volatile content. 30 to 60% by mass is preferable.
• a curing accelerator (excluding those contained in the “curing agent”) can be used in the resin composition of the present invention, if necessary.
• the curing accelerator include imidazole compounds, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, amine complex salts and the like. These curing accelerators may be used alone or in combination of two or more.
• the amount of the curing accelerator to be blended may be appropriately selected according to the purpose of use, but 0.01 to 15 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin component in the resin composition. 0.01 to 10 parts by mass is preferable, 0.05 to 8 parts by mass is more preferable, and 0.1 to 5 parts by mass is further preferable.
• the curing accelerator By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.
• various known flame retardants can be used in the resin composition of the present invention as long as the reliability is not lowered.
• the flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like. From the viewpoint of the environment, halogen-free flame retardants are preferable, and phosphorus-based flame retardants are particularly preferable.
• These flame retardants may be used alone, two or more kinds of flame retardants of the same system may be used in combination, or flame retardants of different systems may be used in combination.
• the resin composition of the present invention may contain components other than those listed above (may be referred to as "other components" in the present invention) for the purpose of further improving its functionality. ..
• Such other components include fillers, thermoplastic resins, thermosetting resins, photocurable resins, UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, rock release agents, smoothing agents. , Colorants, pigments, dispersants, emulsifiers, low elastic agents, mold release agents, defoaming agents, ion trapping agents and the like.
• the filler examples include molten silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, and the like.
• Inorganic fillers such as barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide
• fibrous fillers such as fibers, polyester fibers, cellulose fibers, aramid fibers, and ceramic fibers, and fine particle rubber.
• thermoplastic resin other than the phenoxy resin of the present invention may be used in combination with the resin composition of the present invention.
• the thermoplastic resin include phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, and polymethyl methacrylate resins other than the present invention.
• a phenoxy resin other than the present invention is preferable from the viewpoint of compatibility, and a polyphenylene ether resin or a modified polyphenylene ether resin is preferable from the viewpoint of low dielectric property.
• Other components include organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, and rust preventive pigments, and ultraviolet absorption such as hindered amines, benzotriazoles, and benzophenones.
• Agents antioxidants such as hindered phenol-based, phosphorus-based, sulfur-based, and hydrazide-based, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, leveling agents, leology control agents, and pigment dispersion.
• Additives such as agents, anti-repellent agents, antifoaming agents and the like can be mentioned.
• the blending amount of these other components is preferably in the range of 0.01 to 20% by mass with respect to the total solid content in the resin composition.
• the resin composition of the present invention is obtained by uniformly mixing each of the above components.
• a resin composition containing a phenoxy resin, a curing agent, and if necessary, various components can be easily made into a cured product by the same method as a conventionally known method.
• This cured product has an excellent balance of low hygroscopicity, dielectric properties, heat resistance, adhesion and the like, and exhibits good cured product properties.
• the term "curing" as used herein means that the resin composition is intentionally cured by heat and / or light, and the degree of curing may be controlled according to desired physical properties and applications. The degree of progress may be completely cured or semi-cured, and is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.
• a method for obtaining a cured product from the resin composition of the present invention it may be in the form of casting, injection, potting, dipping, drip coating, transfer molding, compression molding or the like, a resin sheet, a copper foil with resin, a prepreg or the like.
• a method such as laminating and heat-pressurizing to form a laminated board is preferably used.
• the curing temperature at that time is usually in the range of 80 to 300 ° C., and the curing time is usually about 10 to 360 minutes.
• This heating is preferably performed by a two-step treatment of a primary heating at 80 to 180 ° C. for 10 to 90 minutes and a secondary heating at 120 to 200 ° C. for 60 to 150 minutes, and the glass transition temperature (Tg) is high.
• tertiary heating In a compounding system that exceeds the temperature of the secondary heating, it is preferable to further perform the tertiary heating at 150 to 280 ° C. for 60 to 120 minutes. Curing defects can be reduced by performing such secondary heating and tertiary heating.
• the curing reaction of the resin composition is usually advanced to the extent that the shape can be maintained by heating or the like.
• the resin composition contains a solvent, most of the solvent is usually removed by a method such as heating, depressurization, or air drying, but a solvent of 5% by mass or less remains in the resin semi-cured product. May be good.
• the prepreg obtained by using the resin composition of the present invention will be described.
• the sheet-like base material woven fabrics or non-woven fabrics of inorganic fibers such as glass and organic fibers such as polyamine, polyacrylic, polyimide, Kevlar, and cellulose such as polyester can be used, but are limited thereto. is not.
• the method for producing a prepreg from the resin composition and the base material of the present invention is not particularly limited, and for example, the above base material is impregnated by immersing the above base material in a resin varnish whose viscosity is adjusted with a solvent. After that, the resin component is semi-cured (B-staged) by heating and drying, and can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes, for example.
• the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin content.
• a method of manufacturing a laminated board using a prepreg or an insulating adhesive sheet will be described.
• a laminated board using a prepreg one or a plurality of prepregs are laminated, and metal foils are arranged on one side or both sides to form a laminated product, and the laminated material is heated and pressed to integrate the laminated sheets. do.
• the metal foil a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used.
• the temperature can be set to 160 to 220 ° C.
• the pressure can be set to 49 to 490 N / cm 2 (5 to 50 kgf / cm 2 )
• the heating time can be set to 40 to 240 minutes.
• a multilayer plate can be produced by using the single-layer laminated plate thus obtained as an inner layer material.
• a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material.
• An insulating layer is formed on one side or both sides of the circuit forming surface of the inner layer material with a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.
• the insulating adhesive sheet When the insulating layer is formed by the insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is placed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the insulating adhesive sheet is formed as an insulating layer, and a multi-layered inner layer material is formed. Alternatively, the inner layer material and the metal foil which is the conductor layer are formed as the insulating layer by forming the cured product of the insulating adhesive sheet.
• the same metal leaf as that used for the laminated board used as the inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
• the resin composition is applied to the laminated board to form an insulating layer
• the circuit forming surface resin of the outermost layer of the inner layer material is applied to the above resin composition to a thickness of preferably 5 to 100 ⁇ m, and then 100 to 200. Heat and dry at ° C for 1 to 90 minutes to form a sheet. It is formed by a method generally called the casting method. It is desirable to form the thickness after drying to 5 to 80 ⁇ m.
• a printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, it is possible to further form a multi-layer laminated board.
• the insulating layer is formed by the prepreg
• one or a plurality of prepregs are arranged on the circuit forming surface of the inner layer material, and a metal foil is further arranged on the outside to form the laminate. ..
• a cured product of the prepreg is formed as an insulating layer, and a metal foil on the outer side thereof is formed as a conductor layer.
• the metal foil the same metal leaf as that used for the laminated board used as the inner layer material can also be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
• a printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above method using this printed wiring board as an inner layer material, a multi-layer board can be further formed.
• the cured product obtained from the resin composition of the present invention and the laminated board for electric / electronic circuits have excellent flame retardancy and heat resistance.
• Weight average molecular weight (Mw) and number average molecular weight (Mn) Obtained by GPC measurement. Specifically, a main body HLC8320GPC (manufactured by Tosoh Corporation) equipped with columns (TSKgel SuperH-H, SuperHR2000, SuperHM-H, SuperHM-H, and above, manufactured by Tosoh Co., Ltd.) in series is used, and the column temperature is set. The temperature was set to 40 ° C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was 1.0 mL / min, and a differential refractive index detector was used as the detector.
• THF Tetrahydrofuran
• Non-volatile content Measured according to JIS K 7235 standard. The drying temperature was 200 ° C. and the drying time was 60 minutes.
• Dielectric characteristics It was evaluated by the dielectric loss tangent when measured at 1 GHz by the cavity resonator perturbation method. Specifically, using a PNA network analyzer N5230A (manufactured by Agilent Technologies Co., Ltd.) and a cavity resonator CP431 (manufactured by Kanto Electronics Applied Development Co., Ltd.), the width is set in a measurement environment of room temperature 23 ° C. and humidity 50% RH. The measurement was performed using a test piece having a size of 1.5 mm ⁇ length 80 mm ⁇ thickness 150 ⁇ m.
• A1 Bisphenol A type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., YD-128, epoxy equivalent 186, m ⁇ 0.11)
• A2 Fluorene type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., ESF-300, epoxy equivalent 250, m ⁇ 0.08)
• A3 Hydroquinone type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., ZX-1027, epoxy equivalent 131, m ⁇ 0.18)
• A4 Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent 196, m ⁇ 0.13)
• A5 Naphthalene type epoxy resin (manufactured by DIC Corporation, Epicron HP4032D, epoxy equivalent 142, m ⁇ 0.07)
• m has the same meaning as m in the above formula (2).
• B3 Phosphorus-containing diester compound obtained in Synthesis Example 1.
• C2: Bisphenol A (manufactured by Nittetsu Chemical & Materials Co., Ltd., hydroxyl group equivalent 114)
• E1 Acetic anhydride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
• E2 Benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
• H1 Phenolic novolak resin (manufactured by Aica Kogyo Co., Ltd., Shonor BRG-557, hydroxyl group equivalent 105)
• H2 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, Curesol 2E4MZ)
• Synthesis example 1 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction device, cooling tube, and dropping device, 100 parts of C1, 315 parts of E1, 0.05 part of dibutyl summarate, and acetate at room temperature. The temperature was raised to 110 ° C. while stirring with flowing nitrogen gas, and the reaction was carried out for 2 hours. Then, it dried under reduced pressure for 3 hours under the condition of 130 degreeC and 1.3 kPa (10 torr), and 98 parts of B3 was obtained. The active equivalent was 204.
• Example 1 In a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction device, a cooling tube, and a dropping device, 100 parts of A1, 76 parts of B1 and 44 parts of S1 as a reaction solvent were charged at room temperature, and nitrogen was charged. The temperature was raised to 130 ° C. while flowing and stirring the gas, 0.2 part of D1 was added as a catalyst, the temperature was raised to 145 ° C., and the reaction was carried out at the same temperature for 7 hours. Using 44 parts of S1 and 176 parts of S2 as a diluting solvent, they were diluted and mixed to obtain a modified phenoxy resin varnish (R1) having a non-volatile content of 40%.
• R1 modified phenoxy resin varnish
• Example 2 is a phenoxy resin varnish.
• the "equivalent ratio" in the table represents the total equivalent ratio (functional group ratio) of the functional group of the diester compound and the hydroxyl group of the bifunctional phenol compound to the epoxy group of the bifunctional epoxy resin.
• Example 11 100 parts (40 parts in solid content) of the phenoxy resin varnish (RH2) obtained in Comparative Example 2 and 600 parts of S1 were mixed, the temperature was raised to 100 ° C., and 16 parts of E1 was added to carry out the reaction for 4 hours. ..
• the obtained resin varnish was added to methanol, and the precipitated insoluble matter was filtered off, and then the filtrate was dried in a vacuum dryer at 150 ° C. and 0.4 kPa (3 torr) for 1 hour to obtain a phenoxy resin. ..
• To the obtained phenoxy resin 23 parts of S1 and 45 parts of S2 were added and uniformly dissolved to obtain a modified phenoxy resin varnish (R11) having a non-volatile content of 40%.
• Example 12 The same operation as in Example 11 was carried out except that 36 parts of E2 was used instead of E1, 27 parts of S1 of the diluting solvent and 54 parts of S2 were used to obtain a modified phenoxy resin varnish (R12).
• the resin varnishes R1 to R12 and RH1 to RH2 obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were applied to an iron plate so that the film thickness after drying was 150 ⁇ m, and the temperature was 180 ° C. for 1 hour using a dryer. It was dried to obtain a resin film. Mw and storage stability were measured with a phenoxy resin varnish, and dielectric properties were measured with a resin film. The results are shown in Table 3.
• the "acyllation rate" in the table represents the content rate (mol%) of the acyl group in all Z. Examples using the resin varnishes RH1 to RH2 are comparative examples.
• Comparative Example 3 30 parts (12 parts in solid content) of the modified phenoxy resin varnish (R1-5, RH1) obtained in Examples 1 to 5 and Comparative Example 1, 2 parts of A5 as an epoxy resin, and 50% of H1 as a curing agent.
• a resin composition was obtained by blending 2.5 parts of MEK solution and 0.6 part of H2 with 20% MEK solution. Further, these were applied to an iron plate so that the film thickness after drying was 150 ⁇ m, and dried at 180 ° C. for 1 hour using a dryer to obtain a film-like cured product. The dielectric properties were measured and the results are shown in Table 4.
• the modified phenoxy resin of the present invention shown in Examples 1 to 12 is excellent in dielectric properties and storage stability. Further, as can be seen from Table 4, the cured product made of the resin composition of the present invention also has excellent dielectric properties.
• the modified phenoxy resin and resin composition of the present invention can be applied to various fields such as adhesives, paints, building materials for civil engineering, and insulating materials for electric / electronic parts, and in particular, insulating casting in the electric / electronic field, It is useful as a laminating material, a sealing material, and the like.
• the phenoxy resin of the present invention and the resin composition containing the same can be used for multilayer printed wiring boards, laminated boards for electric and electronic circuits such as capacitors, film-like adhesives, adhesives such as liquid adhesives, semiconductor encapsulants, and underfills. It can be suitably used as a material, an interchip fill material for 3D-LSI, an insulating sheet, a prepreg, a heat dissipation substrate, and the like.

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• 2021
  • 2021-09-15 JP JP2022553799A patent/JP7487326B2/ja active Active
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