JP2020176188A - Curable resin composition and cured product thereof - Google Patents

Abstract

To provide a curable resin composition that is suitably used for insulation materials for electric/electronic components, laminates, various composite materials such as CFRP, adhesives, coatings or the like, has excellent heat resistance and tenacity, and contains an epoxy resin having a biphenyl skeleton and an amine compound.SOLUTION: A curable resin composition contains an epoxy resin represented by Formula (1) and an amine compound (In the formula, Ar represents Formula (X) or Formula (Y). n is 0<n<50. Each R is a hydrogen atom, an alkyl group, a phenyl group or the like, and at least one of them is other than the hydrogen atom.)SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition containing an epoxy resin having a biphenyl skeleton and an amine-based compound, and the cured product has high heat resistance, high elastic modulus, and excellent toughness, so that it is electrically and electronic. It is suitably used in the fields of parts, structural materials, adhesives, paints and the like.

It is generally known that a curable resin composition containing an epoxy resin forms a random network structure by a cross-linking reaction and becomes a cured product having excellent heat resistance, water resistance, and insulating properties. Focusing on these excellent features, in recent years it has expanded to advanced technology fields such as high-performance composite materials such as aircraft materials, printed wiring boards, and electronic materials such as encapsulants, and further high performance. Is required.

In particular, the study of toughness has been carried out for a long time. As a method for improving the performance of the epoxy resin itself to obtain toughness, Patent Document 1 discloses a method for introducing a urethane structure into the skeleton of the epoxy resin. However, in the case of urethane-modified epoxy resins made from bisphenol-type epoxy resins, polyol compounds, and polyisocyanate compounds, in addition to lowering the crosslink density during modification, a flexible skeleton is introduced to impart toughness. Therefore, sufficient heat resistance is not exhibited, or the elastic coefficient tends to decrease. That is, in the method for improving the performance of the epoxy resin itself, there was a trade-off between toughness and heat resistance, or toughness and high elastic modulus.

Further, a method for obtaining toughness by blending an elastomer (rubber component) or a thermoplastic resin with an epoxy resin is disclosed in Non-Patent Document 1. However, with this method, it is inevitable that the heat resistance and elastic modulus will decrease, and the amount of addition must be reduced from the viewpoint of compatibility with the thermoplastic resin and viscosity, so that sufficient strength can be exhibited. Not.

International Publication No. 2015/186707

Journal of the Circuit Mounting Society Vol. 11 No. 1 (1996)

The present invention has been made in view of such a situation, and an object of the present invention is to provide a curable resin having both toughness and heat resistance and a cured product thereof.

As a result of diligent studies to solve the above problems, the present inventors have found that a cured product of a curable resin composition containing an epoxy resin having a biphenyl skeleton and an amine compound has both toughness and heat resistance. The present invention has been completed.

That is, the present invention relates to the following [1] to [12].
[1]
A curable resin composition containing an epoxy resin represented by the following formula (1) and an amine compound.

(In the equation (1), Ars existing in a plurality thereof independently indicate the equation (X) or the equation (Y). * Indicates the coupling position. N is the average value of the number of repetitions, and 0 <n <50. R independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.)
[2]
The curable resin composition according to the preceding item [1], which contains at least one of the formula (Y) as Ar of the formula (1).
[3]
The curable resin composition [4] according to the preceding item [1] or [2], wherein all Rs in the formula (1) are methyl groups.
The curable resin composition according to any one of the above items [1] to [3], wherein the epoxy equivalent of the epoxy resin represented by the formula (1) is 200 to 2000 g / eq.
[5]
The epoxy resin represented by the formula (1) is an epoxy resin obtained by reacting an epoxy resin represented by the following formula (2) with a compound represented by the following formula (3). The curable resin composition according to any one of [4].

(In the equation (2), Ar ₁ existing in a plurality thereof independently indicates the equation (X1) or the equation (Y1). * Indicates the coupling position. N ₁ is the average value of the number of repetitions, and 0 ≦ n ₁ <0.5. R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.)

(In the formula (3), a plurality of R _2s are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, allyl groups, or phenyl groups.)
[6]
The sex resin composition according to the preceding item [5], wherein R _{1 of the} formula (2) is all a methyl group.
[7]
The sex resin composition according to the preceding item [5] or [6], wherein R _{2 of the} formula (3) is all hydrogen atoms.
[8]
The curable resin composition according to any one of the preceding items [1] to [7], which further contains an inorganic filler.
[9]
The curable resin composition according to any one of the above items [1] to [8], which further contains a solvent.
[10]
A prepreg obtained by impregnating a fibrous substance with the curable resin composition according to any one of the above items [1] to [9].
[11]
A sheet obtained by applying the curable resin composition according to any one of the above items [1] to [9] to a surface support.
[12]
A cured product obtained by curing the curable resin composition according to any one of the above items [1] to [9].

The present invention relates to a curable resin composition containing an epoxy resin having a biphenyl skeleton and an amine compound, and the cured product has both toughness and heat resistance. Therefore, the present invention relates to insulating materials for electrical and electronic components (highly reliable semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials such as CFRP, adhesives, paints, etc. It is useful for.

It is a GPC chart of synthesis example 2 of this invention. It is ¹ H-NMR chart of synthesis example 2 of this invention. ¹ H-NMR chart of Synthesis Example 3 of the present invention. It is a bending strength test result of the cured product which concerns on Example 1 of this invention. It is a bending strength test result of the cured product which concerns on Example 2 of this invention. It is a bending strength test result of the cured product which concerns on Comparative Example 1 of this invention. It is a bending strength test result of the cured product which concerns on Comparative Example 2 of this invention.

Hereinafter, the curable resin composition of the present invention will be described in detail.
The curable resin composition of the present invention contains an epoxy resin represented by the following formula (1) and an amine compound.

(In the equation (1), Ars existing in a plurality thereof independently indicate the equation (X) or the equation (Y). * Indicates the coupling position. N is the average value of the number of repetitions, and 0 <n <50. R independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.)

In the formula (1), n is preferably 0.6 <n <20, more preferably 0.8 <n <15, and most preferably 1 <n <10.
n can be determined by GPC (Gel Permeation Chromatography) measurement. It is calculated by multiplying the area% of the peak corresponding to each repeating unit of the GPC chart by the number of repetitions to obtain the total sum.

At least one R is other than a hydrogen atom. R is preferably at least one methyl group, and even more preferably all methyl groups.

The epoxy resin represented by the formula (1) is usually in the form of a solid resin at room temperature, and has a softening point of usually 40 to 200 ° C, preferably 60 to 180 ° C, and more preferably 70 to 120 ° C. .. If the softening point is 40 ° C. or lower, it is semi-solid and difficult to handle, and if the softening point exceeds 200 ° C., it becomes difficult to knead the composition.

The epoxy equivalent of the epoxy resin represented by the formula (1) is usually 200 to 2000 g / eq, preferably 250 to 1000 g / eq, more preferably 250 to 750 g / eq, and 300 to 600 g. When it is / eq, it is particularly preferable, and when it is 350 to 550 g / eq, it is most preferable. If the epoxy equivalent is less than 200 g / eq, sufficient toughness cannot be exhibited, and if the epoxy equivalent is more than 2000 g / eq, the crosslinked network becomes coarse and the heat resistance is lowered.

The epoxy resin represented by the formula (1) has low crystallinity and excellent solvent solubility.
In the formula (1), when a large amount of the formula (Y) is provided, the crystallinity becomes high and the solubility in a solvent is lowered. Therefore, Ar of the formula (1) has at least one formula (Y). The above content is preferable, and the molar ratio of the formula (Y) in the total amount of the formula (X) and the formula (Y) is more preferably 50 mol% or more, and particularly preferably 75 mol%. When the formula (Y) is less than 50 mol%, it dissolves less than 10% by weight in cyclopentanone at 50 ° C., and there is a problem in solvent solubility.

The epoxy resin represented by the formula (1) can be obtained by reacting the epoxy resin represented by the following formula (2) with the compound represented by the following formula (3) (post-reaction).

(In the equation (2), Ar ₁ existing in a plurality thereof independently indicates the equation (X1) or the equation (Y1). * Indicates the coupling position. N ₁ is the average value of the number of repetitions, and 0 ≦ n ₁ <0.5. R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.)

(In the formula (3), a plurality of R _2s are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, allyl groups, or phenyl groups.)

In the formula (2), R ₁ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and preferably a methyl group. Especially preferable.
In the above formula (3), R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

As the epoxy resin represented by the formula (2), a commercially available compound may be used, or a phenol compound may be glycidylated and used. When synthesizing, for example, a phenol compound can be reacted with epihalohydrin. The amount of epihalohydrin used is usually 3.0 to 20.0 mol, preferably 3.5 to 10.0 mol, relative to 1 mol of the hydroxyl group of the phenol compound (1 mol of the total hydroxyl group when multiple types are used; the same applies hereinafter). is there.

Alkali metal hydroxides can be used in the above reactions. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be a solid substance or an aqueous solution thereof may be used. When an aqueous solution is used, the aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or under normal pressure, and further separated to remove water. However, a method of continuously returning epihalohydrin into the reaction system may be used. The amount of the alkali metal hydroxide used is usually 0.9 to 2.5 mol, preferably 0.95 to 1.5 mol, based on 1 mol of the hydroxyl group of the phenol compound. If the amount of alkali metal hydroxide used is small, the reaction will not proceed sufficiently. On the other hand, excessive use of an alkali metal hydroxide exceeding 2.5 mol with respect to 1 mol of the hydroxyl group of the phenol compound causes unnecessary by-product of waste.

In the above reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst in order to accelerate the reaction. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of the phenol compound. If the amount used is too small, a sufficient reaction promoting effect cannot be obtained, and if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin increases, which may cause deterioration of electrical reliability.

In the above reaction, it is preferable to add alcohols such as methanol, ethanol and isopropyl alcohol, an aprotonic polar solvent such as dimethyl sulfoxide, dimethyl sulfoxide, tetrahydrofuran and dioxane to carry out the reaction.
When alcohols are used, the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight, based on the amount of epihalohydrin used. When an aprotonic polar solvent is used, it is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.
After completion of the reaction, the reaction product is washed with water, or the epoxy resin represented by the above formula (2) is obtained by removing epihalohydrin, a solvent and the like under heating and reduced pressure without washing with water. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. It is also possible to carry out a reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol compound used for glycidylation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

The compound represented by the formula (3), but selects the normal biphenol, a compound other than at least one hydrogen atom of R ₁ in the formula (3) can be used in combination about 20 mol% .. As the compound represented by the formula (3) that can be used at this time, 3,3', 5,5'-tetramethylbiphenol is preferable.
The amount of the compound represented by the formula (3) to be used is usually 0.05 to 0.8 mol, preferably 0.1 to 0 mol, based on 1 mol of the epoxy group of the epoxy resin represented by the formula (2). It is 0.7 mol, particularly preferably 0.2 to 0.6 mol. If the amount of the compound represented by the formula (3) used is too small, sufficient solvent solubility cannot be ensured, and if the amount used is too large, it becomes difficult to secure fluidity during production or when the composition is prepared.

In the reaction (post-reaction) between the epoxy resin represented by the formula (2) and one or more of the compounds represented by the formula (3), a low molecular weight epoxy resin is used with 2 phenolic hydroxyl groups. It can be obtained by an advanced method in which the chain is extended with a phenol compound having one or more compounds. The advanced method is excellent in that the molecular structure can be controlled.

If necessary, a catalyst can be used for the post-reaction. Specific examples of the catalyst that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride; quaternary phosphine salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide. , Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo [5,4,0] undecene-7; organic phosphine such as triphenylphosphine, triparatrilphosphine, diphenylphosphine, tributylphosphine Kind; Metal compounds such as tin octylate; Tetra-substituted phosphonium-tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N. − Tetraphenylborone salts such as methylmorpholin and tetraphenylborate can be mentioned. These catalysts are generally 10 ppm to 30,000 ppm, preferably 100 ppm, based on the total weight of the epoxy resin represented by the formula (2) and the compound represented by the formula (3), although it depends on the type of the catalyst. ~ 5000 ppm is used as needed. In the post-reaction, the reaction proceeds without adding a catalyst, so the catalyst should be used as appropriate in consideration of the reaction temperature and the amount of reaction solvent.

In the post-reaction, the solvent may or may not be used. When a solvent is used, any solvent can be used as long as it does not affect the reaction. For example, polar solvents, ethers; dimethylsulfoxide, N, N'-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, jiglime, etc. Ester-based organic solvents such as triglime and propylene glycol monomethyl ether; ketone-based organic solvents such as ethyl acetate, butyl acetate, butyl lactate and γ-butyrolactone; aromatic organic solvents such as methylisobutylketone, methylethylketone, methylisobutylketone and cyclohexanone. Solvent; Toluene, xylene and the like can be used.
The amount of the solvent used is 0 to 300% by weight, preferably 0 to 100% by weight, based on the total weight of the epoxy resin represented by the formula (2) and the compound represented by the formula (3).

The reaction temperature and reaction time in the post-reaction depend on the amount of solvent used and the type and amount of catalyst, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. From the viewpoint of productivity, it is preferable that the reaction time is short. The reaction temperature is 0 to 250 ° C, preferably 80 to 150 ° C.

After completion of the reaction, the epoxy resin, which is one of the essential components of the present invention, can be obtained by removing the catalyst or the like by washing with water or the like as necessary, or by further distilling off the solvent under heating and reduced pressure while leaving the catalyst and the like. Depending on the application, the solvent concentration can be adjusted as it is and used as an epoxy resin varnish.

The curable resin composition of the present invention contains an amine compound together with the epoxy resin represented by the above formula (1). Examples of amine compounds include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 2,2. '-Diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoludiamine, diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4, 4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3, 3', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenylmethane, 4,4'-methylenebis (N-methylaniline), bis (aminophenyl) Fluorene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone , 1,3'-bis (4-aminophenoxy) benzene, 1,4'-bis (4-aminophenoxy) benzene, 1,4'-bis (4-aminophenoxy) biphenyl, 4,4'-(1 , 3-Phenylenideisopropyridin) bisaniline, 4,4'-(1,4-phenylenediisopropyriden) bisaniline, naphthalenediamine, benzidine, dimethylbenzidine, WO 2017/170551 Synthetic Example 1 and Synthetic Example 2 Aromatic amine compounds such as the above aromatic amine compounds, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), norbornandiamine, ethylenediamine, propanediamine, tetramethylenediamine, Examples thereof include aliphatic diamines such as pentamethylenediamine, hexamethylenediamine, dimerdiamine, and triethylenetetramine, but the present invention is not limited to this, and can be suitably used depending on the characteristics to be imparted to the composition. It is preferable to use an aromatic amine to secure the pot life, and it is preferable to use an aliphatic amine when it is desired to impart immediate curability. By using an amine compound containing a bifunctional component as a main component as a curing agent, it is possible to construct a highly linear network similar to a thermoplastic resin during a curing reaction, and exhibit particularly excellent toughness. be able to.

The amount of the amine compound used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. If it is less than 0.5 equivalents or more than 1.5 equivalents with respect to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

In the curable resin composition of the present invention, the epoxy resin represented by the formula (1) can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin represented by the formula (1) in the total epoxy resin is preferably 5 to 95% by weight, more preferably 10 to 95% by weight, still more preferably 15 to 95% by weight. If the amount added is small, sufficient toughness may not be exhibited.

Specific examples of the epoxy resin that can be used in combination with the epoxy resin represented by the formula (1) include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol). , Aromatically substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, etc. Polycondensate with phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); the phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diiso) Polymers of propenylbiphenyl, butadiene, isoprene, etc.; polycondensates of the phenols and ketones (acetones, methylethylketones, methylisobutylketones, acetophenones, benzophenones, etc.); phenols and aromatic dimethanols (benzene, etc.) Polycondensate with dimethanol, biphenyldimethanol, etc.; Polycondensate of the phenols with aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.); Polycondensate with bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); glycidyl ether-based epoxy resin obtained by glycidylating the polycondensate of the bisphenols with various aldehydes or alcohols. , Alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin and the like, but are not limited to these as long as they are commonly used epoxy resins. These may be used alone or two or more kinds may be used.

The curable resin composition of the present invention may be used in combination with a curing agent other than an amine compound. For example, acid anhydride compounds, amide compounds, phenol compounds, active ester compounds and the like can be mentioned. Specific examples of the curing agent that can be used in combination are amide compounds such as polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleine anhydride. Acid anhydride compounds such as acids, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol) , Bisphenol AD, etc.) or 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, etc.) , Alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or the phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien). , Vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or the phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.) Polycondensate of the above, or a polycondensate of the phenol and aromatic dimethanol (benzenedimethanol, biphenyldimethanol, etc.), or the phenol and aromatic dichloromethyls (α, α'-dichloroxylene, etc.) A polycondensate with bischloromethylbiphenyl, etc.), or a polycondensate of the phenols with aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or the bisphenols. Phenolic compounds such as polycondensates of and various aldehydes and modified products thereof; imidazole, trifluoroborane-amine complex, guanidine derivative; phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy Activity of phenols of compounds Sexual ester compounds; and the like, but are not limited thereto.

The curable resin composition of the present invention may be used in combination with a curing accelerator. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethyl imidazole, 2-phenyl imidazole and 2-ethyl-4-methyl imidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, and the like. Triethanolamine, tertiary amines such as 1,8-diazabicyclo [5,4,0] undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine, tributylphosphine, metal compounds such as tin octylate, Tetra-substituted phosphonium-tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetras such as 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholin / tetraphenylborate, etc. Examples thereof include carboxylic acid compounds such as phenylboron salt, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid and salicylic acid. A carboxylic acid compound such as salicylic acid is preferable from the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin. As the curing accelerator, 0.01 to 15 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.

Inorganic fillers can be added to the curable resin composition of the present invention, if necessary. Examples of the inorganic filler include powders of crystalline silica, molten silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc. Spherical beads and the like can be mentioned, but the present invention is not limited to these. These may be used alone or two or more kinds may be used. The amount of these inorganic fillers used varies depending on the application, but when used for semiconductor encapsulants, for example, the heat resistance, moisture resistance, mechanical properties, flame retardancy, etc. of the cured product of the curable resin composition, etc. It is preferable to use it in a proportion of 20% by weight or more in the curable resin composition, more preferably 30% by weight or more, and particularly 70 to 95% by weight in order to improve the linear expansion rate with the lead frame. It is more preferable to use it in a proportion of%.

The curable resin composition of the present invention may contain a mold release agent in order to improve the mold release from the mold at the time of molding. Any of the conventionally known release agents can be used. For example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and partiminic acid, metal salts thereof, and polyolefins such as polyethylene oxide and non-polyethylene oxide. Examples include waxes. These may be used alone or in combination of two or more. The blending amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If it is less than this, the mold release from the mold will be poor, and if it is too large, the adhesion to the lead frame or the like will be poor.

The curable resin composition of the present invention can contain a coupling agent in order to enhance the adhesiveness between the inorganic filler and the resin component. As the coupling agent, any conventionally known one can be used, and for example, vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryoxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and isocyanatoalkoxy are used. Examples thereof include various alkoxysilane compounds such as silane, alkoxy titanium compounds, and aluminum chelate. These may be used alone or in combination of two or more. As a method of adding the coupling agent, the surface of the inorganic filler may be treated with the coupling agent in advance and then kneaded with the resin, or the coupling agent may be mixed with the resin and then the inorganic filler may be kneaded. ..

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 products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide-based compound, cyanate ester-based compound, silicone gel, and silicone oil. , And colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components. The curable resin composition of the present invention can be easily obtained as a cured product by the same method as a conventionally known method. For example, the epoxy resin and the curing agent, and if necessary, the curing accelerator, the inorganic filler, the mold release agent, the silane coupling agent, and the additive are uniformly used using an extruder, a kneader, a roll, or the like as necessary. The curable resin composition of the present invention is obtained by sufficiently mixing, and this is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further at 80 to 200 ° C. for 2 to 10 ° C. A cured product can be obtained by heating for an hour.

Further, the curable resin composition of the present invention may contain a solvent. The curable resin composition (crocodile) containing a solvent is impregnated with a fibrous substance (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and heat-dried to obtain a prepreg. By molding, it can be obtained as a cured product of the curable resin composition of the present invention. The solvent content of this curable resin composition is usually 10 to 70% by weight, preferably about 15 to 70% by weight, when divided internally. Examples of the solvent include amide-based solvents such as γ-butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone; and sulfones such as tetramethylene sulfone; Ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether, preferably lower (1 to 3 carbon atoms) alkylene glycol mono or di lower (1 carbon number carbon number). ~ 3) Alkyl ether; Ketone-based solvent such as methyl ethyl ketone and methyl isobutyl ketone, preferably di-lower (1 to 3 carbon atoms) alkyl ketone in which two alkyl groups may be the same or different; aromatic-based solvent such as toluene and xylene. Examples include solvents. These may be used alone or in a mixed solvent of two or more.

Further, a sheet-shaped adhesive (sheet of the present invention) can be obtained by applying the varnish on the release film, removing the solvent under heating, and performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The cured product of the present invention can be used for various purposes. Specifically, general applications in which thermosetting resins such as epoxy resins are used are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed circuit boards, etc.). (Including wire coating, etc.), sealants, additives to other resins, etc. can be mentioned.

Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office work, medical use, and adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, and anisotropic conductive films (an anisotropic conductive film). ACF), adhesives for mounting such as anisotropic conductive paste (ACP) and the like can be mentioned.

Sealants include potting for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, dipping, transfer mold sealing, potting sealing for ICs and LSIs such as COB, COF and TAB, and flip chips. Examples include sealing (including reinforcing underfill) when mounting IC packages such as underfill, QFP, BGA, and CSP.

Next, the present invention will be described in more detail with reference to Examples. Hereinafter, unless otherwise specified, the parts are parts by weight. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
<Epoxy equivalent>
Measured according to JIS K-7236.
<Softening point>
Measured according to JIS K-7234.
<ICI viscosity (150 ° C)>
Measured according to JIS K-7117-2.
<GPC measurement>
GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
Columns: Shodex KF-603, KF-602x2, KF-601x2)
Linked eluent: tetrahydrofuran Flow rate: 0.5 ml / min.
Column temperature: 40 ° C
Detection: RI (Differential Refractometer)

[Synthesis Example 1]
Tetramethylbiphenol type epoxy resin (trade name: YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.) 380 parts, 4,4'-while applying nitrogen purging to a flask equipped with a thermometer, cooling pipe, fractional distillation pipe, and stirrer. 98 parts of biphenol (manufactured by Tokyo Kasei Co., Ltd.) and 100 parts of methylisobutylketone were charged, the temperature was raised to 100 ° C. with stirring, 0.38 parts of triphenylphosphine was added, and the mixture was reacted at 125 ° C. for 15 hours. By distilling off the methylisobutylketone, an epoxy resin (EP1) represented by the above formula (1) was obtained as a resinous solid. The softening point of the obtained resin was 84 ° C., and the epoxy equivalent was 501 g / eq. It was confirmed that EP1 can be dissolved in cyclopentanone at 50 ° C. in an amount of 10% by weight or more.

[Synthesis Example 2]
Tetramethyl bisphenol type epoxy resin (trade name: YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.) 194 parts, 4, 4'-while applying nitrogen purging to a flask equipped with a thermometer, cooling pipe, fractional distillation pipe, and stirrer. 46.6 parts of biphenol (manufactured by Tokyo Kasei Co., Ltd.) and 60.1 parts of methylisobutyl ketone were charged, the temperature was raised to 100 ° C. with stirring, and then 0.12 parts of triparatrilphosphine (manufactured by Hokuko Chemical Co., Ltd.) was added to 125 After reacting at ° C. for 15 hours, methyl isobutyl ketone was distilled off to obtain an epoxy resin (EP2) represented by the above formula (1) as a resinous solid. The softening point of the obtained resin was 93.8 ° C., the epoxy equivalent was 490 g / eq, the ICI viscosity (150 ° C.) was 3.14 Pa · s, and n in the above formula (1) was 6.4. It was confirmed that EP2 can be dissolved in methyl ethyl ketone and acetone in an amount of 50% by weight or more at 50 ° C. The EP2 GPC chart is shown in FIG. 1 and the ¹ H-NМR chart is shown in FIG.
^{1 1} H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.27 (s, 24H), 2.65-2.70 (m, 2H), 2.82 (t, 2H), 3.58 -3.64 (m, 2H), 3.80-3.92 (m, 3H), 4.18-4.23 (m, 7H), 5.40 (s, 1H), 7.25 (s) , 8H), 7.30 (dd, 6H)

[Synthesis Example 3]
Tetramethyl bisphenol type epoxy resin (trade name: YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.) 1164 parts, 4,4'-while applying nitrogen purging to a flask equipped with a thermometer, cooling pipe, fractional distillation pipe, and stirrer. 223.4 parts of biphenol (manufactured by Tokyo Kasei Co., Ltd.) and 346.9 parts of methylisobutyl ketone were charged, the temperature was raised to 100 ° C. with stirring, and then 0.35 parts of tripalatrilphosphine (manufactured by Hokuko Chemical Co., Ltd.) was added. After reacting at 125 ° C. for 15 hours, methyl isobutyl ketone was distilled off to obtain an epoxy resin (EP3) represented by the above formula (1) as a resinous solid. The softening point of EP3 was 78.5 ° C., the epoxy equivalent was 391 g / eq, the ICI viscosity (150 ° C.) was 0.89 Pa · s, and n in the above formula (1) was 4.3. The ¹ H-NМR chart of EP3 is shown in FIG.
^{1 1} H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.27 (s, 24H), 2.65-2.70 (m, 2H), 2.82 (t, 2H), 3.58 -3.64 (m, 2H), 3.80-3.92 (m, 3H), 4.18-4.23 (m, 6H), 5.40 (s, 2H), 7.25 (s) , 8H), 7.30 (dd, 6H)

[Examples 1 and 2]
Epoxy resins (EP2, EP3) obtained in Synthesis Examples 2 and 3, 4,4'-methylenebis (2,6-diethylaniline) (manufactured by Tokyo Kasei Co., Ltd.) as an amine compound, and salicylic acid (Tokyo) as a curing accelerator. (Manufactured by Kasei Co., Ltd.), blend in the ratio (part by weight) shown in Table 1, mix and knead uniformly using a mixing roll, and after demolding, the conditions are 160 ° C for 2 hours and 180 ° C for 6 hours. To obtain a test piece for evaluation.

[Comparative Example 1]
Epoxy resin (EP2) obtained in Synthesis Example 2, phenol novolac resin (manufactured by Meiwa Kasei Co., Ltd., H-1 softening point 85 ° C., hydroxyl group equivalent 104 g / eq, hereinafter referred to as P-1) as a curing agent, cured. Triphenylphosphine (manufactured by Tokyo Kasei Co., Ltd.) is used as an accelerator, blended in the proportions (parts by weight) shown in Table 1, uniformly mixed and kneaded using a mixing roll, and after demolding, at 160 ° C. for 2 hours. , 180 ° C. for 6 hours to obtain a test piece for evaluation.

[Comparative Example 2]
Biphenyl aralkyl type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as EP4), and 4,4'-methylenebis (2,6-diethylaniline) (manufactured by Tokyo Kasei Co., Ltd.) as an amine compound, curing acceleration Using salicylic acid (manufactured by Tokyo Kasei Co., Ltd.) as an agent, mix in the ratio (part by weight) shown in Table 1, mix and knead uniformly using a mixing roll, and after demolding, heat at 160 ° C for 2 hours at 180 ° C. The mixture was cured under the condition of 6 hours to obtain a test piece for evaluation.

<Heat resistance test>
-Glass transition temperature: The temperature when tan δ is the maximum value measured by a dynamic viscoelasticity tester.
Dynamic viscoelasticity measuring instrument: DMA-2980 manufactured by TA-instruments
Temperature rise rate: 2 ° C / min <Bending test>
-Bending strength: Measured at 30 ° C. according to JIS K-6911.
The measurement limit of elongation in the bending test is 18% GL.
Graphs of bending strength measured in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIGS. 4 to 7, respectively.

EP2: Epoxy resin synthesized in Example 2 EP3: Epoxy resin synthesized in Example 3 EP4: Biphenyl aralkyl type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.)
A-1: 4,4'-Methylenebis (2,6-diethylaniline) (manufactured by Tokyo Kasei Co., Ltd.)
P-1: Phenol novolac (manufactured by H-1 Meiwa Kasei Co., Ltd.)
SA: Salicylic acid (manufactured by Tokyo Kasei Co., Ltd.)
TPP: Triphenylphosphine (manufactured by Tokyo Kasei Co., Ltd.)

According to Table 1 and FIGS. 4 to 7, Examples 1 and 2 were superior in elongation during the test as compared with Comparative Examples 1 and 2, and the test piece was not broken after the test, and the toughness was specifically improved. It was confirmed that there was.

The curable resin composition of the present invention comprises an insulating material for electrical and electronic parts (highly reliable semiconductor encapsulation material, etc.), a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), and an adhesive (conductive adhesion). It is useful for various composite materials such as agents), CFRP, and paints.

Claims (12)

A curable resin composition containing an epoxy resin represented by the following formula (1) and an amine compound.
(In the equation (1), Ars existing in a plurality thereof independently indicate the equation (X) or the equation (Y). * Indicates the coupling position. N is the average value of the number of repetitions, and 0 <n <50. R independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.) The curable resin composition according to claim 1, which contains at least one of the formula (Y) as Ar of the formula (1). The curable resin composition according to claim 1 or 2, wherein all Rs in the formula (1) are methyl groups. The curable resin composition according to any one of claims 1 to 3, wherein the epoxy equivalent of the epoxy resin represented by the formula (1) is 200 to 2000 g / eq. Claims 1 to 1 to claim that the epoxy resin represented by the formula (1) is an epoxy resin obtained by reacting an epoxy resin represented by the following formula (2) with a compound represented by the following formula (3). 4. The curable resin composition according to any one of 4.
(In the equation (2), Ar ₁ existing in a plurality thereof independently indicates the equation (X1) or the equation (Y1). * Indicates the coupling position. N ₁ is the average value of the number of repetitions, and 0 ≦ n ₁ <0.5. R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an allyl group or a phenyl group, and at least one of them is other than a hydrogen atom.)
(In the formula (3), a plurality of R _2s are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, allyl groups, or phenyl groups.) The sex resin composition according to claim 5, wherein R _{1 of the} formula (2) is all a methyl group. The sex resin composition according to claim 5 or 6, wherein R _{2 of the} formula (3) is all hydrogen atoms. The curable resin composition according to any one of claims 1 to 7, further comprising an inorganic filler. The curable resin composition according to any one of claims 1 to 8, further comprising a solvent. A prepreg obtained by impregnating a fibrous substance with the curable resin composition according to any one of claims 1 to 9. A sheet obtained by applying the curable resin composition according to any one of claims 1 to 9 to a surface support. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.