JP2006057013A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition excellent in toughness while maintaining heat resistance of an epoxy-silica hybrid substance. <P>SOLUTION: The resin composition comprises an epoxy resin, a silane condensation product, a toughness-imparting agent and a curing agent. A resin obtained by carrying out hydrolytic condensation of an alkoxysilane is preferably used as the silane condensation product. One kind of material selected from a rubber, a thermoplastic resin and an engineering plastic, particularly a butadiene-acrylonitrile rubber is preferably used as the toughness-imparting agent. The composition is cured to provide a resin excellent in heat resistance and toughness of cured product. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition that has excellent heat resistance and toughness and can be suitably used for a sealing material, a coating film, an adhesive, a prepreg, and the like.

In recent years, epoxy resin cured products are required to have a high level of performance in accordance with the application. For example, FRP produced by arranging electronic parts such as printed circuit boards and semiconductor encapsulants and prepregs of reinforcing fiber materials, particularly FRP in the aircraft field, is desired to have improved heat resistance.
As an epoxy resin composition having excellent heat resistance, an epoxy-silica hybrid has attracted attention. For example, Patent Document 1 describes an epoxy group-containing silicon compound having a structure described below and an alkoxy group in the molecule.

(Wherein R ₁ represents a substituent having an epoxy group, an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue, and R ₁ may be the same as or different from each other, but at least 1 One is a substituent containing an epoxy group.)

  However, the conventional epoxy silica hybrid body has excellent heat resistance, but has a problem that flexibility and toughness are lowered (see Non-Patent Document 1).

On the other hand, as a technique for toughening an epoxy resin, a technique of adding rubber or a thermoplastic resin has been proposed (see, for example, Patent Documents 2 and 3). However, there has been a problem that the glass transition temperature (T _g ) is lowered due to the compatibility of components such as rubber and the heat resistance is lowered (see Non-Patent Document 2).

JP 2004-43696 A JP-A-10-182937 Japanese Patent Laid-Open No. 10-60085 Takahashi, Ochi, Wakida, “Phase structure and thermal / mechanical properties of epoxy / silica hybrid”, Polymer Journal, 2000, Vol. 57, p. 220-227 J. et al. Kiefer et. al, “Synthesis of solvent-modified epoxies via chemical, Induced Phase Separation, Vol. 97, A new procureed topoid poverty. 477-483

As described above, a resin composition having excellent toughness while maintaining the excellent heat resistance of the epoxy silica hybrid has not been known.
Then, an object of this invention is to provide the resin composition excellent in the heat resistance and toughness of hardened | cured material.

As a result of intensive studies, the inventor has found that when an epoxy resin, a silane condensate, a toughness imparting agent, and a curing agent are contained, the resin composition is excellent in heat resistance and toughness of the cured product. Completed.
That is, the present invention provides the following (1) to (7).

(1) an epoxy resin;
A silane condensate,
A toughening agent;
A resin composition containing a curing agent.

  (2) The resin composition according to (1), wherein the silane condensate is obtained by hydrolytic condensation of an alkoxysilane represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an organic group that may contain a nitrogen atom, an oxygen atom, or a sulfur atom. And m represents 2 or 3.)

  (3) The resin composition according to (1) or (2), wherein the silane condensate is represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.)

  (4) The resin composition according to any one of (1) to (3), wherein the toughness imparting agent is at least one selected from the group consisting of rubber, thermoplastic resin, and engineering plastic.

  (5) The resin composition according to claim 4, wherein the rubber is a polymer represented by any one of the following formulas (3) to (5).

(In the formulas (3) to (5), the ratio of x to y (x / y) is 1 to 20, z is 10 to 50, and R ⁴ , R ⁵ and R ⁶ are oxygen atom and nitrogen, respectively. It represents a C1-C24 divalent organic group or single bond that may contain an atom or a double bond.)

  (6) A dispersion aid for rubber, thermoplastic resin, and engineering plastic, comprising a silane condensate represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.)

  (7) An epoxy resin heat resistance imparting agent comprising a silane condensate represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.)

  The composition of the present invention has a small change in storage elastic modulus (G ′) from low temperature to high temperature, and is excellent in heat resistance and toughness of the cured product.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) contains an epoxy resin, a silane condensate, a toughness imparting agent, and a curing agent.

<Epoxy resin>
The epoxy resin used in the composition of the present invention is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolak, tetrabromobisphenol. G, glycidyl ether type obtained by the reaction of polychlorophenol and epichlorohydrin such as A, trihydroxybiphenyl, bisresorcinol, bisphenolhexafluoroacetone, tetramethylbisphenol F, bixylenol; glycerin, neopentyl glycol, ethylene glycol, propylene glycol Aliphatic polyvalent amines such as butylene glycol, hexylene glycol, polyethylene glycol and polypropylene glycol Polyglycidyl ether type obtained by reaction of cole with epichlorohydrin; Glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid Polyglycidyl ester type derived from polycarboxylic acids such as acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; amino Glycidylaminoglycidyl ether type derived from phenol, aminoalkylphenol, etc .; Glycidylaminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribu Glycidylamine type derived from romaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc .; epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin Triglycidyl cyanurate, etc .; mono-epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, styrene oxide, etc., and use one or a mixture of two or more thereof Can do.

Among these, bisphenol A type, bisphenol F type, and glycidyl amine type epoxy resin are preferable because they are easily available and have a good balance of properties (performance) of the cured product.
The epoxy resin preferably has an epoxy equivalent of 80 to 1000 in terms of good workability due to low viscosity and good heat resistance of the cured product, more preferably 80 to 700. preferable.
The epoxy resin may be a commercially available product or may be manufactured. The production conditions are not particularly limited, and can be performed under conditions usually used.

<Silane condensate>
The silane condensate used in the composition of the present invention is not particularly limited as long as it is a compound having a siloxane skeleton. For example, a silane condensate obtained by hydrolytic condensation of an alkoxysilane represented by the following formula (1) Preferably mentioned.
In the present specification, “hydrolytic condensation” means hydrolysis of an alkoxysilyl group and condensation of the produced hydroxysilyl group by dealcoholization reaction with other alkoxysilyl groups, or dehydration reaction between hydroxysilyl groups. Means condensation.
In addition, since an alcohol is generated when a siloxane bond is formed by hydrolysis and condensation reaction, it is preferable to remove the alcohol under reduced pressure when the silane condensate is produced.

In formula (1), m represents 2 or 3. As this alkoxysilane, dialkoxysilane and trialkoxysilane can be used in combination, but it is preferable to contain 50 mol% or more of trialkoxysilane from the viewpoint of excellent heat resistance and curability. From the standpoint of this characteristic, it is more preferable to contain 70 mol% or more of trialkoxysilane, and it is more preferable to use only trialkoxysilane.
R ¹ represents an alkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. When R ¹ is more than one, a plurality of R ¹ may each be the same or different.
R ² represents an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. When R ² is more than one, a plurality of R ² may each be the same or different.
R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom. Specifically, at least one selected from the group consisting of epoxy groups, amino groups, ureido groups, mercapto groups, vinyl groups, acrylic groups, methacryl groups, styryl groups, isocyanate groups, phenyl groups, alkyl groups and chloropropyl groups. Is preferably a group bonded to a silicon atom via a C 3-6 divalent acyclic aliphatic group which may contain an oxygen atom or a C 6-10 divalent cycloaliphatic group. Can be mentioned. Among these, those having at least one of an epoxy group, an amino group, and a mercapto group are more preferable.

Specific examples of the alkoxysilane represented by the above formula (1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Silane, epoxy silanes such as 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminosilanes such as aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinyl Trimethoxysilane, vinylto Vinylsilanes such as ethoxysilane; acryloxysilanes such as 3-acryloxypropyltrimethoxysilane; methacryloxysilanes such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane; 1,4-styryltrimethoxy Styryl silane such as silane; isocyanate silane such as 3-isocyanatopropyltriethoxysilane; phenylsilane such as phenyltriethoxysilane; alkyl silane such as methyltriethoxysilane; chloropropylsilane such as 3-chloropropyltrimethoxysilane; Can be mentioned. These may be used alone or in combination of two or more.
Among these, epoxy silane, aminosilane, and mercaptosilane are preferable from the viewpoint of reactivity with epoxy resin and heat resistance. In particular, epoxy silane is preferable because it is excellent in compatibility with the epoxy resin and is excellent in heat resistance.

  The silane condensate may be one obtained by condensing the alkoxysilane represented by the above formula (1) with a tetraalkoxysilane such as tetramethoxysilane or tetraethoxysilane or a condensate thereof or an alkoxysilane other than these. Good. When tetraalkoxysilane is used in combination, the content of tetraalkoxysilane is preferably 50 mol% or less from the viewpoint of excellent toughness. From the standpoint of this characteristic, the tetraalkoxysilane content is more preferably 20 mol% or less.

By the way, as described above, the epoxy group-containing silicon compound described in Patent Document 1 is represented by the above formula and is completely condensed. Therefore, the reactivity with the epoxy resin matrix via silanol is poor and the heat resistance is low. It was disadvantageous for improvement.
As a result of intensive studies, the present inventors have obtained a silane condensate having low viscosity and excellent storage stability while maintaining heat resistance by performing hydrolysis condensation of the alkoxysilane under a certain condition. I found out.
The reaction condition is to react the alkoxysilane represented by the above formula (1) with 1.5 to 4.5 times mol of water with respect to the silicon atom.
Moreover, it is preferable to perform hydrolysis condensation in a solvent. When hydrolytic condensation is performed in a solvent, a silane condensate having a chain skeleton is easily obtained, and further, gelation can be prevented and storage stability is excellent. The solvent is not particularly limited as long as it is a solvent that dissolves the alkoxysilane to be used. Specific examples of such a solvent include polar solvents such as alcohols such as tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, and methanol.

By performing hydrolysis condensation under the conditions described above and adjusting the condensation degree of the resulting silane condensate, a silane condensate having excellent heat resistance and toughness of the cured product, low viscosity, and excellent storage stability can be obtained. . Therefore, the composition of the present invention is excellent in the heat resistance and toughness of the cured product, has a low viscosity, and is excellent in storage stability. The amount of water to be reacted with respect to the silicon atom of the alkoxysilane represented by the above formula (1) is more preferably 2.0 to 4.2 times mol, still more preferably 3.0 to 4.0 times mol. It is. If it is this range, the viscosity of the silane condensate obtained is low, it is excellent in workability | operativity, and is excellent especially in heat resistance. In addition, when hydrolyzing and condensing the alkoxysilane represented by the above formula (1) with tetraalkoxysilane or other alkoxysilane, the above-mentioned amount of water is added to the total of these silicon atoms. Added.
The reaction temperature during hydrolysis condensation is preferably 25 to 120 ° C, more preferably 50 to 100 ° C.

  As the catalyst used for the hydrolysis condensation, a conventionally known catalyst for promoting condensation of alkoxysilanes can be used. Specifically, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zirconium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium And metals such as manganese and transition metals, oxides thereof, organic acid salts, halides, alkoxides, and the like. Among these, organic tin, organic acid tin, alkoxyzirconium, and alkoxytitanium are particularly preferable, and dibutyltin dilaurate is particularly preferable. The addition amount of the catalyst is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass with respect to the total of alkoxysilanes to be hydrolyzed and condensed.

The silane condensate may have a ladder-like or cage-like siloxane skeleton, but preferably has a chain-like skeleton. The silane condensate obtained as described above is mainly a silane condensate having a chain siloxane skeleton represented by the following formula (2). The silane condensate represented by the following formula (2) is preferable from the viewpoints of excellent heat resistance and toughness of the cured product, low viscosity, excellent workability and storage stability. In addition, since this silane condensate has substantially no alkoxy group and is a silanol group, there is no foaming due to a dealcoholization reaction during curing, so that a composition excellent in moldability can be obtained. it can. Furthermore, since there are more silanol groups than a silane condensate in which alkoxy groups remain and a silane condensate having a ladder-like or cage-like skeleton, the epoxy resin can be heat-resistant with a small amount.
It is preferable to produce these condensates using 3-glycidoxypropyltrialkoxysilane as a raw material because the raw materials are easily available and have high reactivity.

In Formula (2), R ³ is the same as above, n represents an integer of 2 to 50, an integer of 2 to 30 is more preferable, and an integer of 2 to 25 is still more preferable.

  The number average molecular weight of the silane condensate is preferably 500 to 10,000 from the viewpoint that heat resistance is excellent and viscosity does not become too high. From the point which is excellent by these characteristics, 1000-8000 are more preferable and 1000-6000 are still more preferable.

  It is preferable that content of the said silane condensate in the composition of this invention is 5-50 mass% with respect to the sum total of the said epoxy resin and a silane condensate. If content of a silane condensate is this range, it will be excellent in heat resistance and toughness. From the point which is excellent by these characteristics, It is more preferable to contain 10-40 mass%, More preferably, it contains 15-30 mass% of silane condensates.

Since the silane condensate represented by the above formula (2) has excellent properties as described above, it can also be used as a heat resistance imparting agent for epoxy resins.
The epoxy resin that is a target to impart heat resistance is not particularly limited, and examples thereof include the above-described epoxy resins.
The usage-amount of the silane condensate represented by said Formula (2) can be suitably adjusted according to the characteristic requested | required, for example, it is preferable to mix | blend 5-50 mass% with respect to an epoxy resin.

  The silane condensate represented by the above formula (2) is also used as a dispersion aid for rubbers, thermoplastic resins and engineering plastics. For example, when a polymer represented by any one of formulas (3) to (5) described later is used as a toughness imparting agent, it acts as a dispersion aid for these polymers, so the particle size of these polymers is Since it becomes small and disperse | distributes uniformly, the toughness of hardened | cured material improves further and the visible light transmittance | permeability of hardened | cured material improves. That is, since the transparency of the cured product is improved, a composition having excellent colorability can be obtained.

<Toughness imparting agent>
The toughness imparting agent used in the present invention is a compound that improves the toughness of the cured product of the composition of the present invention, and is preferably liquid at room temperature, more preferably compatible with an epoxy resin. In particular, those having reactivity with epoxy groups, since the silane condensate acts as a dispersion aid, the particle size is reduced and uniformly dispersed in the epoxy resin, and the toughness of the cured product is further improved, and From the point of improving the visible light transmittance of the cured product.
Specific examples of the toughness imparting agent include rubber, thermoplastic resin, engineering plastic, and the like. Among these, at least one selected from the group consisting of rubber, thermoplastic resin, and engineering plastic is preferably used.

Specific examples of the rubber include polybutadiene, polyisoprene, polychloroprene, butadiene-isoprene copolymer, butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, or These partially hydrogenated products are exemplified. These polymers may be used alone or in combination of two or more. Among these, an acrylonitrile-butadiene copolymer is preferable, and in particular, a polymer represented by the following formula (3) or the following formula (4) modified with an amine at the end (ATBN) or a carboxylic acid modified at the end When the polymer (CTBN) represented by the formula (5) is used, a cured product of the obtained composition is more preferable from the viewpoint of excellent heat resistance and toughness.
The rubber is preferably liquid at normal temperature, and more preferably compatible with the epoxy resin. For example, an acrylonitrile-butadiene copolymer having a number average molecular weight of about 2000 to 6000 is preferable because it is liquid at room temperature, has a large effect of imparting toughness, and is excellent in heat resistance of a cured product. In view of these characteristics, the number average molecular weight is more preferably about 3000 to 4000.

In formula (3)-(5), 1-20 are preferable, as for ratio (x / y) of x and y, 1.5-10 are more preferable, and 2-5 are still more preferable. z is preferably 10-50, more preferably 15-40, and still more preferably 20-30.
R ⁴ , R ⁵ and R ⁶ are each an oxygen atom, a nitrogen atom or a divalent organic group having 1 to 24 carbon atoms which may contain a double bond or a single bond.
The polymer represented by any of the above formulas (3) to (5) is a block copolymer or a random copolymer having a polybutadiene part and a polyacrylonitrile part.

  The said thermoplastic resin means the synthetic resin from which the thermoplasticity of the grade which can be shape | molded by heating except the engineering plastic mentioned later is obtained. Specifically, for example, polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS). , Polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl dichloride (PVDC), polyethylene terephthalate (PET) and the like. These may be used alone or in combination of two or more. Among these, PMMA, ABS, or AS is preferable because it has a large effect of imparting toughness and is excellent in heat resistance of the cured product.

  The engineering plastic generally means a plastic having a heat resistance of 100 ° C. or more, a strength of 49.0 MPa or more, and a flexural modulus of 2.4 GPa or more. Specifically, for example, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, ultrahigh molecular weight polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyetheretherketone, Examples thereof include polyimide, liquid crystal polymer, and fluororesin. These may be used alone or in combination of two or more. Among these, polyethersulfone, polyamide, and polyetheretherketone are preferable because they have a great effect of imparting toughness and are excellent in heat resistance of the cured product.

  The content of the toughening agent is preferably 1 to 50 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the silane condensate. This range is preferable from the viewpoint of improving toughness while maintaining heat resistance. From the point which is excellent by these characteristics, 5-25 mass parts is more preferable, and 10-20 mass parts is still more preferable.

<Curing agent>
Examples of the curing agent used in the composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, thiol compounds, imidazoles, boron trifluoride-amine complexes, and guanidine derivatives. And amine-based compounds, acid anhydride-based compounds, thiol-based compounds, and the like are preferable.

  Specific examples of amine compounds include metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), diaminodiphenylmethane, diethylenetriamine, and triethylene. Amine compounds such as tetramine, tetraethylenepentamine, diaminodiphenylsulfone, isophoronediamine (IPDA), dicyandiamide, dimethylbenzylamine, ketimine compounds, polyamines of polyamide skeleton synthesized from dimer of linolenic acid and ethylenediamine, the following formula The compound etc. which are represented by (6) are mentioned. Among them, metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), triethylenetetramine and the like are liquid at room temperature, have good workability, and are curable. Is preferable from the viewpoint of high. Moreover, since the compound represented by the following formula (6) has an aromatic nucleus in the skeleton, it is suitable because it has high heat resistance and a long pot life. It is done.

  Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl And hexahydrophthalic anhydride. Among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like are preferable because they are liquid at room temperature, have good workability, and have high curability.

  Specific examples of phenolic compounds include polycondensates of bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, phenols, and the like. Examples thereof include polymers with various diene compounds, polycondensates of phenols and aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and modified products thereof.

Specific examples of the thiol-based curing agent include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1 , 4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1, 2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,3,5-triazine-2,4,6-trithiol (tri Mercapto-triazine), 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethyl Thiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris (β-thiopropio Nate), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, Epomate QX10 (manufactured by Japan Epoxy Resin Co., Ltd.) , Dithiols such as Epomate QX11 (manufactured by Japan Epoxy Resin);
Examples include thiol compounds such as polythiol such as Thiocol (manufactured by Toray Fine Chemical Co., Ltd.), Cup Cure 3-800 (manufactured by Japan Epoxy Resin Co., Ltd.), and EpiCure QX40 (manufactured by Japan Epoxy Resin Co., Ltd.). Among these, epoxide QX10, epoxide QX11, cup cure 3-800, epicure QX40 and the like are suitably used as commercially available fast-curing polythiols.

  0.8-1.1 equivalent is preferable with respect to 1 equivalent of epoxy groups in a composition, and, as for the usage-amount of a hardening | curing agent, 0.95-1.05 equivalent is more preferable.

  The composition of the present invention includes, in addition to the above-described components, a curing catalyst, a filler, a plasticizer, an antioxidant, an anti-aging agent, a pigment, a thixotropy imparting agent, and adhesiveness, as long as the object of the present invention is not impaired Various additives such as an imparting agent, a flame retardant, a dye, an antistatic agent, a dispersant, and a solvent can be contained.

  Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and the following formula (7). 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, Examples thereof include metal compounds such as tin octylate and quaternary phosphonium salts. Among these, a compound represented by the following formula (7) is preferable because of its strong catalytic action.

  0.5-10 mass parts is preferable with respect to 100 mass parts of epoxy resins, and, as for content of a curing catalyst, 1-5 mass parts is more preferable.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products. The content of the filler is preferably 90% by mass or less in the entire composition in terms of physical properties of the cured product.

  Specific examples of the plasticizer include dioctyl phthalate (DOP) and dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate, and the like. These may be used alone or in combination of two or more. From the viewpoint of workability, the plasticizer content is preferably 50 parts by mass or less with respect to 100 parts by mass in total of the epoxy resin and the silane condensate.

Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the anti-aging agent include hindered phenol compounds.

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The composition of this invention can be manufactured by a well-known method. For example, it can be obtained by mixing and dispersing the epoxy resin, the silane condensate, the toughness-imparting agent, the curing agent, and an additive that is optionally added under a nitrogen atmosphere using a stirrer.

The composition of the present invention can be used as a two-component type composed of a main agent containing an epoxy resin and a silane condensate and a curing agent. The toughness imparting agent and optionally added additives can be contained in either or both of the main agent and the curing agent. In addition, since it is necessary to disperse | distribute a toughness imparting agent uniformly in a matrix, it is preferable to make it contain in a main ingredient beforehand. If necessary, the toughness imparting agent and the epoxy resin can be reacted in advance, and then the silane condensate and other additives can be added.
When a latent curing agent such as ketimine is used as the curing agent, it can be used as a one-component type that is cured by moisture such as moisture in the air or by heating.

  The composition of the present invention thus obtained has a small change in storage elastic modulus (G ′) from low temperature to high temperature, and is excellent in heat resistance and toughness of the cured product.

  Since the composition of the present invention has excellent properties as described above, it can be suitably used for applications such as a sealing material, a coating film, an adhesive, a prepreg, a paint, a rust preventive paint, and a sealing agent. In particular, it can be suitably used for applications such as printed circuit boards, semiconductor encapsulants, and FRP matrix resins typified by aircraft, which require excellent heat resistance.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Synthesis of silane condensate>
To 40.84 g of 3-glycidoxypropyltrimethoxysilane (A187, manufactured by Nihon Unicar Co., Ltd.), 14.0 g of water, 0.4 g of dibutyltin dilaurate, and 80 g of THF were mixed and then stirred at 80 ° C. for 12 hours. . Thereafter, methanol produced by the reaction was removed under reduced pressure, and a liquid silane condensate was obtained with an epoxy equivalent (theoretical value) of 178 g / eq.
When the structure of the obtained silane condensate was analyzed by ¹ H-NMR, it was confirmed that the peak derived from the methoxy group disappeared. It was estimated that the obtained silane condensate mainly has a structure represented by the following formula.

  In the formula, n represents an integer of 2 to 50.

(Examples 1-3 and Comparative Examples 1-3)
The components shown in Table 1 below were mixed and dispersed using the stirrer at the composition (parts by mass) shown in Table 1 to obtain the resin compositions shown in Table 1.
About the obtained resin composition, heat resistance was evaluated by measuring a glass transition temperature ( _Tg ), a storage elastic modulus (G '), and its retention rate as follows. Further, the fracture toughness value (Kc) was measured. The results are shown in Table 1.

<Measuring method of glass transition temperature, storage elastic modulus (G ′) and retention ratio>
(1) Preparation of test body Each resin composition was poured into a steel mold coated with a release agent, cured at 80 ° C for 2 hours, and further cured at 180 ° C for 4 hours to be cured. The obtained cured product (length 50 mm × width 15 mm × height 2 mm) was used as a test specimen.
(2) Measurement of storage elastic modulus For the specimen of (1), the storage elastic modulus at temperatures of 25 ° C and 230 ° C during torsion mode, 0.01% strain, and forced extension with a frequency of 1 Hz, respectively G ′ (25 C) and G ′ (230 ° C.) were measured, and the retention rate (%) of the storage elastic modulus (G ′) was determined according to the following formula.

       G ′ retention rate (%) = {G ′ (230 ° C.) / G ′ (25 ° C.)} × 100

  Moreover, the glass transition temperature of each resin composition was measured in the range of 25-300 degreeC at this time.

<Measurement method of fracture toughness value (Kc)>
Each resin composition was cured at 80 ° C. for 2 hours and at 180 ° C. for 4 hours to prepare a resin plate having a thickness of 4 mm. Using this resin plate, the test force at breakage was measured by a compact tension test in accordance with the method described in ASTM D5045-99.
Here, values obtained by setting the measured values of the resin composition of Comparative Example 1 as a reference and dividing each measured value by the measured values of the resin composition of Comparative Example 1 are shown in Table 1 below.

*１ 動的粘弾性測定上、明確なガラス転移温度（Ｔ_ｇ）が観察されなかった。

* 1 A clear glass transition temperature (T _g ) was not observed in dynamic viscoelasticity measurement.

Each component shown in Table 1 is as follows.
Epoxy resin (bisphenol A type): EP-4100E, manufactured by Asahi Denka Kogyo Co., Ltd. Curing agent (compound shown in the above formula (5)): Kayabond C-200S, Nippon Kayaku Co., Ltd. Toughness imparting agent (Compound (ATBN) represented by the above formula (3)): Hycar 1300 × 45, Noveon Co. , Ltd., Ltd. Made

As is apparent from the results shown in Table 1, the epoxy resin, the silane condensate, the curing agent, and the toughness imparting agent (ATBN) are included, and the total of the epoxy resin and the silane condensate includes the silane condensate. resin composition content of 25 mass% (example 2) is a T _g less, had both heat resistance and toughness at a high level.
The resin composition (Example 1) in which the content of the silane condensate was 5% by mass with respect to the total of the epoxy resin and the silane condensate was excellent in toughness. Moreover, although heat resistance fell from Example 2, it had the outstanding heat resistance (G 'retention) compared with the resin composition (Comparative Examples 1 and 3) which does not contain a silane condensate.
The content of the silane condensates of the total of the epoxy resin and the silane condensate resin composition is 50 wt% (Example 3) is a T _g less, were excellent in heat resistance. Moreover, although toughness falls rather than Example 2, it has toughness equivalent to or more than the resin composition of Comparative Example 1 and superior toughness compared to a resin composition not containing a toughening agent (Comparative Example 2). Was. That is, it was possible to maintain toughness even when a silane condensate was added to improve heat resistance.
Further, the cured products of the resin compositions of Examples 2 and 3 were translucent. This is presumably because the silane condensate functions as a dispersion aid for the toughness imparting agent (ATBN), the rubber particle size is reduced, and the visible light transmittance is improved.

Claims (7)

Epoxy resin,
A silane condensate,
A toughening agent;
A resin composition containing a curing agent. The resin composition according to claim 1, wherein the silane condensate is obtained by hydrolytic condensation of an alkoxysilane represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an organic group that may contain a nitrogen atom, an oxygen atom, or a sulfur atom. And m represents 2 or 3.) The resin composition according to claim 1 or 2, wherein the silane condensate is represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.)   The resin composition according to any one of claims 1 to 3, wherein the toughening agent is at least one selected from the group consisting of rubber, thermoplastic resin, and engineering plastic. The resin composition according to claim 4, wherein the rubber is a polymer represented by any one of the following formulas (3) to (5).

(In the formulas (3) to (5), the ratio of x to y (x / y) is 1 to 20, z is 10 to 50, and R ⁴ , R ⁵ and R ⁶ are oxygen atom and nitrogen, respectively. It represents a C1-C24 divalent organic group or single bond that may contain an atom or a double bond.) A dispersion aid for rubber, thermoplastic resin and engineering plastic, comprising a silane condensate represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.) An epoxy resin heat resistance imparting agent comprising a silane condensate represented by the following formula (2).

(In the formula, R ³ represents an organic group which may contain a nitrogen atom, an oxygen atom or a sulfur atom, and n represents an integer of 2 to 50.)