JP2001302750A - Resin and curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured resin article which strongly adheres to a substrate, or the like, and has low moisture absorption properties, especially a one useful for an adhesive or insulating agent used in electrical and electronic parts. SOLUTION: This resin article is obtained by synthesizing a resin represented by formula (1) [wherein each R is independently H, a 1-10C hydrocarbon group, an alkoxy or a halogen; each X is independently a single bond, O, S, sulfoxide, an alkyl or a group represented by formula (2) (wherein each R is the same as above); each Y is independently H, glycidyl or a group represented by formula (3) (wherein each R is the same as above; and G is H or glycidyl) provided at least one Y is a group represented by formula (3); (n) is a mean value, being 1-10; both (h) and each (i) are independently 1 or 2; and both (j) and each (k) are independently an integer of 0-6], preparing a curable resin composition containing the resin, and curing the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high reliability semiconductor encapsulation, and a laminate (printed wiring board, build-up board) and CFRP (carbon fiber reinforced plastic). Various composite materials,
The present invention relates to a resin useful for an adhesive, a paint, and the like, a curable resin composition, and a cured product thereof.

[0002]

2. Description of the Related Art Phenolic resins and epoxy resins are used in electrical and electronic parts, structural materials, etc. due to their excellent workability and excellent electrical properties, heat resistance, adhesiveness and moisture resistance (water resistance) of the cured product.
Widely used in the fields of adhesives, paints, etc.

However, in recent years, particularly in the electric and electronic fields, with the development of the resin or the resin composition to be used, the resin or the resin composition has been improved in moisture resistance, adhesion, and viscosity reduction for highly filling the filler. Further improvements in various properties such as increased reactivity for shortening the molding cycle are required. As structural materials, lightweight materials having excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. To meet these requirements, many proposals have been made on phenolic resins and epoxy resins and curable resin compositions containing them, but they have not been satisfactory yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and a laminate which exhibit excellent moisture resistance (water resistance) and adhesion in the cured product. (Printed wiring boards, build-up boards, etc.), CFRP and other composite materials, adhesives, paints, and other useful curable resin compositions and their cured products are required to be developed.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for imparting the above-mentioned properties to a curable resin composition and a cured product thereof, and have completed the present invention. That is,
The present invention provides the following formula (1):

[0006]

Embedded image

(Wherein, a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group or a halogen atom. A plurality of Xs independently represent a single bond,
Oxygen atom, sulfur atom, sulfoxide group, alkyl group or formula (2)

[0008]

Embedded image

(In the formula, a plurality of Rs represent the same groups as described above. L represents an integer of 1 to 2, and m represents an integer of 0 to 6.) Represents A plurality of Y are independently a hydrogen atom, a glycidyl group or a formula (3)

[0010]

Embedded image

(Wherein, a plurality of Rs represent the same group as described above; G represents a hydrogen atom or a glycidyl group). n is an average value and represents a real number of 1 to 10. h, l and a plurality of i's independently represent an integer of 1 or 2. j, m and a plurality of k are independently 0 to 6
Indicates an integer. Further, at least one Y is any group of the formula (3). ). (2) a curable resin composition containing the resin of the above item (1), (3) a cured product obtained by curing the curable resin composition of the above item (2),
(4) An electric / electronic component having a cured product of the curable resin composition of the above item (2) as a constituent material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Among the resins of the present invention, a resin having a phenolic hydroxyl group is represented by the following formula (4):

[0013]

Embedded image

(Where X, R, h, i, j, and k are the same as those described above), and the phenolic hydroxyl group of a part of the phenolic resin represented by the following formula (5)

[0015]

Embedded image

Wherein R is as defined above, or a compound represented by the following formula (6):

[0017]

Embedded image

It is obtained by reacting a compound represented by the formula (where R is as defined above) in the presence of a catalyst if necessary (hereinafter referred to as a phenolic resin of the present invention). As a method for obtaining a resin having a glycidyl group among the resins (hereinafter referred to as the epoxy resin of the present invention), all of the phenolic hydroxyl groups of the phenolic resin of the present invention and, if necessary, the reaction with the epoxy compound of the formula (5) are used. The phenolic hydroxyl group of formula (4) is reacted with the compound of formula (5) to glycidylate all or a part of the alcoholic hydroxyl group generated at this time, and all or one of the alcoholic hydroxyl groups generated is reacted. And glycidylation of the part.

The reaction between the phenolic resin of the formula (4) and the epoxy compound of the formula (5) is carried out by heating using a catalyst in the presence of a solvent if necessary. Although the solvent is not particularly limited, specific examples that can be used include toluene,
Examples thereof include xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are solutes of the formula (4)
Is usually 20 to 500 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of the total weight of the phenol resin and the epoxy compound of the formula (5). The catalyst may be any as long as it can catalyze the reaction between the glycidyl group and the phenolic hydroxyl group, such as triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane, and tetraphenylphosphonium / tetraphenylborate. And quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride, boron trifluoride, and tertiary amine compounds. The reaction temperature is usually 50 to 200 ° C, preferably 70 to 180 ° C.
It is. The amounts of the phenolic resin of the formula (4) and the epoxy compound of the formula (5) to be used depend on how much the phenolic hydroxyl group in the phenolic resin of the formula (4) needs to be reacted with the compound of the formula (5). . For example, when a part of the phenolic hydroxyl group is reacted with the compound of the formula (5) to be used as a raw material in the above-mentioned step, the compound of the formula (5) is usually added in an amount of 0 to 1 hydroxyl equivalent of the phenol resin of the formula (4). 0.1 to 0.9 mol, preferably 0.2 to 0.8 mol. After completion of the reaction, although it depends on the catalyst used and the intended use of the synthesized resin, it is usually preferable to remove the catalyst by washing with water or the like and then remove the solvent under heating and reduced pressure. When all of the phenolic hydroxyl groups are reacted with the compound of the formula (5) to be used as a raw material in the above-mentioned step, the amount of the epoxy compound of the formula (5) used is the equivalent of the phenol resin of the formula (4) The compound of the formula (5) is usually 1.0 to 2 mol, preferably 1.
The range is from 0 to 1.5 mol. When the compound of the formula (5) is used in an equivalent amount or more, it is necessary to remove excess compound of the formula (5) together with the solvent under heating and reduced pressure after completion of the reaction.

The resins thus obtained include the following types. (A) A phenolic hydroxyl group of the phenolic resin of the formula (4) reacted with the compound of the formula (5) except for a part thereof. Therefore, a compound having a phenolic hydroxyl group derived from the compound of the formula (4) and an alcoholic hydroxyl group derived from the compound of the formula (5) is the phenolic resin of the present invention and can be a raw material in the above step. (B) All phenolic hydroxyl groups of the phenolic resin of the formula (4) reacted with the compound of the formula (5). Therefore, it has only an alcoholic hydroxyl group derived from the compound of the formula (5) and can be a raw material in the above step. (C) A compound in which the phenolic hydroxyl group of the phenol resin of the formula (4) has reacted with the compound of the formula (6) except for a part thereof. Therefore, the compound having only the phenolic hydroxyl group derived from the compound of the formula (4) is the phenolic resin of the present invention, and can be a raw material in the above step.

The reaction between the phenolic resin of the formula (4) and the compound of the formula (6) is carried out by heating in the presence of a solvent if necessary and optionally using a catalyst. Although the solvent is not particularly limited, specific examples that can be used include toluene,
Examples thereof include xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are solutes of the formula (4)
Total weight of phenolic resin of formula (6) and acid chloride of formula (6) 10
It is usually 20 to 500 parts by weight, preferably 50 to 300 parts by weight, based on 0 parts by weight. As the catalyst, magnesium, dimethylaniline, pyridine, triethylamine,
Examples thereof include alkali metal hydroxides and alkali metal carbonates. The reaction temperature is usually 40 to 200 ° C, preferably 5 to 200 ° C.
0-150 ° C. In this case, the use amount of the compound of the formula (6) needs to be equal to or less than the equivalent of the phenolic hydroxyl group because it is necessary to leave one part of the phenolic hydroxyl group in the phenol resin of the formula (4). Equation (4)
The compound of the formula (6) is usually 0.1 to 0.9 mol, preferably 0.2 to 0.
It is in the range of 8 moles. After completion of the reaction, it is preferable to remove the used catalyst or the by-produced amine salt or inorganic salt of hydrogen chloride, usually by washing with water, and then remove the solvent or the catalyst under heating and reduced pressure.

The epoxy resin of the present invention can be obtained by glycidylation of the phenolic hydroxyl group and / or alcoholic hydroxyl group of the phenolic resin of the present invention according to a conventionally known method. The glycidylation may be carried out by reacting the phenolic resin of the present invention with epihalohydrins. Epihalohydrins used in the glycidylation reaction include epichlorohydrin, epibromhydrin,
Epiiodohydrin, β-methylepichlorohydrin,
There are β-methyl epibromohydrin, β-ethyl epichlorohydrin and the like, but epichlorohydrin which is easily available industrially and is inexpensive is preferable.

The glycidylation reaction is carried out, for example, at 20 to 120 ° C. while adding or gradually adding a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a mixture of the phenolic resin of the present invention and an epihalohydrin. Perform the reaction for ~ 20 hours. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution, in which case the aqueous solution of the alkali metal hydroxide is continuously added and the reaction system is reduced in pressure or under normal pressure, and water and water are continuously added. A method may be employed in which epihalohydrins are distilled off, liquids are separated, water is removed, and epihalohydrins are continuously returned to the reaction system. In the above method, the amount of the epihalohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, per equivalent of the phenolic hydroxyl group and / or alcoholic hydroxyl group of the phenolic resin of the present invention. The amount of the alkali metal hydroxide used is usually 0.5 to 3.0 with respect to 1 equivalent of the hydroxyl group and / or alcoholic hydroxyl group of the phenol resin of the present invention.
Mol, preferably 0.7 to 2.5 mol. In addition, in the above reaction, by adding an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, and 1,3-dimethyl-2-imidazolidinone, an epoxy resin having a low hydrolyzable halogen concentration can be obtained, This is suitable for use as an electronic material sealing material. The amount of the aprotic polar solvent to be used is usually 5 to 200% by weight, preferably 10 to 200% by weight based on the weight of the epihalohydrins.
１００100% by weight. In addition, the reaction can easily proceed by adding an alcohol such as methanol or ethanol in addition to the above-mentioned solvents. Further, toluene, xylene, dioxane and the like can also be used.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of the phenolic resin of the present invention and an excess epihalohydrin at 30 to 150 ° C. 1
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the halohydrin ether of the phenolic resin of the present invention obtained by reacting for 20 to 20 hours. The epoxy resin of the present invention can also be obtained by reacting to close the ring of the halohydrin ether. The amount of the quaternary ammonium salt used in this case is usually 0.001 to 0.2 with respect to 1 equivalent of the hydroxyl group and / or alcoholic hydroxyl group of the phenolic resin of the present invention.
Mole, preferably 0.05 to 0.1 mole.

Usually, these reactants are washed with water, or without heating, after removing excess epihalohydrin under heating and reduced pressure, dissolved in a solvent such as toluene, xylene, methyl isobutyl ketone, and the like. Then, an aqueous solution of an alkali metal hydroxide is added to react again. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol per equivalent of the phenolic hydroxyl group and / or alcoholic hydroxyl group of the phenolic resin of the present invention. Is a mole. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours. After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like, and further, by distilling off solvents such as toluene, xylene, and methyl isobutyl ketone under reduced pressure under heating, an epoxy resin having a low hydrolyzable halogen can be obtained. Since the alcoholic hydroxyl group has lower reactivity than the phenolic hydroxyl group, it may not be glycidylated in the above step, but even in such a case, the above (b)
It is included in the epoxy resin of the present invention except for the case where the resin is used.

Further, by utilizing the difference in reactivity between the phenolic hydroxyl group and the alcoholic hydroxyl group, only the phenolic hydroxyl group is first glycidylated, excess epihalohydrin and the like are removed, and further dissolved in epihalohydrin to form an alcoholic alcohol. The hydroxyl group can be glycidylated. In this case, the amount of the alkali metal hydroxide used for glycidylation of the phenolic hydroxyl group is 0.9 to 1.1 mol, preferably 0.95 to 1.1 mol per equivalent of the phenolic hydroxyl group.
It is in the range of 05 mol. Further, in the glycidylation of the alcoholic hydroxyl group, the glycidylation ratio can be freely adjusted by the amount of the alkali metal hydroxide used. The amount of the alkali metal hydroxide used in this case is usually 0.2 to 3.0 mol, preferably 0.4 to 2.0 mol, per equivalent of the alcoholic hydroxyl group.

Hereinafter, the curable resin composition of the present invention will be described. When the curable resin composition of the present invention contains the phenolic resin of the present invention, it contains an epoxy resin and / or a cyanate ester resin and / or a maleimide compound as other components. In this case, the phenolic resin of the present invention is used alone. Or with other curing agents. When used in combination, the proportion of the phenolic resin of the present invention in the total curing agent is preferably at least 20% by weight, particularly preferably at least 30% by weight.

When the curable resin composition of the present invention contains the epoxy resin of the present invention, it contains a curing agent such as the phenolic resin of the present invention as another component. or,
The epoxy resin of the present invention can be used alone or in combination with another epoxy resin. In this case, the proportion of the epoxy resin of the present invention in the total epoxy resin is 20% by weight.
Or more, and particularly preferably 30% by weight or more.

Examples of other curing agents that can be used in combination with the phenolic resin of the present invention or curing agents for the epoxy resin of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Can be Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. Merritic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, Mud carboxymethyl benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.)
And various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde,
Polycondensates with naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene,
Polymers with norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene), phenols and ketones (acetone,
Polycondensates with methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc., phenols and aromatic dimethanols (benzene dimethanol,
polycondensates with α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol, phenols and aromatic dichloromethyls (α, α′-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and modified products thereof.
Examples include, but are not limited to, imidazole, BF ₃ -amine complex, guanidine derivative, dicyandiamide, and the like. When the curable resin composition contains an epoxy resin, the curing agent is used at a ratio of 0.5 to 1.5 equivalents of the epoxy resin to 1 equivalent of the curing agent, and when the curable resin composition contains a cyanate ester resin, the curing agent is used. : Cyanate ester resin (weight ratio) = 20: 80-80: 20, and when a maleimide compound is contained, curing agent: maleimide compound (weight ratio) = 20: 80-80: 20. It is preferred to use.

Specific examples of epoxy resins that can be used in the curable resin composition of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol, Aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalate) Aldehydes, crotonaldehyde, cinnamaldehyde, etc.), phenols and various die Polymers with compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone) , Methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α,
polycondensates with α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol, phenols and aromatic dichloromethyls (α, α′-dichloro) Xylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidyl etherification of alcohols, etc., alicyclic epoxy resins, glycidylamine epoxy resins, Glycidyl ester-based epoxy resins and the like can be mentioned, but are not limited to these as long as they are commonly used epoxy resins. These may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains an epoxy resin, if necessary, a composition generally used as a curing accelerator for an epoxy resin may be contained. Examples of the curing accelerator include 2-methylimidazole, 2
-Imidazole compounds such as ethylimidazole, boron trifluoride complex, phosphorus compounds such as triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane, tetraphenylphosphonium / tetraphenylborate, tertiary Amine compounds and the like are used, and the amount thereof is usually 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin.
Parts by weight, preferably 0.1 to 10 parts by weight.

Specific examples of the cyanate ester resin that can be used in the curable resin composition of the present invention include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2′-bis (4 -Cyanatophenyl) propane, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2′-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2′-bis (4-cyanatophenyl) ethane, 2,2′-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether,
Phenol novolak cyanate and phenol / dicyclopentadiene cocondensate in which a hydroxyl group is converted to a cyanate group are exemplified, but not limited thereto. These may be used alone or in combination of two or more.

When the cured resin composition of the present invention contains a cyanate ester resin, if necessary, the cyanate group is trimerized to form a sym-triazine ring.
Zinc naphthenate, cobalt naphthenate, copper naphthenate,
A catalyst such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate and the like can be contained. The catalyst is used in an amount of 0.0001 to 0.10 part by weight, preferably 0.00015 to 0.0015 part by weight, based on 100 parts by weight of the resin component in the curable resin composition. These may be used alone,
Two or more types may be used.

The maleimide compound that can be used in the curable resin composition of the present invention may be any compound having a maleimide group, and can be obtained by subjecting a compound having a secondary amine and maleic anhydride to a condensation / dehydration reaction. And specific examples thereof include phenylmaleimide, hydroxyphenylmaleimide, N, N′-ethylenebismaleimide, N, N′-hexamethylenebismaleimide, N, N′-phenylenebismaleimide,
4'-Bismaleimidodiphenylmethane, 4,4'-Bismaleimidediphenylpropane, 4,4'-Bismaleimidediphenylsulfone, Maleimide resin obtained by condensation dehydration of maleic anhydride with amino group of aniline / aldehyde polycondensate, aniline Maleimide resin obtained by condensation dehydration of an amino group of a polycondensate of aromatics and aromatic dimethanols with maleic anhydride, and the like, but not limited thereto. These may be used alone or in combination of two or more.

When a maleimide compound is contained in the curable resin composition of the present invention, a curing accelerator such as an epoxy resin or a cyanate ester resin, or a radical polymerization initiator such as an organic peroxide or an azo compound is used. May be used. The curing accelerator or the polymerization initiator is usually 0.01 to 10 parts by weight per 100 parts by weight of the resin component in the curable resin composition.
Use in proportions by weight. These may be used alone or in combination of two or more.

When the curable resin composition contains the epoxy resin or the maleimide compound of the present invention, the resin composition can be cured by light by using a photo-radical initiator or a photo-cationic initiator. .

Further, known additives can be added to the curable resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified acrylonitrile copolymer, indene resin, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, silica, alumina, Calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride,
Inorganic filler such as asbestos, mica, glass powder, glass fiber, glass non-woven fabric or carbon fiber, surface treatment agent for filler such as silane coupling agent, release agent, coloring of carbon black, phthalocyanine blue, phthalocyanine green, etc. Agents.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio. 20 to 100 ° C from the softening point of each of the above components if necessary
It can be performed by heating and melting at a high temperature. Further, the components of the curable resin composition can be mixed by uniformly dispersing or dissolving the components in a solvent or the like. The solvent in this case is not particularly limited, but specific examples that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are usually used in an amount of 5 to 300 parts per 100 parts by weight of the resin component.
Parts by weight, preferably 10 to 150 parts by weight, are used.

The cured product of the present invention can be obtained by treating the above curable resin composition at room temperature to 250 ° C. for 30 seconds to 50 hours. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and after the solvent is removed, the composition may be cured under the above-described conditions. When the curable resin composition contains a photoradical initiator, a photocationic initiator, or the like, the composition can be cured mainly by irradiating ultraviolet rays.

The cured product of the present invention thus obtained has high moisture resistance and high adhesiveness. Therefore, the curable resin composition of the present invention can be used in a wide range of fields where moisture resistance and adhesiveness are required. Specifically, it is useful as a compounding component of all electric and electronic materials such as an insulating material, a laminate, and a sealing material, but the outermost layer is a copper frame plated with palladium, gold, silver, or nickel, or the above-mentioned plating is applied. It is preferably used to seal a semiconductor device using a copper frame without a lead frame.

The electric / electronic product of the present invention has a cured product of the resin composition of the present invention, for example, a product sealed with the resin composition of the present invention. A semiconductor device is preferable as the electric / electronic component. Here, as the semiconductor device, for example, DIP
(Dual inline package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), and the like.

[0042]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to these examples. In Reference Examples and Examples, epoxy equivalent, melt viscosity, softening point, and hydrolyzable chlorine concentration were measured under the following conditions. 1) Epoxy equivalent It measured by the method according to JISK-7236. 2) Melt viscosity Melt viscosity in the cone plate method at 150 ° C Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 3 (measurement range: 0 to 20 poise) Sample amount: 0.15 ± 0.005 (g) 3) Softening point Measured by a method according to JIS K-7234.

Reference Example 1 555 parts by weight of epichlorohydrin (ECH, the same applies hereinafter) and 6 parts by weight of tetramethylammonium chloride were charged into a reaction vessel with respect to 118 parts by weight of furfuryl alcohol, heated and stirred, and the temperature was maintained at 40 ° C. Meanwhile, 72 parts by weight of flaky sodium hydroxide was continuously added over 1.5 hours. After completion of the addition of sodium hydroxide,
The reaction was carried out for a further time. Subsequently, washing with water was repeated to remove by-product salts and tetramethylammonium chloride. After that, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 470 parts by weight of toluene was added to the residue to dissolve it. This toluene solution was heated to 70 ° C., 12 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was allowed to react for 1 hour. Then, the reaction solution was repeatedly washed with water until the washing solution became neutral. Then, toluene was distilled off from the oil layer under heating and reduced pressure, and the product was subjected to molecular distillation to obtain 115 parts by weight of an epoxy compound (C1) in which R in the above formula (5) is all hydrogen atoms. The epoxy equivalent of this epoxy compound (C1) was 157 g / eq.

Reference Example 2 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 188 parts by weight of phenol, 50 parts by weight of water, and 6 parts of furfural.
7 parts by weight and 20 parts by weight of sodium hydroxide are charged and stirred.
After dissolution, heat to reflux (about 100-110 ° C)
The reaction was continued for an hour, and the temperature in the system was raised to about 140 to 150 ° C. while distilling off water and phenol by heating, and the reaction was carried out for 4 hours while maintaining the temperature. Then, after cooling, it was neutralized with concentrated hydrochloric acid. Next, 300 parts by weight of methyl isobutyl ketone was added, and after removing the separated aqueous layer, washing with water was repeated several times to remove sodium chloride, and methyl isobutyl ketone and unreacted phenol were removed from the oil layer under heating and reduced pressure. Equation (7)

[0045]

Embedded image

A phenolic resin (C2) 140 represented by
Parts by weight were obtained. This phenol resin (C2) has a softening point of 87 ° C., a melt viscosity of 3.0 poise and a hydroxyl equivalent of 15
It was 2 g / eq.

Example 1 In a flask equipped with a stirrer, a reflux condenser and a stirrer, 47 parts by weight of the epoxy compound (C1) obtained in Reference Example 1 were added.
46 parts by weight of the phenol resin (C2) obtained in Reference Example 2, 100 parts by weight of toluene, and 2 parts by weight of tetramethylammonium chloride were charged, stirred, dissolved, and heated to about 100 parts.
At 50 ° C. for 50 hours.
The washing was repeated several times to remove tetramethylammonium chloride. Toluene and methyl isobutyl ketone were removed from the oil layer under reduced pressure by heating to obtain 90 parts by weight of a resin. 88 parts by weight of this resin were charged into a reaction vessel together with 280 parts by weight of epichlorohydrin and 1 part by weight of tetramethylammonium chloride, and heated, stirred,
After dissolution, while maintaining the temperature at 40 ° C., 24 parts by weight of sodium hydroxide in the form of flakes were continuously added over 1.5 hours. After the completion of the addition of sodium hydroxide, the reaction was further performed at 40 ° C. for 3 hours and at 70 ° C. for 1 hour. Then, washing with water was repeated to remove by-product salts and tetramethylammonium chloride. After that, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 150 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. This methyl isobutyl ketone solution was heated to 70 ° C., and 3 parts by weight of a 30% aqueous sodium hydroxide solution was added. After reacting for 1 hour, the reaction solution was repeatedly washed with water until the washing solution became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 63 parts by weight of the epoxy resin (E1) of the present invention. The epoxy resin (E1) was a highly viscous liquid resin having an epoxy equivalent of 368 g / eq.

Example 2 In a flask equipped with a stirrer, a reflux condenser and a stirrer, 23 parts by weight of the epoxy compound (C1) obtained in Reference Example 1 were added.
46 parts by weight of the phenol resin (C2) obtained in Reference Example 2, 100 parts by weight of toluene, and 2 parts by weight of tetramethylammonium chloride were charged, stirred, dissolved, and heated to about 100 parts.
At 50 ° C. for 50 hours.
The washing was repeated several times to remove tetramethylammonium chloride. Toluene and methyl isobutyl ketone were removed from the oil layer by heating under reduced pressure, and 90 parts by weight of the phenol resin (P1) 67 of the present invention were obtained.
Parts by weight were obtained. The hydroxyl equivalent of the obtained phenol resin was 439 g / eq.

Example 3 Epichlorohydrin (ECH, hereinafter the same) 1 based on 439 parts by weight of the phenol resin (P1) obtained in Example 2
500 parts by weight and 300 parts by weight of dimethyl sulfoxide (DMSO, the same applies hereinafter) are charged into a reaction vessel, heated, stirred and dissolved. After maintaining the temperature at 45 ° C., the mixture is heated, stirred and dissolved, and flakes are maintained at 40 ° C. 48 parts by weight of sodium hydroxide were added continuously over 1.5 hours. After completion of sodium hydroxide addition, 3 hours at 40 ° C, 1 hour at 70 ° C
The reaction was carried out for a further time. Then, repeat washing with water, DMS
After removing O and by-product salts, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 1000
A part by weight of methyl isobutyl ketone was added and dissolved. This methyl isobutyl ketone solution was heated to 70 ° C.
After adding 20 parts by weight of an aqueous sodium hydroxide solution and reacting for 1 hour, washing of the reaction solution with water was repeated until the washing solution became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 378 parts by weight of the epoxy resin (E2) of the present invention. Epoxy resin (E
2) was a highly viscous liquid resin having an epoxy equivalent of 544 g / eq.

Example 4 In a flask equipped with a stirrer, a reflux condenser and a stirrer, 544 parts by weight of the epoxy resin (E2) obtained in Example 3 was added together with 1500 parts by weight of epichlorohydrin and 20 parts by weight of tetramethylammonium chloride. Charge the reaction vessel, heat,
After stirring and dissolving, 40 parts by weight of flaky sodium hydroxide was continuously added over 1.5 hours while maintaining the temperature at 40 ° C. After completion of sodium hydroxide addition, 40 ° C
For 3 hours and at 70 ° C. for 1 hour. Subsequently, washing with water was repeated to remove by-product salts and tetramethylammonium chloride. After that, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 1500 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. This methyl isobutyl ketone solution was heated to 70 ° C., and 15 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1 hour, washing with water of the reaction solution was repeated until the washing solution became neutral. Next, 460 parts by weight of the epoxy resin (E3) of the present invention was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The epoxy resin (E3) was a highly viscous liquid resin with an epoxy equivalent of 382 g / eq.

Examples 5 to 8 The mixture blended at the weight ratio shown in Table 1 was kneaded with a biaxial roll, pulverized and tableted, and a resin molded product was prepared by transfer molding. 1
Cured at 80 ° C. for 8 hours.

Table 1 shows the results of measuring the physical properties of the cured product thus obtained. In addition, the measurement of the physical property value was performed by the following method. -Moisture absorption: Weight increase rate (%) after leaving a disc-shaped test piece of 5 cm in diameter x 4 mm in thickness at 121 ° C / 100% RH for 24 hours-Copper foil peel strength: 180 ° peel test Measurement temperature 30 ° C. Pulling speed; 200 mm / min Copper foil; JTC foil 70 μm manufactured by Nikko Gould Co., Ltd.

[0053]

The abbreviations in Table 1 indicate the following. TPM: Kayahard TPM (manufactured by Nippon Kayaku Co., Ltd., OH equivalent 97 g / eq, softening point 110 ° C.) EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., softening point ° C. Epoxy equivalent 103 g / eq) TPP: triphenylphosphine ( Junsei Chemical Co., Ltd.)

[0055]

The curable resin composition containing the resin of the present invention has excellent moisture resistance (water resistance) and adhesiveness in the cured product. Materials, etc.) and laminated boards (printed wiring boards, etc.)
It is extremely useful when used for various composite materials including CFRP and CFRP, adhesives, paints, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 4J040 C09J 201/00 C09J 201/00 F term (Reference) 4F071 AA41 AA42 AF53 AF58 AH12 BA01 BB03 BC03 4J032 CA16 CB01 CB04 CC01 4J033 CA04 CA05 CA07 CA11 CA12 CA24 CA26 CA33 CA34 CA36 CB18 CC04 CD02 CD03 CD04 HA28 HB02 HB03 HB06 HB08 HB09 4J036 AJ11 AJ13 AJ16 FB08 DB2 JA01 JA08 DB161 DF051 DK001 DN011 GA02 GA05 GA07 GA12 GA13 PB09 4J040 EB051 EC061 EC071 EC081 EC151 EC171 EE061 EJ011 EL011 EL031 GA03 GA05 GA11 GA24 GA25 JB02 LA06 LA07 LA08 LA09 NA19

Claims (4)

[Claims] (1) Formula (1) (Wherein, a plurality of Rs are independently a hydrogen atom,
And represents a hydrocarbon group, an alkoxy group or a halogen atom. A plurality of Xs are independently a single bond, an oxygen atom, a sulfur atom, a sulfoxide group, a hydrocarbon group or a compound of the formula (2) (In the formula, a plurality of Rs represent the same group as described above.
Represents an integer of 1 to 2, and m represents an integer of 0 to 6, respectively. ). A plurality of Ys are independently a hydrogen atom, a glycidyl group or a compound of the formula (3) (Wherein, a plurality of R represent the same groups as described above; G represents a hydrogen atom or a glycidyl group). n is an average value and represents a real number of 1 to 10. h and a plurality of i's independently represent an integer of 1 to 2. j and a plurality of k's independently represent an integer of 0 to 6. Further, at least one Y is any group of the formula (3). )
A resin represented by 2. A curable resin composition containing the resin according to claim 1. 3. A cured product obtained by curing the curable resin composition according to claim 2. 4. An electric / electronic part comprising a cured product of the curable resin composition according to claim 2 as a constituent material.