JP6715249B2 - Epoxy resin, modified epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

The present invention relates to an epoxy resin, a modified epoxy resin, an epoxy resin composition, and a cured product thereof, which can be used for semiconductor encapsulating materials, liquid crystal encapsulating materials, EL encapsulating materials, printed wiring boards, build-up laminated boards, and other electrical materials. -Suitable for electronic parts and lightweight high strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

2. Description of the Related Art In recent years, a laminated board on which electric/electronic components are mounted has been required to have a wide range of required characteristics due to the expansion of its application field. For example, conventionally, semiconductor chips have been mainly mounted on metal lead frames, but semiconductor chips with high processing capabilities such as CPUs are often mounted on laminated plates made of polymer materials. ing. As the speed of devices such as CPU increases and the clock frequency increases, signal propagation delay and transmission loss become a problem, and wiring boards are required to have low dielectric constant and low dielectric loss tangent. At the same time, as the speed of the device increases, the heat generation of the chip increases, so that it is necessary to increase the heat resistance.
In addition, mobile electronic devices such as mobile phones have become widespread in recent years, and precision electronic devices have come to be used and carried in outdoor environments or in the immediate vicinity of the human body. Tolerance is needed.
Further, in the field of automobiles, computerization is progressing, and precision electronic devices may be arranged near the engine, so that heat resistance and humidity resistance are required at a higher level.
Further, in recent years, the weight of airplanes, automobiles, trains, ships and the like has been reduced due to the need for energy saving. In the field of vehicles, a study is being made in particular to replace a metal material that has been used in the past with a lightweight and high-strength carbon fiber composite material. For example, in the Boeing 787, the ratio of the composite material is increased to reduce the weight, and the fuel efficiency is significantly improved. In the automobile field, although it is partly equipped with a shaft made of composite material, there is also a movement to make the body of the composite material for luxury cars. In response to these requirements, many proposals have been made on epoxy resins and resin compositions containing the same (Patent Documents 1 and 2). Patent Document 3 discloses an epoxy resin having an allyl group-containing bisphenol A structure (Patent Document 3).

Japanese Patent Laid-Open No. 11-140163 Japanese Patent Laid-Open No. 11-255866 Japanese Patent Laid-Open No. 2004-107501

However, the epoxy resin having a bisphenol S structure containing an allyl group in Patent Document 3 is still insufficient in performance, and further improvement is required. Then, an object of the present invention is to provide an epoxy resin, a modified epoxy resin, an epoxy resin composition which shows excellent low hygroscopicity (low water absorption) heat resistance and strength in the cured product, and a cured product thereof.

The present inventors have conducted extensive studies to solve the above problems, and found that the epoxy resin having a bisphenol structure containing a propenyl group has excellent low hygroscopicity (low water absorption), excellent heat resistance and elastic modulus, The present invention has been completed.

That is, the present invention is
[1] The following formula (1)

(In the formula, plural Rs independently represent an allyl group or a propenyl group, and 10% or more of all Rs are propenyl groups. G represents a glycidyl group. Plural Xs independently represent hydrogen. Represents an atom or a glycidyl group, n is 0 to 10, and the average value thereof represents a real number of 0 to 10.),
[2] A modified epoxy resin obtained by polymerizing the epoxy resin described in [1] above and a bisphenol.
[3] An epoxy resin composition containing the epoxy resin described in [1] above or the modified epoxy resin described in [2] above,
[4] The epoxy resin composition according to the above [3], which contains a curing agent,
[5] The epoxy resin composition according to the above [3] or [4], which contains a curing accelerator,
[6] The epoxy resin composition according to any one of items [3] to [5], which contains a radical polymerization initiator,
[7] A cured product obtained by curing the epoxy resin composition according to any one of [3] to [6] above is provided.

The present invention provides an insulating material (such as a highly reliable semiconductor encapsulating material) for electric and electronic parts, which exhibits excellent low hygroscopicity (low water absorption) and heat resistance (solder reflow resistance) in its cured product, and a laminate (print). Wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.), CFRP and other composite materials, epoxy resins useful for paints, modified epoxy resins, epoxy resin compositions and The cured product is provided.

Hereinafter, the epoxy resin of the present invention will be described in detail.
The epoxy resin of the present invention is represented by the following formula (1).

(In the formula, a plurality of Rs each independently represent an allyl group or a propenyl group (a propenyl group represents a 1-propenyl group, but hereinafter referred to as a propenyl group), and 10% or more of all Rs are propenyl. G is a glycidyl group, plural X's each independently represent a hydrogen atom or a glycidyl group, n is 0 to 10, and the average value thereof is a real number of 0 to 10.)

Epoxy resins produce polar groups (hydroxyl groups and ester groups) at the cross-linking points during the curing reaction, and it is known that their hydrophilicity greatly affects hygroscopicity. As a measure for lowering moisture absorption of the cured product, lowering the concentration of the polar group (increasing the epoxy equivalent) effectively works. However, on the other hand, in many cases, the glass transition temperature is lowered due to the decrease in crosslink density.
The epoxy resin of the present invention converts a part or all of the allyl group to a more reactive propenyl group, and as a result, the reaction between propenyl groups (while the allyl group does not crosslink) in the curing process. As a result, the crosslink density is increased and the heat resistance (glass transition temperature) is improved. On the other hand, unlike the reaction of the epoxy group, a polar group is not generated, so that the deterioration of water absorption (wetness) accompanying the improvement of heat resistance can be reduced.

In the epoxy resin of the present invention, in the above formula (1), each R represents an allyl group or a propenyl group, 10% or more of all Rs are propenyl groups, more preferably 20% or more, particularly preferably 30% or more. Is. If it is less than 10%, the heat resistance may not be sufficiently improved.
In the formula (1), n is preferably 0-10, and particularly preferably 0-5. The average value of n is 0 to 10, preferably 0 to 5.

The epoxy equivalent of the epoxy resin of the present invention is 221 to 8100 g/eq. Is preferable, and more preferably, 221 to 4300 g/eq. Is. Epoxy equivalent is 8100 g/eq. When it exceeds, it means that the amount of epoxy groups per unit structure decreases, which means that the number of epoxy groups decreases. Therefore, it may not be preferable in terms of heat resistance.

The total chlorine content remaining in the epoxy resin of the present invention obtained by the reaction is preferably 1500 ppm or less, more preferably 1000 ppm or less, and particularly preferably 500 ppm or less.

The epoxy resin of the present invention has a resin-like form having a softening point. Here, the softening point is preferably 50 to 100°C. If the softening point is too low, there will be no problem when it is used by dissolving it in a solvent, but when it is handled as a solid resin, blocking occurs and tack may occur, resulting in poor handling. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.
The melt viscosity is preferably 0.01 to 5 Pa·s (ICI melt viscosity 150° C. cone plate method), more preferably 0.02 to 4 Pa·s, and particularly preferably 0.02 to 3 Pa·s. preferable. When the viscosity is too low, even if a large amount of a filler such as a filler is blended, it has the advantage of good fluidity, while causing blocking and tacking.

Next, a method for producing the epoxy resin of the present invention will be described.
First, the epoxy resin of the present invention described in (1) above has the following formula (2)

(In the formula, each R independently represents an allyl group or a propenyl group.) It is obtained by reacting a compound represented by epihalohydrin. Specific examples of the compound of the formula (2) include 2,2′-diallyl-4,4′-sulfonyldiphenol, 2-allyl-2′-propenyl-4,4′-sulfonyldiphenol, 2,2. '-Dipropenyl-4,4'-sulfonyldiphenol, 2,2'-diallyl-6,6'-sulfonyldiphenol, 2-allyl-2'-propenyl-6,6'-sulfonyldiphenol, 2,2 Examples include'-dipropenyl-6,6'-sulfonyldiphenol and the like, and the compounding ratio is such that propenyl group/(propenyl group+allyl group)≧0.1.

The epihalohydrins used in the reaction of the compound of the formula (2) with epihalohydrins include epichlorohydrin, epibromhydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-ethyl. Although epichlorohydrin and the like are available, epichlorohydrin, which is industrially easily available and inexpensive, is preferable. This reaction can be performed according to a conventionally known method.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added all at once or gradually to a mixture of the compound of the formula (2) and epihalohydrin and reacted at 20 to 120° C. for 1 to 20 hours. At this time, an aqueous solution may be used as the alkali metal hydroxide, in which case the alkali metal hydroxide is continuously added and water and epihalohydrins are continuously added from the reaction system under reduced pressure or normal pressure. It is also possible to use a method of distilling the water, further separating the water, removing the water, and continuously returning the epihalohydrins to the reaction system.

In the above method, the amount of epihalohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, per 1 equivalent of the hydroxyl group of the compound of the formula (2). The amount of the alkali metal hydroxide used is usually 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol, based on 1 equivalent of the hydroxyl group of the compound of the above formula (2). Further, in the above reaction, an epoxy resin having a low hydrolyzable halogen concentration can be obtained by adding an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide (DMSO), dimethylformamide, and 1,3-dimethyl-2-imidazolidinone. It is obtained and suitable for use as an electronic material encapsulant. For example, the total chlorine concentration is preferably 1500 ppm or less, more preferably 1000 ppm or less. The amount of the aprotic polar solvent used is in the range of 5 to 200% by weight, preferably 10 to 100% by weight, based on the weight of the epihalohydrin. The reaction can be facilitated by adding alcohols such as methanol and ethanol in addition to the above solvents. Further, toluene, xylene, dioxane and the like can also be used.

In addition, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride is used as a catalyst in a mixture of the compound represented by the formula (2) and an excess of epihalohydrins at 50° C. 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 compound of the formula (2) obtained by reacting at 150° C. for 1 to 20 hours, and then 20 to 120. The epoxy resin of the present invention can be obtained by ring-closing the halohydrin ether by reacting at 1° C. for 1 to 20 hours. In this case, the amount of the quaternary ammonium salt used is usually 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, relative to 1 equivalent of the hydroxyl group of the compound of the formula (2).

Usually, these reaction products are washed with water or after removing excess epihalohydrin under heating and reduced pressure without water washing, and then dissolved in a solvent such as toluene, xylene or methyl isobutyl ketone, and then alkali sodium such as sodium hydroxide or potassium hydroxide. The reaction is carried out again by adding an aqueous solution of metal hydroxide. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol, relative to 1 equivalent of the hydroxyl group of the compound of the formula (2). 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, the by-produced salt is removed by filtration, washing with water and the like, and the solvent such as toluene, xylene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy resin having less hydrolyzable halogen.

Further, the epoxy resin of the formula (1) once obtained is polymerized with the compound of the formula (2) to obtain the epoxy resin of the formula (1) having a large value of n. Polymerization is carried out by dissolving the epoxy resin of the above formula (1) and the compound of the above formula (2) in a solvent such as toluene, xylene or methyl isobutyl ketone, if necessary, and then adding sodium hydroxide, triphenylphosphine, a tertiary ammonium salt or the like. It is carried out by adding a catalyst and heating. The epoxy resin of the formula (1) and the compound of the formula (2) are usually used so that the epoxy group is more than the hydroxyl group in an equivalent ratio.

The epoxy resin obtained as described above is an epoxy resin in which all Xs are hydrogen atoms in the above formula (1), but by further reacting epihalohydrin with a secondary alcoholic hydroxyl group, X It is possible to obtain a polyfunctional epoxy resin in which all or a part of these are glycidyl groups.

As a specific method, the secondary alcoholic hydroxyl group of this epoxy resin and epihalohydrin are treated with DMSO, a quaternary ammonium salt, 1,3-dimethyl-2-imidazolidinone or cyclic ethers and an alkali metal hydroxide. By reacting in the presence of a substance, epoxidation can be performed, and by adjusting the amount of the alkali metal hydroxide, the proportion of X being a glycidyl group can be arbitrarily controlled.

The amount of DMSO, 1,3-dimethyl-2-imidazolidinone, or cyclic ether used is preferably 5 to 300% by weight with respect to the epoxy resin in which all X in the formula (1) are hydrogen atoms. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide and the like, and the amount thereof is 0 with respect to 1 equivalent of the secondary alcoholic hydroxyl group of the epoxy resin in which X is a hydrogen atom in the formula (1). 0.3 to 50 g is preferable, and 0.5 to 20 g is particularly preferable.

As the epihalohydrin used in this reaction, there are epichlorohydrin, epibromhydrin, epiiodohydrin and the like as described above, but epichlorohydrin which is industrially easily available and inexpensive is preferable. The amount used is preferably 1 equivalent or more with respect to 1 equivalent of the secondary alcoholic hydroxyl group of the epoxy resin in which all X are hydrogen atoms in the formula (1).

As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide and the like can be used, but sodium hydroxide is preferable. The amount of the alkali metal hydroxide used is preferably 1 to 10 times, particularly preferably 1 to 10 times the equivalent of the secondary alcoholic hydroxyl group to be epoxidized in the epoxy resin in which all X are hydrogen atoms in the formula (1). 1 to 2 times equivalent may be used. The alkali metal hydroxide may be solid or aqueous solution. Further, when an aqueous solution is used, the reaction can be carried out during the reaction while distilling the water in the reaction system out of the reaction system under normal pressure or reduced pressure.

The reaction temperature is preferably 30 to 100°C. After completion of the reaction, excess epihalohydrin and solvents may be distilled and recovered under reduced pressure, the resin may be dissolved in an organic solvent, and a dehydrohalogenation reaction may be carried out with an alkali metal hydroxide. On the other hand, after the reaction is complete, the product is washed with water to separate by-product salts and solvents, and excess epihalohydrin and solvents from the oil layer are recovered by distillation under reduced pressure, and then the resin is dissolved in an organic solvent and alkali metal hydroxide is added. A dehydrohalogenation reaction may be performed. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene and the like can be used, but methyl isobutyl ketone is preferable. They can be used alone or in a mixed system. Thus, an epoxy resin in which a part or all of X in the above formula (1) is a glycidyl group is obtained.

Further, in the production of the epoxy resin of the present invention, epoxidation and rearrangement of an allyl group to a propenyl group can be carried out simultaneously. In this case, it is necessary to add an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide (DMSO), dimethylformamide, 1,3-dimethyl-2-imidazolidinone to epihalohydrin.
For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added all at once or gradually to a mixture of the compound of the formula (2), epihalohydrin and an aprotic polar solvent at 20 to 70° C., preferably Is reacted at 20-40°C for 1-20 hours. In this case, the amount of the alkali metal hydroxide used is usually in the range of 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol per 1 equivalent of the hydroxyl group of the compound of the formula (2).
Usually, these reaction products are washed with water, or after removing excess epihalohydrins and aprotic polar solvent under heating and reduced pressure without washing with water, toluene, xylene, dissolved in a solvent such as methyl isobutyl ketone, sodium hydroxide, The reaction is carried out again by adding an aqueous solution of an alkali metal hydroxide such as potassium hydroxide. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol, relative to 1 equivalent of the hydroxyl group of the compound of the formula (2). 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, the salt produced as a by-product is removed by filtration, washing with water, etc., and a solvent such as toluene, xylene and methyl isobutyl ketone is distilled off under heating and reduced pressure, whereby a part or all of the allyl group is converted to a propenyl group. An epoxy resin can be obtained.

The modified epoxy resin of the present invention described in [2] above will be described below.
The modified epoxy resin of the above [2] (hereinafter, modified epoxy resin) can be obtained by polymerizing the once obtained epoxy resin of the above formula (1) with bisphenols. Polymerization is carried out by dissolving the epoxy resin of the above formula (1) and bisphenols in a solvent such as toluene, xylene or methyl isobutyl ketone, and adding a catalyst such as sodium hydroxide, triphenylphosphine or a tertiary ammonium salt, if necessary. It is done by heating. The epoxy resin of the above formula (1) and the bisphenol are used in such a ratio that the epoxy group is usually larger than the hydroxyl group in an equivalent ratio.
Examples of the bisphenols used in this case include bisphenol A, bisphenol F, bisphenol AD, bisphenol Z, bisphenol S, tetrabromobisphenol A, tetrabromobisphenol F, biphenol, dihydroxybenzene, dihydroxyphenyl sulfide, dihydroxyphenyl ether. However, the present invention is not limited to these. These may be used alone or in combination of two or more.
During this reaction, a secondary alcoholic hydroxyl group is also formed, and this hydroxyl group can be glycidylated in whole or in part by the method described above.

The epoxy resin or modified epoxy resin of the present invention can also be used as a raw material for an epoxy acrylate resin.

In the epoxy resin composition of the present invention, the epoxy resin of the formula (1) or the modified epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of formula (1) or the modified epoxy resin of the present invention in the total epoxy resin is preferably 20% by weight or more, and particularly preferably 30% by weight or more.

As the epoxy resin of the formula (1) or the epoxy resin which can be used in combination with the modified epoxy resin, any conventionally known epoxy resin can be used. Specific examples of the epoxy resin include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, polycondensates of bisphenols and various aldehydes. And alicyclic epoxy represented by glycidyl ether-based epoxy resin obtained by glycidylating alcohols and the like, 4-vinyl-1-cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, and the like. Examples of the resin include, but are not limited to, a glycidylamine-based epoxy resin represented by tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidyl-p-aminophenol, and the like, a glycidyl ester-based epoxy resin, and the like. These may be used alone or in combination of two or more.
Further, a phenol aralkyl resin obtained by subjecting a phenol and the bishalogenomethylaralkyl derivative or the aralkyl alcohol derivative to a condensation reaction as a raw material, an epoxy resin obtained by reacting with epichlorohydrin and dehydrochlorination has low hygroscopicity, It is particularly preferable as an epoxy resin because it has excellent flame retardancy and dielectric properties.

The epoxy resin composition of the present invention may contain a cyanate ester resin.
As the cyanate ester compound that can be added to the epoxy resin composition of the present invention, a conventionally known cyanate ester compound can be used. Specific examples of the cyanate ester compound include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Examples thereof include cyanate ester compounds obtained by reacting compounds with cyanogen halide, but are not limited thereto. These may be used alone or in combination of two or more.
Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene and dihydroxynaphthalene.
Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde and the like.
Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene and isoprene.
Examples of the above-mentioned ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
Specific examples of the cyanate ester resin include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 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-cya) Natophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, phenol di Examples thereof include cyclopentadiene cocondensation products in which hydroxyl groups are converted to cyanate groups, but are not limited thereto.
Further, the cyanate ester compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2004-041055 is particularly preferable as a cyanate ester compound because it has low hygroscopicity, flame retardancy and dielectric properties.

In the case where the epoxy resin composition of the present invention contains a cyanate resin, zinc naphthenate, cobalt naphthenate, copper naphthenate, and naphthene are used in order to trimerize the cyanate group to form a sym-triazine ring, if necessary. A catalyst such as lead acid salt, zinc octylate, tin octylate, lead acetylacetonate, and dibutyltin maleate may be contained. The catalyst is generally used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, based on 100 parts by weight of the total weight of the epoxy resin composition.

The epoxy resin composition of the present invention may contain a maleimide compound.
As the maleimide compound that can be blended with the epoxy resin composition of the present invention, a conventionally known maleimide compound can be used. Specific examples of the maleimide compound include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3. ′-Dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenyl sulfone bismaleimide 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and the like, but are not limited thereto. These may be used alone or in combination of two or more. The blending amount of the maleimide compound is preferably in the range of 5 times or less, more preferably 2 times or less, the weight of the epoxy resin of the present invention.
Further, the maleimide compound described in Japanese Patent Application Laid-Open No. 2004-107501 (Patent Document 3) is particularly preferable as the maleimide compound because of its low hygroscopicity, flame retardancy and dielectric properties.

In the epoxy resin composition of the present invention, it is preferable to use a radical polymerization initiator for reacting the propenyl groups of the epoxy resin of the formula (1) with each other or with the propenyl group and the maleimide group. Specific examples of the radical polymerization initiator that can be used include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, t-butyl peroxy. Organic peroxides such as benzoate and lauroyl peroxide, azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2,4-dimethylvaleronitrile), etc. Known curing accelerators for azo compounds may be mentioned, but the curing accelerators are not particularly limited thereto. 0.01 to 5 parts by weight is preferable, and 0.01 to 3 parts by weight is particularly preferable, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.

The epoxy resin composition of the present invention contains a curing agent in a preferred embodiment thereof. As the curing agent, amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like can be used. 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. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted) (Phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and polycondensates of various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, biphenols and These modified products, imidazole, BF ₃ -amine complex, guanidine derivative and the like can be mentioned. The amount of the curing agent used is preferably 0.5 to 1.5 equivalents, and particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy groups of the epoxy resin. If the amount is less than 0.5 equivalents or more than 1.5 equivalents to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

A catalyst (curing accelerator) for curing an epoxy resin can be blended in the epoxy resin composition of the present invention, if necessary. For example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and other imidazoles, triethylamine, Amines such as triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, benzyldimethylamine, triphenylphosphine, Examples thereof include phosphines such as tributylphosphine and trioctylphosphine. The compounding amount of the curing catalyst is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the total curable resin composition.

Further, the epoxy resin composition of the present invention, if necessary, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, Forsterite, steatite, spinel, mullite, titania, talc, and other powders, or spherical or crushed inorganic fillers, silane coupling agents, release agents, various compounding agents such as pigments, and various heat A curable resin or the like can be added. Further, particularly when an epoxy resin composition for semiconductor encapsulation is obtained, the amount of the inorganic filler used is usually 80 to 92% by weight, preferably 83 to 90% by weight in the epoxy resin composition.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components in a predetermined ratio, and is usually pre-cured at 130 to 180° C. for 30 to 500 seconds, and further at 150 to 200° C. By post-curing for 2 to 15 hours, a sufficient curing reaction proceeds to obtain the cured product of the present invention. It is also possible to uniformly disperse or dissolve the components of the epoxy resin composition in a solvent or the like, remove the solvent, and then cure.

The thus obtained cured product of the present invention has moisture resistance, heat resistance, and high adhesiveness. Therefore, the epoxy resin composition of the present invention can be used in a wide range of fields where moisture resistance, heat resistance, and high adhesiveness are required. Specifically, it is useful as an insulating material, a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, a resist, or any other material for electric/electronic parts. Further, in addition to molding materials and composite materials, it can be used in fields such as coating materials and adhesives. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.

The epoxy resin composition of the present invention can be used for sealing a semiconductor device. A semiconductor device using the epoxy resin composition of the present invention for sealing has a cured product of the epoxy resin composition of the present invention. As a semiconductor device using the epoxy resin composition of the present invention for sealing, 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), TQFP (think quad flat package) and the like.

An organic solvent may be added to the epoxy resin composition of the present invention to form a varnish-like composition (hereinafter, simply referred to as varnish). Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone Examples of the solvent include aromatic solvents such as toluene and xylene. The solvent is used in such a range that the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.

Further, known additives can be added to the epoxy resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and silica, alumina, calcium carbonate, Quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, inorganic powder such as glass powder, surface treatment agent for filler such as silane coupling agent, release agent , Carbon black, phthalocyanine blue, phthalocyanine green, and the like. The amount of these additives to be blended is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, relative to 100 parts by weight of the epoxy resin composition.

The method for preparing the epoxy resin composition of the present invention is not particularly limited, but each component may be uniformly mixed or prepolymerized. For example, the maleimide resin and the cyanate ester compound are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, an aromatic amine resin and/or a maleimide resin and, if necessary, an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound and other additives may be prepolymerized. Good. In the absence of a solvent, for example, an extruder, a kneader, or a roll is used for mixing or prepolymerization of each component, and in the presence of a solvent, a reaction vessel equipped with a stirrer is used.

A prepreg can be obtained by heating and melting the epoxy resin composition of the present invention to reduce its viscosity and impregnating it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers and alumina fibers.
Further, a prepreg can be obtained by impregnating the varnish with a reinforcing fiber and heating and drying.
Cutting the above prepreg into a desired shape, laminating with a copper foil or the like if necessary, and then heat-curing the curable resin composition while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. Thus, a laminated board for electric/electronics (printed wiring board) or a carbon fiber reinforced material can be obtained.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to these examples. In the examples, the epoxy equivalent, melt viscosity, softening point and total chlorine concentration were measured under the following conditions.
Epoxy equivalent: measured by a method according to JIS K-7236.
Melt viscosity: Melt viscosity in the cone and plate method at 150°C.
Softening point: Measured by a method according to JIS K-7234.
Ratio of propenyl groups in total R: measured by NMR.

Reference example 1
165 parts by weight of 2,2'-diallyl-4,4'-sulfonyldiphenol (TG-SH manufactured by Nippon Kayaku Co., Ltd.) and 200 parts by weight of methanol were charged into a reaction vessel, stirred, dissolved, and then granular hydroxylated. 105 parts by weight of potassium (purity 85%) was added. After the addition, methanol was distilled off while heating, and the reaction was carried out for 4 hours while maintaining the internal temperature at 100°C. After neutralizing with hydrochloric acid, 330 parts by weight of methyl isobutyl ketone was added and washing with water was repeated. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 161 parts by weight of 2,2′-dipropenyl-4,4′-sulfonyldiphenol. The softening point of the obtained 2,2′-dipropenyl-4,4′-sulfonyldiphenol was 81° C.

Example 1
The reaction vessel was charged with 165 parts by weight of 2,2'-dipropenyl-4,4'-sulfonyldiphenol obtained in Reference Example 1, 510 parts by weight of epichlorohydrin, 130 parts by weight of dimethyl sulfoxide, and the mixture was heated, stirred and dissolved, and then the temperature was changed. Was maintained at 45° C., 41 parts by weight of flaky sodium hydroxide was continuously added over 1.5 hours. After the addition of sodium hydroxide was completed, the reaction was carried out at 45°C for 2 hours and at 70°C for 1 hour. Then, excess epichlorohydrin and dimethyl sulfoxide were distilled off under heating and reduced pressure, and 330 parts by weight of methyl isobutyl ketone was added to the residue to dissolve the residue. After removing the by-product salt from this methyl isobutyl ketone solution by washing with water, 10 parts by weight of a 30% aqueous sodium hydroxide solution was added and reacted at 70° C. for 1 hour, followed by washing the reaction solution with water to make the washing solution neutral. Repeated until. Then, 207 parts by weight of the epoxy resin (E1) of the present invention was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The epoxy equivalent of the obtained epoxy resin (E1) was 236 g/eq, the softening point was 64° C., the melt viscosity was 0.09 Pa·s, and the proportion of propenyl groups in all R in the formula (1) was 100%.

Example 2
In Example 1, 165 parts by weight of 2,2'-dipropenyl-4,4'-sulfonyldiphenol was changed to 17 parts by weight, and further 148 parts by weight of 2,2'-diallyl-4,4'-sulfonyldiphenol was added. A similar operation was performed except that the epoxy resin (E2) of the present invention was obtained in an amount of 204 parts by weight. The epoxy equivalent of the obtained epoxy resin (E2) was 237 g/eq, a highly viscous liquid at room temperature, and the proportion of propenyl groups in all R in the formula (1) was 11%.

Example 3
In Example 1, 165 parts by weight of 2,2'-dipropenyl-4,4'-sulfonyldiphenol was changed to 107 parts by weight, and 58 parts by weight of 2,2'-diallyl-4,4'-sulfonyldiphenol was further added. When the same operation was performed except that the addition was performed, 200 parts by weight of the epoxy resin (E3) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin (E3) was 243 g/eq, the softening point was 56° C., and the proportion of propenyl groups in all Rs in the formula (1) was 67%.

Example 4
In Example 1, 165 parts by weight of 2,2'-dipropenyl-4,4'-sulfonyldiphenol was changed to 135 parts by weight, and further 30 parts by weight of 2,2'-diallyl-4,4'-sulfonyldiphenol was added. A similar operation was performed except that the epoxy resin (E4) was added in an amount of 203 parts by weight. The epoxy equivalent of the obtained epoxy resin (E4) was 239 g/eq, the softening point was 64° C., and the proportion of propenyl groups in all Rs in the formula (1) was 85%.

Comparative Synthesis Example 1
The same operation as in Example 1 except that 165 parts by weight of 2,2′-dipropenyl-4,4′-sulfonyldiphenol was changed to 165 parts by weight of 2,2′-diallyl-4,4′-sulfonyldiphenol. Then, 200 parts by weight of an epoxy resin (ER2) was obtained. The epoxy equivalent of the obtained epoxy resin (ER2) was 224 g/eq, and it was semi-solid at room temperature. The proportion of propenyl groups in all Rs in the formula (1) was less than 10%.

Examples 5-6, Comparative Example 1
Various components are mixed in the proportions shown in Table 1 below, kneaded with a mixing roll, tabletted, and then transfer molded to prepare a resin molded product, which is cured at 160°C for 2 hours and further at 180°C for 8 hours, and the physical properties of the cured product Was measured.
-Glass transition temperature (TMA): manufactured by Vacuum Riko Co., Ltd. TM-7000
Temperature rising rate 2℃/min
Water absorption rate: Weight increase rate (%) before and after boiling a disc-shaped test piece having a diameter of 5 cm and a thickness of 4 mm in water at 100° C. for 24 hours

P1: Kayahard GPH (manufactured by Nippon Kayaku Co., Ltd.)
C1:2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
R1: Dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd.)
ER1: diglycidyl bisphenol A (Mitsubishi Chemical Corporation jER-1001)

Examples 8-9, Comparative Examples 2-3
The various components are blended in the proportions shown in Table 2 below, kneaded with a mixing roll, tabletted, and then transfer molded to prepare a resin molded body, which is cured at 160° C. for 2 hours and further at 180° C. for 6 hours to obtain the physical properties of the cured product. Was measured.
・Dynamic viscoelasticity measurement Measurement item: Storage elastic modulus at 30°C
: Glass transition temperature (temperature at maximum tan δ)
Bending elasticity test Measurement item: Modulus of elasticity According to JIS K 6911 A test was performed at room temperature.

From Table 1, it can be confirmed that the cured product using the epoxy resin of the present invention exhibits excellent low hygroscopicity (low water absorption) and heat resistance (solder reflow resistance) as compared with Comparative Examples.
Further, from Table 2, the cured product using the epoxy resin containing a propenyl group of the present invention has excellent heat resistance (glass transition temperature) as compared with the cured product using the epoxy resin of the comparative example having no propenyl group. , It can be confirmed that the strength (elastic modulus) is exhibited. Moreover, it can be confirmed that a cured product having higher heat resistance and strength can be obtained by curing using a radical initiator.

Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the Japanese patent application (Japanese Patent Application No. 2015-156589) filed on August 7, 2015, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated in their entirety.

The epoxy resin of the present invention is used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material), a laminated board (such as a printed wiring board, a board for BGA and a build-up board), and an adhesive (such as a conductive adhesive). It is useful for various composite materials including CFRP and CFRP, and for applications such as paints.

Claims (5)

Formula (1) below

(In the formula, a plurality of Rs each independently represent an allyl group or a 1-propenyl group, and 10% or more of all Rs are 1-propenyl groups. G represents a glycidyl group. Each independently represent a hydrogen atom or a glycidyl group, n is a number from 0 to 10, and the average value thereof represents a real number from 0 to 10), and the epoxy equivalent is 236 to 2151 g/eq. An epoxy resin composition containing the epoxy resin , a curing agent which is a phenolic compound , and a radical polymerization initiator . Formula (1) below

(In the formula, a plurality of Rs each independently represent an allyl group or a 1-propenyl group, and 10% or more of all Rs are 1-propenyl groups. G represents a glycidyl group. Each independently represent a hydrogen atom or a glycidyl group, n is a number from 0 to 10, and its average value represents a real number from 0 to 10), and the epoxy equivalent is 236 to 2151 g/eq. Epoxy resin composition containing a epoxy resin and polymerized modified epoxy resin and a bisphenol, and a curing agent at. The epoxy resin composition according to claim 2 , which contains a radical polymerization initiator. The epoxy resin composition according to any one of claims 1 to 3, which contains a curing accelerator. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4.