JP2018154735A - Thermosetting resin composition and bending strength improver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of obtaining a cured product having excellent mechanical strength and heat resistance. SOLUTION: (A) an epoxy resin having an average number of epoxy groups of 2 or more, (B) (R1SiO3 / 2) m (R2R3SiO) n are repeated constituent units, and m and n are (R1SiO3 / 2) and (R2R3SiO), respectively. ) Unit molar ratio, m: n is 99.2: 0.8 to 95.0: 5.0, and the substituents R1, R2, and R3 are organic groups containing epoxy groups and aryl, respectively. It is one group selected from the group consisting of a group and an alkyl group having 1 to 12 carbon atoms, and is an organic group containing an epoxy group among the total number of moles of the substituents R1, R2 and R3 contained in one molecule. Contains 90 mol% or more and 100 mol% or less, a silsesquioxane derivative having a weight average molecular weight of Mw 2,000 or more and 10,000 or less, and (C) an amine-based compound, and 100 parts by weight of the (A) epoxy resin. On the other hand, the heat-curable resin composition in which the (B) silsesquioxane derivative is 5 parts by weight or more and 30 parts by weight or less. [Selection diagram] None

Description

  The present invention relates to a thermosetting resin composition and a bending strength 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 fields of automotive / aircraft and electrical / electronic materials such as semiconductor sealants, laminates, FRP (composite materials), interlayer insulating materials, adhesives, etc., bisphenol A has a good balance of heat resistance and mechanical strength. Aromatic epoxy resins such as type epoxy resins are widely used.

  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, demands for long-term reliability of epoxy resins have been advanced, and there is a strong demand for further improving mechanical strength and heat resistance. However, conventional epoxy compounds are insufficient in terms of both mechanical strength and heat resistance. An object of this invention is to provide the thermoplastic resin composition which can obtain the hardened | cured material excellent in mechanical strength and heat resistance.

In the first aspect of the present invention, (A) an epoxy resin having an average number of epoxy groups of 2 or more, (B) (R ¹ SiO _3/2 ) _m (R ² R ³ SiO) _n is used as a repeating structural unit, and m, n Are molar ratios of (R ¹ SiO _3/2 ) and (R ² R ³ SiO) units, respectively, and m: n is 99.2: 0.8 to 95.0: 5.0, R ¹ , R ² , and R ³ are each one group selected from the group consisting of an organic group containing an epoxy group, an aryl group, and an alkyl group having 1 to 12 carbon atoms, and are included in one molecule. Of the total number of moles of the substituents R ¹ , R ² and R ³ , the silsesquialkyl having an epoxy group-containing organic group of 90 mol% to 100 mol% and a weight average molecular weight Mw of 2,000 to 10,000. An oxane derivative and (C) an amine compound, A) It is related with the thermosetting resin composition whose said (B) silsesquioxane derivative is 5 to 30 weight part with respect to 100 weight part of epoxy resins.

In the thermosetting resin composition, the (B) silsesquioxane derivative is preferably a silsesquioxane derivative having an organic group containing an epoxy group as R ¹ .

In the thermosetting resin composition, the (B) silsesquioxane derivative is a sil having an organic group containing an epoxy group as R ² and an aryl group and / or an alkyl group having 1 to 12 carbon atoms as R ^3. A sesquioxane derivative is preferred.

  In the thermosetting resin composition, the (A) epoxy resin is preferably an aromatic epoxy resin.

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

A third aspect of the present invention is an additive for improving the bending strength of an epoxy resin, wherein (R ¹ SiO _3/2 ) _m (R ² R ³ SiO) _n is a repeating structural unit, and m and n are The molar ratio of (R ¹ SiO _3/2 ) and (R ² R ³ SiO) units, respectively, m: n is 99.2: 0.8 to 95.0: 5.0, and the substituent R ¹ , R ² , and R ³ are each a group selected from the group consisting of an organic group containing an epoxy group, an aryl group, and an alkyl group having 1 to 12 carbon atoms, and the substitution contained in one molecule Silsesquioxane whose organic group containing an epoxy group is 90 mol% or more and 100 mol% in the total number of moles of the groups R ¹ , R ² and R ^{3 and} whose weight average molecular weight Mw is 2,000 or more and 10,000 or less. The present invention relates to a bending strength improver containing a derivative.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can obtain the hardened | cured material excellent in 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]
The thermosetting resin composition of the present invention comprises (A) an epoxy resin, (B) a silsesquioxane derivative, and (C) an amine-based compound, and (B) with respect to 100 parts by weight of (A) the epoxy resin. The silsesquioxane derivative is 5 parts by weight or more and 30 parts by weight or less.

[(A) Epoxy resin]
(A) The epoxy resin has an average number of epoxy groups of 2 or more. (A) The epoxy resin 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 an aromatic epoxy resin, an aliphatic epoxy resin, and an alicyclic epoxy resin are used. be able to. Of these, aromatic epoxy resins are preferred because of their excellent heat resistance.

  The (A) 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 Derivatives; 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. Bisphenol A is preferred because the resulting cured product has an excellent balance between heat resistance and mechanical strength.

  The aliphatic epoxy resin is not particularly limited as long as it has an aliphatic skeleton in one molecule 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, hexanediol, ethylene glycol, propylene glycol, pentaerythritol, or an epoxy resin obtained by epoxidizing these derivatives is preferred 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, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferably used 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 (R ¹ SiO _3/2 ) _m (R ² R ³ SiO) _n as a repeating structural unit, and m and n are (R ¹ SiO _3/2 ) and (R ² , respectively). R ³ SiO) units, wherein m: n is 99.2: 0.8 to 95.0: 5.0, and the substituents R ¹ , R ² , and R ³ are each an epoxy group. The total number of moles of substituents R ¹ , R ² and R ³ included in one molecule, which is one group selected from the group consisting of an organic group containing an aryl group, an aryl group, and an alkyl group having 1 to 12 carbon atoms Among them, the organic group containing an epoxy group is 90 mol% or more and 100 mol% or less, and the weight average molecular weight Mw is 2,000 or more and 10,000 or less.

Molar ratio of (R ¹ SiO _3/2 ) unit to (R ² R ³ SiO) unit, (R ¹ SiO _3/2 ) unit m: (R ² R ³ SiO) unit n is 99.2: 0. 8-95.0: 5.0, it may be 99.1: 0.9-95.0: 5.0, 99.0: 1.0-95.0: 5.0 It may be 99.0: 1.0-97.0: 3.0. This is because the resulting cured product has more excellent mechanical strength and heat resistance. If the molar ratio m: n is outside the range of 99.2: 0.8 to 95.0: 5.0, the mechanical strength is particularly lowered, which is not preferable.

The substituents R ¹ , R ² , and R ³ are each one group selected from the group consisting of an organic group containing an epoxy group, an aryl group, and an alkyl group having 1 to 12 carbon atoms. Of the substituents R ¹ , R ² , and R ³ , two or more substituents may be the same group, and the substituents R ¹ , R ² , and R ³ may be different groups.

The substituent R ¹ preferably has an organic group containing an epoxy group. This is because the resulting cured product has particularly good heat resistance and mechanical strength.

It is preferable to have an organic group containing an epoxy group as the substituent R ² and an aryl group and / or an alkyl group having 1 to 12 carbon atoms as R ³ . This is because the resulting cured product has particularly good heat resistance and mechanical strength.

(B) Of the total moles of substituents R ¹ , R ² and R ³ contained in one molecule of the silsesquioxane derivative, the organic group containing an epoxy group is contained in a proportion of 90 mol% or more and 100 mol% or less. Therefore, the ratio is preferably 95.0 mol% or more and 100 mol% or less, may be 98.0 mol% or more and 100 mol% or less, and may be 99.0 mol% or more and 100 mol% or less. This is because the resulting cured product has more excellent mechanical strength and heat resistance. If it is less than 90 mol%, both the mechanical strength and the heat resistance are lowered, which is not preferable.

  Examples of the organic group containing an epoxy 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 an epoxy group, a glycidoxyalkyl group is preferred because of its excellent reactivity with the (C) amine compound. Sufficient cured product characteristics (heat resistance and mechanical strength) can be obtained due to excellent reactivity with amine compounds.

  Examples of the aryl group include a phenyl group; 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, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl 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 aryl groups or alkyl groups having 1 to 12 carbon atoms, the cured product obtained by curing the resulting thermosetting resin composition is excellent in heat resistance and is compatible with (A) an epoxy resin without any problem. Group, phenyl group, isobutyl group, isooctyl group and the like are preferable.

(B) composition of R ¹ SiO _3/2 in the silsesquioxane derivative; composition of R ² R ³ SiO; molar ratio of (R ¹ SiO _3/2 ) units, (R ² R ³ SiO) units; and The ratio of the organic group containing an epoxy group can be analyzed by ¹ H-NMR or FTIR. As an apparatus, JNM-ECZR (manufactured by JEOL Ltd., 400 MHz) can be used for ¹ H-NMR, and Frontier Optica (manufactured by Perkin Elmer, KBr method) can be used for FTIR.

  In general, it is known that a silsesquioxane derivative 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. (B) It is preferable that the silsesquioxane derivative has a ladder structure or a random structure, or has both a ladder structure and a random structure. In particular, since the (B) silsesquioxane derivative has excellent mechanical strength, the resulting cured product has a ladder structure and / or a random structure of 80% by weight or more of the (B) silsesquioxane derivative. It is preferably contained, more preferably 85% by weight or more, and even 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.

  The (B) silsesquioxane derivative may contain a structure other than the ladder type and 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 performs a hydrolysis / condensation reaction by combining trialkoxysilane leading (R ¹ SiO _3/2 ) and dialkoxysilane leading (R ² R ³ SiO) _n. Can be obtained.

Examples of trialkoxysilane for deriving (R ¹ SiO _3/2 ) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Examples thereof include 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 dialkoxysilane for deriving (R ² R ³ SiO) _n include dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, Examples thereof include diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. 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.

  A catalyst may be used for the hydrolysis / condensation reaction, and 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.

  Moreover, 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; 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 has a weight average molecular weight Mw of 2,000 or more and 10,000 or less in order to achieve both mechanical strength and heat resistance of a cured product obtained by curing the thermosetting resin composition obtained. is there. 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. And (A) the compatibility with the epoxy resin is lowered, and the optical properties (transparency) of a cured product obtained by curing the resulting thermosetting resin composition is deteriorated. The weight average molecular weight Mw is a value measured by polystyrene permeation gel permeation chromatography (GPC). For measurement, a Shodex KF-803L column manufactured by Waters can be used.

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

  Content of (B) silsesquioxane derivative in the thermosetting resin composition of this invention is 5 to 30 weight part with respect to 100 weight part of (A) epoxy resin. (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. And has particularly excellent mechanical strength. On the other hand, if the amount 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 heat resistance are lowered, and the mechanical strength is particularly deteriorated.

  (B) The silsesquioxane derivative is used as a bending strength improver that improves the bending strength of an epoxy resin by adding it to various epoxy resins including an epoxy resin (A) having an average number of epoxy groups of 2 or more. be able to.

[(C) amine compound]
The (C) amine compound 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 of the (A) epoxy resin, and is not limited to aliphatic amine, alicyclic amine, aromatic. Various amine compounds such as 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 the alicyclic amine 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 the aromatic amine 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, it is preferable to use 4,4′-methylenebis (2-methylcyclohexaneamine) 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 disclosure 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. (A) Thermosetting resin composition obtained when (C) amine compound is 10 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total of (A) epoxy resin and (B) silsesquioxane derivative The cured product obtained by curing can have 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.

[Cured product]
A cured product can be produced by advancing curing of the thermosetting resin composition of the present invention. In the production, the thermosetting resin composition of the present disclosure is heated, and then cooled and cured, for example, by molding with a mold.

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

  The bending strength of a cured product obtained by curing the thermosetting resin composition of the present disclosure is more preferable in the order of 80 MPa or more, 85 MPa or more, 88 MPa or more, 95 MPa or more, 100 MPa or more, 110 MPa or more. The bending strength is preferably higher, and the upper limit value is not particularly limited. For example, it may be 115 MPa or less from the viewpoint of practical use. The deflection amount is preferably 11 mm or more, and more preferably 13 mm or more. From the viewpoint of practical use, it may be 18 mm or less.

  The bending strength and the deflection amount are both in accordance with JIS K7171, using a strograph VG20-E (manufactured by Toyo Seiki Seisakusho), measuring temperature 25 ° C., measuring humidity 50% RH, load cell 1.0 kN, head moving speed. It can be measured under the condition of 5 mm / min.

  The glass transition temperature Tg of the cured product obtained by curing the thermosetting resin composition of the present disclosure is preferably 150 ° C. or higher, more preferably 155 ° C. or higher, further preferably 160 ° C. or higher, and most preferably 165 ° 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 (manufactured by Seiko Instruments Inc.) under the conditions of a temperature range of 30 to 250 ° C., a heating rate of 2 ° C./min, and a frequency of 1 MHz. be able to.

  As described above, a cured product obtained by curing a thermosetting resin composition has excellent mechanical strength and excellent heat resistance. Therefore, a semiconductor sealing agent, a laminate, an FRP (composite material), an interlayer insulating material, Suitable for use in parts and materials that require high mechanical and electrical connection reliability despite being exposed to high temperatures and high humidity, such as in adhesives and other automotive / aircraft and electrical / electronic materials fields be able to.

  The present invention will be described in more detail with reference to the following 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 50 g (528 mmol), 49.7 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were gradually added at 50 to 55 ° C. and left to stir for 3 hours. did. 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 4,330. 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. In the SQ derivative 1, among the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 98.0 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.

(Synthesis Example 2)
Synthesis of Silsesquioxane (SQ) Derivative 2 49.7 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 49. The target compound SQ derivative 2 was obtained in the same manner as in Synthesis Example 1 except that 6 g (210 mmol) and γ-glycidoxypropylmethyldimethoxysilane 0.420 g (1.91 mmol) were used. Mw was 4,530. 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. In the SQ derivative 2, out of the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 99.1 mol%. 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%.

(Synthesis Example 3)
Synthesis of Silsesquioxane (SQ) Derivative 3 49.7 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 49. The target compound SQ derivative 3 was obtained in the same manner as in Synthesis Example 1 except that 5 g (210 mmol) and γ-glycidoxypropylmethyldimethoxysilane 0.470 g (2.13 mmol) were used. Mw was 4,560. 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. In the SQ derivative 3, among the total moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 99.0 mol%. 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%.

(Synthesis Example 4)
Synthesis of Silsesquioxane (SQ) Derivative 4 49.6 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to γ-glycidoxypropyltrimethoxysilane 47. The target compound SQ derivative 4 was obtained in the same manner as in Synthesis Example 1 except that 7 g (202 mmol) and γ-glycidoxypropylmethyldimethoxysilane 2.34 g (10.6 mmol) were used. Mw was 4,270. 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. In the SQ derivative 4, among the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 95.2 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the random type structure and / or the ladder type structure was 90% by weight.

(Comparative Synthesis Example 1)
Synthesis of Silsesquioxane (SQ) Derivative 5 49.6 g (210 mol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 49. The target compound SQ derivative 5 was obtained in the same manner as in Synthesis Example 1 except that 8 g (211 mmol) and γ-glycidoxypropylmethyldimethoxysilane 0.230 g (1.04 mmol) were used. Mw was 4,630. 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. In the SQ derivative 5, among the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 99.5 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the thing of a random type structure and / or the thing of a ladder type structure was 91 weight%.

(Comparative Synthesis Example 2)
Synthesis of Silsesquioxane (SQ) Derivative 6 49.6 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 47. The target compound SQ derivative 6 was obtained in the same manner as in Synthesis Example 1 except that 2 g (200 mmol) and γ-glycidoxypropylmethyldimethoxysilane (2.81 g, 12.8 mmol) were used. Mw was 4,120. 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. In the SQ derivative 6, out of the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 94.3 mol%. In addition, as a result of calculating the m / z peak area by liquid chromatograph mass spectrometry, the content of the random type structure and / or the ladder type structure was 90% by weight.

(Comparative Synthesis Example 3)
Synthesis of Silsesquioxane (SQ) Derivative 7 49.6 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 45. The target compound SQ derivative 7 was obtained in the same manner as in Synthesis Example 1 except that 3 g (192 mmol) and 4.69 g (21.3 mmol) of γ-glycidoxypropylmethyldimethoxysilane were used. Mw was 3,880. 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. In the SQ derivative 7, out of the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 90.9 mol%. 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%.

(Comparative Synthesis Example 4)
Synthesis of Silsesquioxane (SQ) Derivative 8 49.6 g (210 mmol) of γ-glycidoxypropyltrimethoxysilane and 0.260 g (2.16 mmol) of dimethyldimethoxysilane were added to 49. The target compound SQ derivative 8 was obtained in the same manner as in Synthesis Example 1 except that 7 g (210 mmol) and 0.290 g (2.13 mmol) of methyltrimethoxysilane were used. Mw was 4,560. 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. In the SQ derivative 8, out of the total number of moles of the substituents R ¹ , R ² and R ³ contained in one molecule, the organic group containing an epoxy group was 99.0 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.

  Table 1 shows each blending ratio and other measurement results in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 4.

(Examples 1 to 6 and Comparative Examples 1 to 9)
Each component was mixed according to the formulation shown in Table 2 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, the glass transition temperature Tg (degreeC), the bending strength (MPa), and the deflection amount (mm) were measured with the following method. The results are shown in Table 2.

In addition, the meaning of the symbol in Table 2 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 Nippon Nippon Chemical Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

<Glass transition temperature Tg (° C.)>
Using a differential scanning calorimetry (DSC) apparatus DMS6100 (manufactured by Seiko Instruments Inc.), measurement was performed under the conditions of a temperature range of 30 to 250 ° C., a heating 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 deflection (mm)>
In accordance with JIS K7171, the measurement was performed 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 6 and Examples 3 and 4, and the comparison between Comparative Example 7 and Example 6, the glass transition temperature Tg is maintained or increased by blending the (B) silsesquioxane derivative. In addition, both the bending strength and the amount of deflection were improved.

  Here, as can be seen from Comparative Example 8, the cured product of (B) silsesquioxane derivative has a glass transition temperature Tg of 43 ° C., and (A) the glass transition temperature Tg of the epoxy resin shown in Comparative Examples 6 and 7 Compared to 100 ° C. or more. 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 of the (A) epoxy resin could be maintained or increased. (Comparative Example 6 and Examples 1 to 5, and Comparative Example 7 and Example 6).

As shown by comparison between Comparative Examples 1 to 3 and Comparative Example 6, the molar ratio m: n of (R ¹ SiO _3/2 ) and (R ² R ³ SiO) units is 99.2: 0.8. When not included in ˜95.0: 5.0, the bending strength was reduced as compared with the case where the (B) silsesquioxane derivative was not blended.

  Moreover, as shown by the comparison between Comparative Example 5 and Examples 1 to 5, when the blending ratio of (B) silsesquioxane derivative exceeds 30 parts by weight with respect to 100 parts by weight of (A) epoxy resin. The bending strength and the amount of deflection are both lower than those in the range of 5 to 30 parts by weight. (B) Bending strength and the amount of deflection decreased even when compared with the case where no silsesquioxane derivative was blended (Comparative Example 6).

  As mentioned above, it was shown that the hardened | cured material (Example 1 thru | or 6) formed by hardening | curing the thermosetting resin composition of an Example has the outstanding mechanical strength and the outstanding heat resistance.

Claims (6)

(A) an epoxy resin having an average number of epoxy groups of 2 or more,
(B) (R ¹ SiO _3/2 ) _m (R ² R ³ SiO) _n is a repeating structural unit,
m and n are molar ratios of (R ¹ SiO _3/2 ) and (R ² R ³ SiO) units, respectively, and m: n is 99.2: 0.8 to 95.0: 5.0. ,
The substituents R ¹ , R ² , and R ³ are each one group selected from the group consisting of an organic group containing an epoxy group, an aryl group, and an alkyl group having 1 to 12 carbon atoms, and in one molecule Of the total moles of substituents R ¹ , R ² and R ³ included, the organic group containing an epoxy group is 90 mol% or more and 100 mol% or less,
A silsesquioxane derivative having a weight average molecular weight Mw of 2,000 to 10,000,
And (C) an amine compound,
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. The thermosetting resin composition according to claim 1, wherein the (B) silsesquioxane derivative is a silsesquioxane derivative having an organic group containing an epoxy group as R ¹ . The (B) silsesquioxane derivative is a silsesquioxane derivative having an organic group containing an epoxy group as R ² and an aryl group and / or an alkyl group having 1 to 12 carbon atoms as R ^3. The thermosetting resin composition according to 1 or 2.   The thermosetting resin composition according to any one of claims 1 to 3, wherein the (A) epoxy resin is an aromatic epoxy resin.   Hardened | cured material formed by hardening | curing the thermosetting resin composition of any one of Claims 1-4. An additive for improving the bending strength of epoxy resin,
(R ¹ SiO _3/2 ) _m (R ² R ³ SiO) _n is a repeating structural unit,
m and n are molar ratios of (R ¹ SiO _3/2 ) and (R ² R ³ SiO) units, respectively, and m: n is 99.2: 0.8 to 95.0: 5.0. ,
The substituents R ¹ , R ² , and R ³ are each one group selected from the group consisting of an organic group containing an epoxy group, an aryl group, and an alkyl group having 1 to 12 carbon atoms, and in one molecule Of the total number of moles of substituents R ¹ , R ² and R ³ contained, the organic group containing an epoxy group is 90 mol% or more and 100 mol%, and the weight average molecular weight Mw is 2,000 or more and 10,000 or less. A bending strength improver containing a sesquioxane derivative.