WO2018110550A1

WO2018110550A1 - Thermosetting resin composition, photocurable resin composition, cured product and heat resistance improving agent

Info

Publication number: WO2018110550A1
Application number: PCT/JP2017/044570
Authority: WO
Inventors: 慎吾金谷
Original assignee: ナガセケムテックス株式会社
Priority date: 2016-12-15
Filing date: 2017-12-12
Publication date: 2018-06-21
Also published as: JPWO2018110550A1

Abstract

The purpose of the present invention is to provide: a thermosetting resin composition or a photocurable resin composition, which enables the achievement of a cured product that has excellent mechanical strength and excellent heat resistance. A thermosetting resin composition which contains (A) an epoxy resin having an average number of epoxy groups of 2 or more, (B) a silsesquioxane derivative which has a weight average molecular weight Mw of from 2,000 to 10,000 (inclusive), while containing RSiO_3/2 groups as repeating constituent units, and wherein from 50% by mole to 100% by mole (inclusive) of all the repeating constituent units contained in each molecule are essential repeating constituent units wherein R is an organic group containing a glycidyl group and from 0% by mole to 50% by mole (inclusive) of all the repeating constituent units contained in each molecule are optional repeating constituent units wherein R is an aryl group and/or an alkyl group having 1 to 12 carbon atoms (inclusive), and (C) an amine compound having two or more amino groups which are reactive with the epoxy groups. From 5 parts by weight to 30 parts by weight (inclusive) of the silsesquioxane derivative (B) is contained per 100 parts by weight of the epoxy resin (A).

Description

Thermosetting resin composition, photocurable resin composition, cured product and heat resistance improver

The present invention relates to a thermosetting resin composition, a photocurable resin composition, a cured product, and a heat resistance improver.

Generally, an epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, it is used in a wide range of fields such as electrical / electronic materials, structural materials, and paints. In particular, in the field of electrical and electronic materials such as semiconductor sealants, laminates, FRP (composite materials), adhesives, etc., epoxy resins such as bisphenol A type epoxy resins are used because of a good balance between heat resistance and mechanical strength. It is used a lot.

Patent Document 1 gives a cured product excellent in low viscosity, low stress, and adhesiveness, and is suitable as an epoxy compound suitable for electrical / electronic device materials such as semiconductor sealing materials and underfill materials. Epoxy obtained by condensing an epoxy group-containing alkoxysilicon compound in the presence of a basic catalyst as an epoxy group-containing silicon compound that can be a component of a thermosetting resin composition that gives a cured product with excellent heat resistance Compounds are disclosed.

JP 2006-008747 A International Publication No. 2004/072150 Pamphlet

In recent years, the demand for long-term reliability of epoxy resins has advanced, and there is a strong demand for improving heat resistance without impairing mechanical strength. However, conventional epoxy compounds are particularly difficult to obtain sufficient heat resistance, and are insufficient in terms of both mechanical strength and heat resistance. An object of this invention is to provide the thermosetting resin composition or photocurable resin composition which can obtain the hardened | cured material excellent in mechanical strength and heat resistance.

The first of the present invention is (A) an epoxy resin having an average epoxy group number of 2 or more, and (B) RSiO _3/2 as a repeating structural unit, and among all the repeating structural units contained in one molecule, it is essential. A repeating unit in which R is an organic group containing a glycidyl group as a component is 100 mol% or less and 50 mol% or more, and R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms as an optional component Silsesquioxane derivatives having a weight average molecular weight Mw of 2,000 to 10,000, and (C) an amine having two or more amino groups capable of reacting with the epoxy group, wherein the unit is 50 mol% or less and 0 mol% or more. A thermosetting compound comprising 5 parts by weight to 30 parts by weight of the (B) silsesquioxane derivative with respect to 100 parts by weight of the (A) epoxy resin. This invention relates to a curable resin composition.

In the thermosetting resin composition, it is preferable that (A) the epoxy resin is an aromatic epoxy resin.

The second of the present invention relates to a cured product obtained by curing the thermosetting resin composition.

In the third aspect of the present invention, (A) an epoxy resin having an average number of epoxy groups of 2 or more and (B) RSiO _3/2 as a repeating structural unit, among all the repeating structural units contained in one molecule, essential A repeating unit in which R is an organic group containing a glycidyl group as a component is 100 mol% or less and 50 mol% or more, and R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms as an optional component A unit containing 50 mol% or less and 0 mol% or more of a weight average molecular weight Mw of 2,000 or more and 10,000 or less of a silsesquioxane derivative, and (D) a photocationic polymerization initiator, and the (A) epoxy resin 100 It is related with the photocurable resin composition whose said (B) silsesquioxane derivative is 30 to 150 weight part with respect to a weight part.

4th of this invention is related with the hardened | cured material formed by hardening | curing the said photocurable resin composition.

A fifth aspect of the present invention is an additive for improving the heat resistance of an epoxy resin, wherein RSiO _3/2 is a repeating structural unit and is an essential component among all the repeating structural units contained in one molecule. The repeating structural unit in which R is an organic group containing a glycidyl group is 100 mol% or less and 50 mol% or more, and R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms as an optional component Relates to a heat resistance improver comprising a silsesquioxane derivative having a weight average molecular weight Mw of 2,000 to 10,000.

According to the present invention, a thermosetting resin composition or a photocurable resin composition capable of obtaining a cured product having excellent mechanical strength and heat resistance can be obtained.

Hereinafter, an example of a preferred embodiment of the present invention will be specifically described.

[Thermosetting resin composition and photocurable resin composition]
The thermosetting resin composition of the present invention comprises (A) an epoxy resin, (B) a silsesquioxane derivative, and (C) an amine-based compound, and (A) 100 parts by weight of the epoxy resin (B) The silsesquioxane derivative is 5 parts by weight or more and 30 parts by weight or less.

The photocurable resin composition of the present invention comprises (A) an epoxy resin, (B) a silsesquioxane derivative, and (D) a photocationic polymerization initiator, and (A) 100 parts by weight of the epoxy resin ( B) The silsesquioxane derivative is 30 parts by weight or more and 150 parts by weight or less.

[(A) Epoxy resin]
(A) The epoxy resin has an average number of epoxy groups of 2 or more. It is not particularly limited as long as it is an epoxy resin having two or more average epoxy groups, and various epoxy resins such as aromatic epoxy resins, aliphatic epoxy resins, and alicyclic epoxy resins can be used. Of these, aromatic epoxy resins are preferred because of their excellent heat resistance.

(A) The epoxy resin is not particularly limited as long as the average number of epoxy groups is 2 or more, but the average number of epoxy groups is preferably 2 or more and 4 or less. By setting it as this range, since (A) epoxy resin can take a crosslinked structure, it is excellent in heat resistance. On the other hand, if the average number of epoxy groups is less than 2, a sufficient cross-linked structure cannot be obtained, so that (A) epoxy resin cannot obtain sufficient cured product properties, and electrical / electronic materials, structural materials, paints, etc. Can not be used as.

The average number of epoxy groups can be determined by dividing the weight average molecular weight determined by gel permeation chromatography (GPC) by the epoxy equivalent determined in accordance with JIS K7236.

The aromatic epoxy resin is not particularly limited as long as it has an aromatic ring in one molecule and has an average number of epoxy groups of 2 or more. For example, bisphenol compounds such as bisphenol A and bisphenol F or derivatives thereof; biphenyl compounds such as 4,4′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol or the like Derivative; Trifunctional phenyl resin having trihydroxyphenylmethane skeleton and aminophenol skeleton; Phenol novolak resin; Cresol novolak resin; Phenol aralkyl resin having phenylene skeleton; Phenol aralkyl resin having biphenylene skeleton; Naphthol aralkyl resin; An epoxy resin obtained by epoxidizing a derivative of

Among these aromatic epoxy resins, bisphenol compounds such as bisphenol A and bisphenol F or their derivatives, phenol novolac resins, cresol novolac resins, and diaminodiphenylmethane skeletons because the cured products obtained have good heat resistance and mechanical strength. Epoxy resins obtained by epoxidizing these derivatives are preferred.

The aliphatic epoxy resin is not particularly limited as long as it has an aliphatic skeleton and has an average number of epoxy groups of 2 or more. For example, epoxy resins obtained by epoxidizing aliphatic diols such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, nonanediol, decanediol, polyhydric alcohols such as pentaerythritol, sorbitol, or derivatives thereof Etc.

Among these aliphatic epoxy resins, epoxy resin obtained by epoxidizing hexanediol, ethylene glycol, propylene glycol, pentaerythritol, or a derivative thereof is preferable because of its excellent compatibility with the (B) silsesquioxane derivative.

The alicyclic epoxy resin is not particularly limited as long as it has an alicyclic skeleton in one molecule and has an average number of epoxy groups of 2 or more. For example, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate; 2,3-bis (hydroxymethyl) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol; dicyclopentadiene type epoxy resin; and hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol And diols having an alicyclic structure such as sirolohexanediethanol or derivatives thereof.

Among these alicyclic epoxy resins, it is preferable to use 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate because the resulting cured product has particularly excellent heat resistance and mechanical strength.

Various epoxy resins such as the aromatic epoxy resin, aliphatic epoxy resin, and alicyclic epoxy resin may be used alone or in combination of two or more.

[(B) Silsesquioxane derivative]
(B) The silsesquioxane derivative has a repeating structure in which RSiO _3/2 is a repeating structural unit, and R is an organic group containing a glycidyl group as an essential component among all the repeating structural units contained in one molecule. The repeating unit in which the unit is 100 mol% or less and 50 mol% or more and R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms as an optional component is 50 mol% or less and 0 mol% or more, The weight average molecular weight Mw is 2,000 or more and 10,000 or less.

(B) Among all the above repeating structural units contained in one molecule of the silsesquioxane derivative, the repeating structural unit in which R is an organic group containing a glycidyl group is 100 mol% or less and 50 mol% or more as an essential component. When included in a ratio, the ratio is preferably 100 mol% or less and 75 mol% or more, more preferably 100 mol% or less and 90 mol% or more, further preferably 100 mol% or less and 95 mol% or more, and more preferably 100 mol%. Most preferred. This is because the resulting cured product has more excellent mechanical strength and heat resistance. If it is less than 50 mol%, both mechanical strength and heat resistance tend to decrease.

(B) Of all the above repeating structural units contained in one molecule of the silsesquioxane derivative, a repeating structural unit in which R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms is an optional component of 50 When included in a proportion of not more than mol% and not less than 0 mol%, the proportion is preferably not more than 25 mol% and not less than 0 mol%, more preferably not more than 10 mol% and not less than 0 mol%, most preferably 0 mol%. . This is because the resulting cured product has more excellent mechanical strength and heat resistance. When it exceeds 50 mol%, both mechanical strength and heat resistance tend to decrease.

Examples of the organic group containing a glycidyl group include a glycidoxyalkyl group to which an oxyglycidyl group having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, and γ-glycidoxybutyl is bonded; Glycidyl group: β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxy) Substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as (cyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, and β- (3,4-epoxycyclohexyl) pentyl group. And alkyl groups.

Among these organic groups containing a glycidyl group, (C) a glycidoxyalkyl group is preferred in the thermosetting resin composition because of its excellent reactivity with amine compounds. Moreover, (D) Since it is excellent in the reactivity with a photocationic polymerization initiator, in a photocurable resin composition, a glycidoxyalkyl group is preferable. Sufficient cured product characteristics (heat resistance and mechanical strength) can be obtained by excellent reactivity with (C) amine compound or (D) photocationic polymerization initiator.

Examples of the aryl group include a phenyl group; and alkylaryl groups such as a methylphenyl group and a dimethylphenyl group. The alkyl group having 1 to 12 carbon atoms may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group. Group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, isopentyl group, 2-methylbutyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 4-methylpentyl group, 3-methylpentyl group Group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, heptyl group, n-octyl group, isooctyl group Nonyl group, decyl group, and undecyl group.

Among the aryl group or the alkyl group having 1 to 12 carbon atoms, the cured product obtained by curing the resulting thermosetting resin composition and the cured product obtained by curing the photocurable resin composition are excellent in heat resistance, (A) A methyl group, phenyl group, isobutyl, isooctyl group, and the like are preferable because they are compatible with the epoxy resin without any problem.

(B) in the silsesquioxane derivative, R is the composition of _{RSiO 3/2} is an organic group containing a glycidyl group, and R is an aryl group and / or one or more carbon atoms and 12 or less alkyl groups _{RSiO 3/2} The composition of can be analyzed by ¹ H-NMR or FTIR. As the apparatus, JNM-ECZR (manufactured by JEOL Ltd., 400 MHz) can be used for ¹ H-NMR, and Frontier Optica (manufactured by PerkinElmer, KBr method) can be used for FTIR.

Generally, it is known that silsesquioxane derivatives can be obtained in a ladder type, a random type, or other structures (such as a cage type structure) depending on hydrolysis and condensation conditions. The (B) silsesquioxane derivative of the present invention preferably has a ladder type structure or a random type structure, or has both a ladder type structure and a random type structure. In particular, the (B) silsesquioxane derivative preferably contains a ladder type structure and / or a random type structure in an amount of 80% by weight or more, and 85% by weight or more because the resulting cured product has excellent impact resistance. It is preferably contained, and more preferably 90% by weight or more. Furthermore, among these, since the mechanical strength of the hardened | cured material obtained is excellent, the one where the content rate of a ladder type structure is higher is preferable.

Further, the (B) silsesquioxane derivative may contain a structure other than the ladder type and the random type. (B) In the production of the silsesquioxane derivative, other structures are inevitably produced as by-products, and this may coexist in small amounts as impurities. Examples of the structure other than the ladder type and the random type include what is usually called a cage structure. The cage structure includes an incomplete cage structure in which a part of the cage structure is opened.

(B) The content of the ladder structure and / or the random structure in the silsesquioxane derivative can be determined as follows. A cage structure (a part of the cage structure was opened from the m / z peak area derived from the cage structure of the silsesquioxane derivative (B) by liquid chromatography mass spectrometry (LC-MS). The content of the ladder structure and / or the random structure is obtained by subtracting the weight of the cage structure obtained from the weight of the silsesquioxane derivative (B). The content can be determined.

(B) The silsesquioxane derivative is an essential component in which R is an RSiO _3/2 introduction of an organic group containing a glycidyl group, so that a trialkoxysilane in which R has an organic group containing a glycidyl group; A trialkoxysilane having an aryl group and / or an alkyl group having 1 to 12 carbon atoms in order to introduce RSiO _3/2 in which R, which is an optional component, is an aryl group and / or an alkyl group having 1 to 12 carbon atoms; And can be obtained by performing a hydrolysis / condensation reaction.

Specific examples of trialkoxysilane in which R has an organic group containing a glycidyl group include, for example, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxy Examples include silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

Examples of the trialkoxysilane having an aryl group and / or an alkyl group having 1 to 12 carbon atoms include phenyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, and butyltrimethoxysilane. And isobutyltrimethoxysilane, hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, n-decyltrimethoxysilane and the like. These may be used alone or in combination of two or more.

The conditions for the hydrolysis / condensation reaction are preferably 30 to 120 ° C. and 1 to 24 hours, more preferably 40 to 90 ° C. and 2 to 12 hours, still more preferably 50 to 70 ° C. 3-8 hours.

In the hydrolysis / condensation reaction, a catalyst may be used. Examples of the catalyst include a basic catalyst and an acidic catalyst. Examples of the basic catalyst include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, tetramethylammonium hydroxide or sodium hydroxide is preferably used because of its high catalytic activity. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Among these, hydrochloric acid, nitric acid, or acetic acid is preferably used because of its high catalytic activity.

In addition, a solvent can be used for the hydrolysis / condensation reaction as necessary. Examples of such solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. Glycol ethers such as ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether; alkylene glycol compounds such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate and 3-methoxybutyl-1-acetate Alkyl ether acetates; toluene, aromatic hydrocarbons such as xylene; methyl ethyl ketone, methyl isobutyl ketone (MIBK), may be mentioned ketones such as methyl amyl ketone, cyclohexanone. These solvents may be used alone or in a combination of two or more.

Of the manufacturing methods capable of obtaining a ladder-type or random-type structure, the method described in JP-A-6-306173 can be exemplified mainly for the ladder-type structure.

(B) The silsesquioxane derivative is a cured product obtained by curing the resulting thermosetting resin composition or a cured product obtained by curing the photo-curable resin composition. The weight average molecular weight Mw is 2,000 or more and 10,000 or less. The lower limit of the weight average molecular weight Mw is preferably 2,500 or more, and more preferably 3,000 or more. Further, the upper limit value of the weight average molecular weight Mw is preferably 8,000 or less, and more preferably 7,000 or less. When the weight average molecular weight Mw is less than 2,000, the mechanical strength is remarkably lowered, and when the weight average molecular weight Mw exceeds 10,000, the viscosity becomes too high and (A) workability when blended with an epoxy resin. Optical properties of a cured product obtained by curing a thermosetting resin composition or a photocurable resin composition obtained by curing the thermosetting resin composition obtained by reducing the compatibility with the epoxy resin. (Transparency) tends to deteriorate. The weight average molecular weight Mw is a value measured by polystyrene permeation gel permeation chromatography (GPC). A Waters Shodex KF-803L column can be used for the measurement.

(B) The viscosity of the silsesquioxane derivative is preferably 1,000 mPa · s to 50,000 mPa · s at 25 ° C., more preferably 3,000 mPa · s to 30,000 mPa · s. It is because it is excellent in workability | operativity and compatibility because it is this range.

The thermosetting resin composition of the present invention contains (A) an epoxy resin, (B) a silsesquioxane derivative, and (C) an amine compound. The content of (B) the silsesquioxane derivative is: (A) It is 5 to 30 weight part with respect to 100 weight part of epoxy resins. (B) The lower limit of the content of the silsesquioxane derivative may be 10 parts by weight or more, or 15 parts by weight or more, and the upper limit may be 25 parts by weight or less, or 20 parts by weight or less. . (B) When the silsesquioxane derivative is 5 parts by weight or more and 30 parts by weight or less, the cured product obtained by curing the obtained thermosetting resin composition has both excellent mechanical strength and heat resistance. Can do. On the other hand, if it is less than 5 parts by weight, both the mechanical strength and the heat resistance are insufficient, and if it exceeds 30 parts by weight, both the mechanical strength and the impact resistance are lowered, and the mechanical strength is particularly deteriorated.

The photocurable resin composition of the present invention contains (A) an epoxy resin, (B) a silsesquioxane derivative, and (D) a photocationic polymerization initiator. (A) It is 30 to 150 weight part with respect to 100 weight part of epoxy resins. (B) The lower limit of the content of the silsesquioxane derivative may be 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more, and the upper limit is 130 parts by weight or less, or 100 parts by weight or less. It may be. (B) When the silsesquioxane derivative is 30 parts by weight or more and 150 parts by weight or less, the cured product obtained by curing the obtained photocurable resin composition has both excellent mechanical strength and heat resistance. Can do. On the other hand, if the amount is less than 30 parts by weight, both the mechanical strength and the heat resistance are insufficient. If the amount exceeds 150 parts by weight, both the mechanical strength and the impact resistance are lowered, and the mechanical strength is particularly deteriorated.

(B) The silsesquioxane derivative can be used as a heat resistance improver that improves the heat resistance of the (A) epoxy resin by being added to the (A) epoxy resin.

[(C) amine compound]
The (C) amine compound contained in the thermosetting resin composition is not particularly limited as long as it is an amine compound having two or more amino groups capable of reacting with the epoxy group contained in the (A) epoxy resin. Various amine compounds such as alicyclic amines, aromatic amines, ketimine compounds, and guanidine derivatives can be used.

Examples of the aliphatic amine include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Examples of alicyclic amines include isophorone diamine, 1,2-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4′-methylenebis (2-methylcyclohexaneamine), 1- (2-amino And alicyclic polyamines such as ethyl) piperazine, bis (4-aminocyclohexyl) methane, and norbornanediamine.

Examples of aromatic amines include aromatic polyamines such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dimethylbenzylamine, diethyltoluenediamine, and m-xylylenediamine.

The various (C) amine compounds may be used alone or in combination of two or more. Among the (C) amine compounds, 4,4′-methylenebis (2-methylcyclohexaneamine) is preferably used because of excellent reactivity with (A) epoxy resin and (B) silsesquioxane derivative. .

The content of the (C) amine compound in the thermosetting resin composition of the present invention is 0.5 equivalent or more and 1.1 equivalent or less with respect to 1 equivalent of the epoxy group in the thermosetting resin composition. It is preferable to set it to 0.7 equivalent or more and 1.0 equivalent or less. In terms of weight ratio, the lower limit of (C) amine compound is 10 parts by weight or more or 20 parts by weight or more with respect to 100 parts by weight of the total of (A) epoxy resin and (B) silsesquioxane derivative. The upper limit may be 50 parts by weight or less or 40 parts by weight or less. The amount of the (C) amine compound is preferably 20 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total of (A) the epoxy resin and (B) the silsesquioxane derivative. When the (C) amine compound is within this range, a cured product obtained by curing the resulting thermosetting resin composition can achieve both excellent mechanical strength and excellent heat resistance. On the other hand, when the content is less than 10 parts by weight, curing is delayed, and when it exceeds 50 parts by weight, the mechanical strength is lowered and the resulting cured product is strongly colored. When a silsesquioxane derivative having a structure other than a ladder type or random type is included as an impurity, the content of the (C) amine compound may be appropriately reduced and increased in consideration of the content.

[(D) Photocationic polymerization initiator]
The photocationic polymerization initiator (D) possessed by the photocurable resin composition generates a strong acid such as tetrafluoroboric acid or hexafluorophosphoric acid by UV irradiation or heating, and (A) an epoxy resin or ( B) There is no particular limitation as long as the silsesquioxane derivative is activated and can initiate a polymerization reaction.

(D) As the photocationic polymerization initiator, for example, as commercially available products, IRGACURE (registered trademark) 270, IRGACURE (registered trademark) 290 (manufactured by BASF), Adekaoptomer (registered trademark) SP-150, Adekatop Triarylsulfonium salts such as Mer (registered trademark) SP-170 (manufactured by ADEKA), CPI (registered trademark) -100P, CPI (registered trademark) -101A, and CPI (registered trademark) -200K (manufactured by San Apro); IRGACURE (registered trademark) 250 (manufactured by BASF), WPI (registered trademark) -113, WPI (registered trademark) -116, WPI (registered trademark) -124 (manufactured by Wako Pure Chemical Industries, Ltd.), and PI (registered trademark)- Diaryliodonium salts such as 2074 (manufactured by Solvay Japan) can be used.

The various (D) photocationic polymerization initiators may be used alone or in combination of two or more. Among the above (D) photocationic polymerization initiators, a triarylsulfonium salt is preferably used because of excellent reactivity with the (A) epoxy resin and the (B) silsesquioxane derivative.

The content of the (D) photocationic polymerization initiator in the photocurable resin composition of the present invention is (D) a photocation with respect to a total of 100 parts by weight of the (A) epoxy resin and (B) silsesquioxane derivative. The lower limit of the polymerization initiator may be 0.1 parts by weight or more or 0.5 parts by weight or more, and the upper limit may be 10 parts by weight or less or 5 parts by weight or less. The total amount of (A) epoxy resin and (B) silsesquioxane derivative is 100 parts by weight, and (D) the cationic photopolymerization initiator is preferably 0.5 parts by weight or more and 5 parts by weight or less. (D) When the content of the cationic photopolymerization initiator is within this range, the cured product obtained by curing the photocurable resin composition obtained has both excellent mechanical strength and excellent heat resistance. Can do. On the other hand, when the content is less than 0.1 parts by weight, curing is delayed, and when it exceeds 10 parts by weight, the cured product becomes brittle and the mechanical strength is remarkably reduced. In addition, when the silsesquioxane derivative having a structure other than the ladder type and the random type is included as an impurity, the content of the (D) photocationic polymerization initiator is appropriately reduced and increased in consideration of the content as appropriate. Good.

[Cured product]
A cured product can be produced by advancing curing of the thermosetting resin composition or the photocurable resin composition of the present invention. The production is performed by heating the thermosetting resin composition of the present invention and, if necessary, post-curing by heating, or by UV irradiation and, if necessary, UV irradiation or heating by heating the photocurable resin composition. After post-curing, for example, cooling with a mold or the like, and curing may be mentioned.

The cured product obtained by curing the thermosetting resin composition of the present invention and the cured product obtained by curing the photocurable resin composition can achieve both excellent mechanical strength and heat resistance.

The cured product obtained by curing the thermosetting resin composition of the present invention and the cured product obtained by curing the photo-curable resin composition are partially entangled when the cut surface is observed by SEM (500 times). A fibrous substance showing a certain direction can be confirmed. The cured product can be said to be in a state where the fibrous substance and other regions are phase-separated, and by taking such a state, the fibrous substance has an effect as a molecular chain molecular filler in the cured product. In order to suppress the micro Brownian motion, it is presumed that both excellent mechanical strength and excellent heat resistance can be achieved.

Such a state in which the fibrous substance and other regions are phase-separated can be obtained as follows. The (B) silsesquioxane derivative has a glass transition temperature Tg of a cured product obtained when (C) an amine compound or (D) a photocationic polymerization initiator is used as a curing agent, compared with (A) an epoxy resin. And very low. A fiber obtained by curing (A) an epoxy resin with (C) an amine compound or (D) a photocationic polymerization initiator together with (B) a silsesquioxane derivative having a relatively low glass transition temperature Tg. The state-like substance and other regions are in a phase-separated state. For example, when an acid anhydride curing agent is used as the curing agent instead of (C) the amine compound, it cannot be obtained.

The bending strength of a cured product obtained by curing the thermosetting resin composition of the present invention is preferably 80 MPa or more, more preferably 81 MPa or more, and further preferably 82 MPa or more. The bending strength is preferably higher, and the upper limit is not particularly limited, but for example, it can be practically used if it is 100 MPa or less. The elongation percentage is preferably 4.0% or more, more preferably 4.1% or more, still more preferably 4.3% or more, and most preferably 4.5% or more. From a practical viewpoint, it may be 5% or less.

The bending strength and elongation of the cured product can be measured by a test method based on JIS K7171.

The glass transition temperature of the cured product obtained by curing the thermosetting resin composition and the photocurable resin composition of the present invention depends on the type of epoxy resin used, but compared with the case where the epoxy resin is used alone. The temperature is preferably increased by 10 ° C or more, more preferably by 15 ° C or more, and further preferably by 20 ° C or more.

The glass transition temperature Tg of a cured product obtained by curing the thermosetting resin composition and the photocurable resin composition of the present invention is 165 ° C. or higher when an aromatic epoxy resin is used as the (A) epoxy resin. It is preferably 168 ° C. or higher, more preferably 170 ° C. or higher. The glass transition temperature Tg is preferably higher, and the upper limit value is not particularly limited.

The glass transition temperature Tg of the cured product obtained by curing the thermosetting resin composition and the photocurable resin composition of the present invention is 90 ° C or higher when an alicyclic epoxy resin is used as the (A) epoxy resin. Preferably, it is 100 ° C. or higher, more preferably 105 ° C. or higher. The glass transition temperature Tg is preferably higher, and the upper limit value is not particularly limited.

The glass transition temperature Tg of the cured product is measured using a differential scanning calorimetry (DSC) apparatus or a dynamic viscoelasticity measuring apparatus such as DMS6100 (manufactured by Seiko Instruments Inc.) in a temperature range of 30 to 250 ° C. and a temperature increase rate of 2 It can be measured under the conditions of ° C / min and frequency of 1 MHz.

The elastic modulus of a cured product obtained by curing the photocurable resin composition of the present invention is preferably 1.5 GPa or more, more preferably 1.8 GPa or more, and further preferably 2.0 GPa or more. The higher elastic modulus is preferable, and the upper limit is not particularly limited, but for example, it can be practically used if it is 5.0 GPa or less.

The elastic modulus of the cured product can be measured using a dynamic viscoelasticity measuring device such as DMS6100 (manufactured by Seiko Instruments Inc.) under conditions of a frequency of 1 Hz and 25 ° C.

The pencil hardness of a cured product obtained by curing the photocurable resin composition of the present invention is preferably 3H or more, and more preferably 4H or more. Although an upper limit is not specifically limited, From a viewpoint of mechanical strength, it is 6H or less, for example. The pencil hardness can be measured by a test method based on JIS K 5600-5-4.

As described above, a cured product obtained by curing a thermosetting resin composition or a cured product obtained by curing a photocurable resin composition has excellent mechanical strength and excellent heat resistance. High mechanical and electrical connection, despite being easily exposed to high temperatures and high humidity, used in the fields of electrical and electronic materials such as laminates, FRP (composite materials), adhesives, and automotive materials It can be suitably used as a component material that requires reliability.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
Synthesis of Silsesquioxane (SQ) Derivative 1 In a reaction vessel equipped with a stirrer and a thermometer, 50.0 g of MIBK, 0.700 g of a 20% aqueous solution of sodium hydroxide (3.50 mmol of sodium hydroxide), distilled water 9. After charging 00 g (500 mmol), 50.0 g (212 mmol) of γ-glycidoxypropyltrimethoxysilane was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 50.0 g of MIBK was added, and further washed with 25.0 g of distilled water until the pH of the aqueous layer became neutral. Next, MIBK was distilled off under reduced pressure to obtain the target compound, SQ derivative 1. Mw was 3,850. When IR analysis supports that include ladder or random structure was confirmed a peak around 1100 cm ^-1 and 1050 cm ^-1 based on the stretching vibration of Si-O-Si bonds. As for the repeating structural unit constituting the SQ derivative 1, RSiO _3/2 in which R is a glycidoxypropyl group was 100 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the random structure and / or the ladder structure was 87% by weight.

(Synthesis Example 2)
Synthesis of Silsesquioxane (SQ) Derivative 2 In a reaction vessel equipped with a stirrer and a thermometer, 50.0 g of MIBK, 0.700 g of a 20% aqueous solution of sodium hydroxide (3.50 mmol of sodium hydroxide), distilled water 9. After charging 10 g (506 mmol), 48.5 g (205 mmol) of γ-glycidoxypropyltrimethoxysilane and 1.50 g (11.0 mmol) of methyltrimethoxysilane were gradually added at 50 to 55 ° C. and stirred for 3 hours. I left it alone. After completion of the reaction, 50.0 g of MIBK was added, and further washed with 25.0 g of distilled water until the pH of the aqueous layer became neutral. Next, MIBK was distilled off under reduced pressure to obtain the target compound, SQ derivative 2. Mw was 5,300. When IR analysis supports that include ladder or random structure was confirmed a peak around 1100 cm ^-1 and 1050 cm ^-1 based on the stretching vibration of Si-O-Si bonds. As for the repeating structural units constituting the SQ derivative 2, RSiO _3/2 in which R is a glycidoxypropyl group was 95 mol%, and RSiO _{3/2 in} which R was a methyl group was 5 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the random structure and / or the ladder structure was 89% by weight.

(Synthesis Example 3)
Synthesis of Silsesquioxane (SQ) Derivative 3 In a reaction vessel equipped with a stirrer and a thermometer, MIBK 50.0 g, sodium hydroxide 2050 aqueous solution 0.750 g (sodium hydroxide 3.75 mmol), distilled water 9. After charging 80 g (544 mmol), 27.2 g (115 mmol) of γ-glycidoxypropyltrimethoxysilane and 22.8 g (115 mmol) of phenyltrimethoxysilane were gradually added at 50 to 55 ° C. and left to stir for 3 hours. . After completion of the reaction, 50.0 g of MIBK was added, and further washed with 25.0 g of distilled water until the pH of the aqueous layer became neutral. Next, MIBK was distilled off under reduced pressure to obtain the target compound, SQ derivative 3. Mw was 3,350. When IR analysis supports that include ladder or random structure was confirmed a peak around 1100 cm ^-1 and 1050 cm ^-1 based on the stretching vibration of Si-O-Si bonds. As for the repeating structural units constituting the SQ derivative 3, RSiO _3/2 in which R is a glycidoxypropyl group was 50 mol%, and RSiO _{3/2 in} which R was a phenyl group was 50 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the random structure and / or the ladder structure was 92% by weight.

(Comparative Synthesis Example 4)
Synthesis of Silsesquioxane (SQ) Derivative 4 In a reaction vessel equipped with a stirrer and a thermometer, MIBK 50.0 g, sodium hydroxide 20% aqueous solution 0.790 g (sodium hydroxide 3.95 mmol), distilled water 10. After charging 2 g (567 mmol), 14.2 g (60 mmol) of γ-glycidoxypropyltrimethoxysilane and 35.8 g (181 mmol) of phenyltrimethoxysilane were gradually added at 50 to 55 ° C. and left to stir for 3 hours. . After completion of the reaction, 50.0 g of MIBK was added, and further washed with 25.0 g of distilled water until the pH of the aqueous layer became neutral. Next, MIBK was distilled off under reduced pressure to obtain the target compound, SQ derivative 4. Mw was 4,730. When IR analysis supports that include ladder or random structure was confirmed a peak around 1100 cm ^-1 and 1050 cm ^-1 based on the stretching vibration of Si-O-Si bonds. The repeating structural unit constituting the SQ derivative 4 was 25 mol% of RSiO _3/2 in which R is a glycidoxypropyl group, and 75 mol% of RSiO _{3/2 in} which R is a phenyl group. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, content of the thing of a random type structure and / or a ladder type structure was 93 weight%.

(Examples 1 to 3 and Comparative Examples 1 to 8)
Each component was mixed according to the formulation shown in Table 1 to obtain the desired composition. Each composition obtained was defoamed and stirred for 5 minutes and then cured at 80 ° C. for 1 hour and further at 150 ° C. for 5 hours to obtain a cured product having a thickness of 2 mm and cut into a size of 10 mm × 50 mm. And a cured product having a thickness of 6 mm and cut into a size of 13 mm × 140 mm were prepared as test pieces. About the obtained test piece, glass transition temperature Tg (degreeC), bending strength (MPa), and elongation rate (%) were measured with the following method. The results are shown in Table 1.

In addition, the meaning of the symbol in Table 1 is as follows.
・ JER828: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation)
・ JER152: Phenol novolac type epoxy resin (Mitsubishi Chemical Corporation)
113: 4,4'-methylenebis (2-methylcyclohexaneamine) (Mitsubishi Chemical Corporation)
・ MH-700G: Mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd.)
・ 2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

<Glass transition temperature Tg (° C.)>
Using a dynamic viscoelasticity measuring device DMS6100 (manufactured by Seiko Instruments Inc.), measurement was performed under the conditions of a temperature range of 30 to 250 ° C., a temperature rising rate of 2 ° C./min, and a frequency of 1 MHz. A test piece having a thickness of 2 mm and 10 mm × 50 mm was used.

<Bending strength (MPa) and elongation (%)>
According to JIS K7171, the measurement was carried out using a strograph VG20-E (manufactured by Toyo Seiki Seisakusho) under the conditions of a measurement temperature of 25 ° C., a measurement humidity of 50% RH, a load cell of 1.0 kN and a head moving speed of 5 mm / min. A test piece having a thickness of 6 mm and 13 mm × 140 mm was used.

As shown by the comparison between Comparative Example 1 and Examples 1 and 2, and the comparison between Comparative Example 2 and Example 3, the glass transition temperature Tg is 17 ° C. by blending the (B) silsesquioxane derivative. As it increased above, both bending strength and elongation increased.

Here, as can be seen from Comparative Example 3, the cured product of (B) silsesquioxane derivative has a glass transition temperature Tg of 45 ° C., which is 100 compared with (A) the epoxy resin shown in Comparative Examples 1 and 2. More than ℃. Thus, even when the (B) silsesquioxane derivative having a very low glass transition temperature Tg was blended with the (A) epoxy resin, the glass transition temperature Tg could be increased. This is because (C) an amine compound is used as a curing agent, and when an acid anhydride is used as a curing agent (Comparative Examples 6 to 8), such a glass transition temperature Tg is increased. Was not seen.

As shown by the comparison between Comparative Example 1, Comparative Example 4 and Example 2, (B) Of all the repeating structural units RSiO _3/2 in which the silsesquioxane derivative is contained in one molecule, R is a glycidyl group. When the repeating structural unit which is an organic group containing is less than 50 mol%, the glass transition temperature Tg was lowered by blending the (B) silsesquioxane derivative, and both the bending strength and the elongation were also lowered.

Further, as shown by comparison between Comparative Example 5 and Examples 1 to 3, (B) Silsesquioxane derivative is blended in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of (A) epoxy resin. When the ratio was out of the range, the glass transition temperature Tg was lowered, and the bending strength and elongation were both lowered.

(Examples 4 to 5 and Comparative Example 9)
Each component was mixed according to the formulation shown in Table 2 to obtain the desired composition. Each composition obtained was degassed and stirred for 5 minutes, and then a table-top conveyor UV (LH6 / LC-6B manufactured by Heraeus) was used with a high-pressure mercury lamp at a peak illuminance of 80 mW / cm ² and an integrated exposure amount of 1000 mJ. / Cm ² irradiation, and further cured at 120 ° C. for 30 minutes. About the obtained test piece (thickness 2 mm, 10 mm × 50 mm), the glass transition temperature Tg (° C.) was measured by the above method, and the elastic modulus (GPa) and pencil hardness were measured by the following method. The results are shown in Table 2.

In addition, the meaning of the symbol in Table 2 is as follows.
EX-252: Hydrogenated bisphenol A skeleton epoxy resin (manufactured by Nagase ChemteX Corporation)
CPI-200K: Triarylsulfonium salt-based photocationic polymerization initiator (manufactured by San Apro, CPI is a registered trademark)

<Elastic modulus (GPa)>
The elastic modulus at a frequency of 1 Hz and 25 ° C. was measured with a dynamic viscoelasticity measuring device DMS6100 (manufactured by Seiko Instruments Inc.).

<Pencil hardness>
The pencil hardness (750 ± 10 g load) based on JIS K5600-5-4 was measured at 25 ° C. using a pencil hardness tester (manufactured by Yasuda Seiki Co., Ltd.).

As shown by the comparison between Comparative Example 9 and Examples 4 and 5, the glass transition temperature Tg increased by 10 ° C. or more due to the blending of the (B) silsesquioxane derivative. Also improved.

As described above, the cured product (Examples 1 to 3) obtained by curing the thermosetting resin composition of the present invention and the cured product (Examples 4 to 5) obtained by curing the photocurable resin composition are as follows. It was shown that both have excellent mechanical strength and excellent heat resistance.

Claims

(A) an epoxy resin having an average number of epoxy groups of 2 or more,
(B) 100% by mole or less of the repeating structural unit having RSiO 3/2 as a repeating structural unit, wherein R is an organic group containing a glycidyl group as an essential component among all the repeating structural units contained in one molecule. The weight average molecular weight Mw is 2,000 or more and 10 or more, wherein the repeating structural unit in which R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms is 50 mol% or less and 0 mol% or more. 2,000 or less silsesquioxane derivatives, and (C) an amine compound having two or more amino groups capable of reacting with the epoxy group,
The thermosetting resin composition whose said (B) silsesquioxane derivative is 5 to 30 weight part with respect to 100 weight part of said (A) epoxy resin.
(A) The thermosetting resin composition according to claim 1, wherein the epoxy resin is an aromatic epoxy resin.
Hardened | cured material formed by hardening | curing the thermosetting resin composition of Claim 1 or 2.
(A) an epoxy resin having an average number of epoxy groups of 2 or more,
(B) 100% by mole or less of the repeating structural unit having RSiO 3/2 as a repeating structural unit, wherein R is an organic group containing a glycidyl group as an essential component among all the repeating structural units contained in one molecule. The weight average molecular weight Mw is 2,000 or more and 10 or more, wherein the repeating structural unit in which R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms is 50 mol% or less and 0 mol% or more. 1,000 or less silsesquioxane derivatives, and (D) a photocationic polymerization initiator,
The photocurable resin composition whose said (B) silsesquioxane derivative is 30 to 150 weight part with respect to 100 weight part of said (A) epoxy resin.
Hardened | cured material formed by hardening | curing the photocurable resin composition of Claim 4.
An additive for improving the heat resistance of an epoxy resin,
RSiO 3/2 is a repeating structural unit, and among all the repeating structural units contained in one molecule, the repeating structural unit in which R is an organic group containing a glycidyl group as an essential component is 100 mol% or less and 50 mol% or more Wherein R is an aryl group and / or an alkyl group having 1 to 12 carbon atoms as an optional component, and the weight average molecular weight Mw is 2,000 or more and 10,000 or less, wherein the repeating structural unit is 50 mol% or less and 0 mol% or more. A heat resistance improver comprising a silsesquioxane derivative.