JP6536407B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition that has rapid curing and is suitable for fixing neodymium.

  In recent years, neodymium magnets (also called neodymium magnets or neodymium magnets) are widely used in various fields such as electric / electronic fields and in-vehicle fields because of their strong magnetic force. In the electronic device, the neodymium magnet is used in the actuator portion of a hard disk drive, and also in the motor portion of a hybrid car for on-vehicle use. In general, the magnet expands when it is heated and shrinks when it is cooled, but the neodymium magnet shrinks when it is heated and expands when it is cooled. Adhesives and sealants are used to fix neodymium magnets, but the assembled parts are subjected to a high temperature test (100 ° C atmosphere), a low temperature test (0 ° C or -40 ° C atmosphere), a heat shock test (0 In durability tests such as 1 hour in 100 ° C atmosphere and 1 hour cycle in 100 ° C atmosphere) and heat cycle test (cycles for 15 minutes in 0 ° C and 15 minutes in 100 ° C atmosphere) Defects such as generation of cracks in the cured product are likely to occur. This is caused by the fact that the expansion and contraction of the neodymium magnet and the adhesive are reversed. As a prior art, it is known to fix a neodymium magnet with an epoxy resin (refer to JP 2007-68270 A).

  With the improvement in reliability of parts and the like in recent years, neodymium adhesives and the like are required to cope with further endurance tests. However, in the technique described in the above-mentioned JP-A-2007-68270, it is difficult to stably fix the neodymium magnet even after the endurance test. Moreover, in fixation of a neodymium, the thermosetting resin composition which is excellent in rapid curability and storage stability was calculated | required.

  Therefore, it is an object of the present invention to provide a thermosetting resin composition which has fast curing and is excellent in storage stability, and which enables stable fixation even after a durability test in the fixation of neodymium.

  The present inventors diligently studied to achieve the above object. As a result, the thermosetting resin composition containing the following (A)-(D) component discovers that the said objective is achieved, and came to complete this invention.

That is, the first embodiment of the present invention comprises the following components (A) to (D), and the following component (A) is 25 to 75 to the total of the following component (A) and the following component (B) Thermosetting resin composition containing mass%:
Component (A): Epoxy Resin (B) Component: Cyanate Ester Resin (C) Component: First Curing Agent Containing Modified Amine Compound of the Following Component (C1) and Phenolic Resin, and Component (C2) Second curing agent comprising a modified amine compound and a phenol resin (C1) component: a polyamine compound having one or more tertiary amino groups and at least one of one or more primary amino groups and secondary amino groups Modified amine compound obtained by reacting an epoxy compound with (C2) component: at least one of two primary amino groups and secondary amino groups having no tertiary amino group in the molecule and having different reactivity A polyamine compound having the following formula, and having no tertiary amino group in the molecule, and having at least one of two or more primary amino groups and secondary amino groups in the molecule, At least one selected from the group consisting of an aromatic polyamine, an alicyclic polyamine and an aliphatic polyamine in which the reactivity between the remaining amino group and the epoxy group is lowered due to the structure in which one amino group is reacted with the epoxy group. Modified amine compound (D) having at least one active hydrogen-containing amino group in the molecule, which is obtained by reacting at least one of the polyamine compounds of the type with an epoxy compound: Component (D): organic filler.

  A second embodiment of the present invention is the thermosetting resin composition according to the first embodiment, wherein the component (A) contains an epoxy resin having an alicyclic skeleton.

  In the third embodiment of the present invention, the cyanate ester resin of the component (B) is a compound represented by the following general formula (1), a compound represented by the following general formula (2), and prepolymers thereof The thermosetting resin composition according to the first or second embodiment, which is at least one selected from the group consisting of

(In the above general formula (1), R ¹ is a divalent hydrocarbon group which is unsubstituted, substituted by a fluorine atom or substituted by a cyanate group, or a sulfur atom, and R ² and R ³ are Each of them is independently a phenylene group which is unsubstituted or substituted by 1 to 4 alkyl groups.)

(In the above general formula (2), n is an integer of 1 or more, R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ is each independently It is a group selected from the groups represented by the following general formulas (B-1) to (B-9).

(Here, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group which is unsubstituted or substituted with a fluorine atom, and m is an integer of 4 to 12.)
In the fourth embodiment of the present invention, the cyanate ester resin of the component (B) is at least one selected from the group consisting of a compound represented by the following general formula (3), and prepolymers thereof It is a thermosetting resin composition as described in the said 3rd embodiment.

(In the above general formula (3), R ⁵ is a group selected from the groups represented by the above general formulas (B-1) to (B-9), and R ⁸ is each independently hydrogen An atom or a methyl group which is unsubstituted or substituted by a fluorine atom)
In the fifth embodiment of the present invention, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and a compound represented by the following general formula The thermosetting resin composition according to any one of the above first to fourth embodiments, which is at least one polyamine compound selected from the group consisting of compounds represented by (III) .

(In the above general formula (I), each of R ²¹ and R ²² independently represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, which is substituted with a hydroxy group, a thiol group, or an amino group, R ²¹ and R ²² may be bonded to each other to form a ring, R ²³ is a (p + q) -valent hydrocarbon group, p is an integer of 1 or more, and q is 1 or 2. R ²⁴ is a hydrogen atom or an unsubstituted or oxygen atom, a sulfur atom, or an alkyl group having 1 to 10 carbon atoms containing a nitrogen atom.)

(In the above general formula (II), R ³¹ and R ³² are each independently an unsubstituted or an alkylene group containing an oxygen atom, a nitrogen atom or a sulfur atom. R ³³ is an alkyl having 1 to 10 carbon atoms And r is an integer of 1 or more.)

(In the above general formula (III), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently unsubstituted or substituted with a hydroxy group, a thiol group or an amino group, and have 1 to 10 carbon atoms R ⁴¹ and R ⁴² , or R ⁴³ and R ⁴⁴ may combine with each other to form a ring, and R ⁴⁵ and R ⁴⁶ each independently represent an unsubstituted or oxygen atom And an alkylene group containing a nitrogen atom or a sulfur atom, s is an integer of 1 or more.)
The sixth embodiment of the present invention is the thermosetting as described in the fifth embodiment, wherein the polyamine compound of the general formula (I) is a polyamine compound represented by the following general formula (I-1) It is a resin composition.

(In the above general formula (I-1), R ²¹ and R ²² each independently represent a non-substituted or alkyl group having 1 to 10 carbon atoms substituted with a hydroxy group, a thiol group, or an amino group, At this time, R ²¹ and R ²² may be bonded to each other to form a ring, and R ²⁵ is an alkylene group having 1 to 10 carbon atoms.)
The seventh embodiment of the present invention is characterized in that the polyamine compound constituting the component (C2) is isophorone diamine, p-menthane-1,8-diamine, 2,2,4-trimethylhexamethylene diamine, 1,2- In any one of the above-described first to sixth embodiments, which is at least one polyamine compound selected from the group consisting of diaminopropane, m-xylylenediamine, and 1,3-bisaminomethylcyclohexane. It is a thermosetting resin composition as described.

  In the eighth embodiment of the present invention, the epoxy compound used in the component (C) is a polyglycidyl ether compound having two or more epoxy groups in the molecule. It is a thermosetting resin composition as described in any one of these.

  In the ninth embodiment of the present invention, the modified amine compound of the component (C1) or the component (C2) has an epoxy equivalent of 0.5 to 2.0 equivalents with respect to an amount of 1 mole of the polyamine compound. The thermosetting resin composition according to any one of the above-mentioned first to eighth embodiments, which is obtained by reacting the epoxy compound in an amount of

  The tenth embodiment of the present invention is characterized in that the phenolic resin used in the component (C) has a number average molecular weight of 750 to 1200 according to any one of the first to ninth embodiments. It is a thermosetting resin composition.

  In an eleventh embodiment of the present invention, the amount of the phenolic resin used in the component (C) is 10 to 100 based on 100 parts by mass of the component (C1) or the modified polyamine of the component (C2). It is a thermosetting resin composition as described in any one of the said 1st to 10th embodiment which is a mass part.

  The twelfth embodiment of the present invention is characterized in that the component (D) comprises a filler comprising a polymer or copolymer of (meth) acrylic acid ester, or a polymer or copolymer of styrene compound. The thermosetting resin composition according to any one of the first to eleventh embodiments.

  The thirteenth embodiment of the present invention is the thermosetting resin composition according to any one of the first to twelfth embodiments, which is used to fix a neodymium magnet.

The present invention comprises the following components (A) to (D), and a thermosetting resin composition containing 25 to 75% by mass of the following component (A) based on the total of the following components (A) and (B): It is a thing:
Component (A): Epoxy Resin (B) Component: Cyanate Ester Resin (C) Component: First Curing Agent Containing Modified Amine Compound of the Following Component (C1) and Phenolic Resin, and Component (C2) Second curing agent comprising a modified amine compound and a phenol resin (C1) component: a polyamine compound having at least one of one or more tertiary amino groups and one or more primary amino groups and secondary amino groups Modified amine compound obtained by reacting an epoxy compound with (C2) component: at least one of two primary amino groups and secondary amino groups having no tertiary amino group in the molecule and having different reactivity And a polyamine compound having at least one of a primary amino group and a secondary amino group in the molecule without having a tertiary amino group in the molecule, At least one selected from the group consisting of an aromatic polyamine, an alicyclic polyamine and an aliphatic polyamine in which the reactivity of the remaining amino group with the epoxy group is lowered due to the structure in which one amino group is reacted with the epoxy group. A modified amine compound (D) having at least one amino group having an active hydrogen in the molecule, which is obtained by reacting at least one of the polyamine compounds of the above and an epoxy compound. Component (D): an organic filler.

  The thermosetting resin composition having such a constitution enables stable fixation even after the endurance test in fixing neodymium. In addition, the thermosetting resin composition of the present invention is excellent in rapid curability and storage stability.

  Although the detailed reason why the above effect is obtained by the thermosetting resin composition of the present invention is unclear, the curing behavior and the crosslinked structure of the cured product are obtained by using two kinds of curing agents having different curing reaction mechanisms. Etc. are optimized, adhesion and toughness are improved, and in fixing neodymium, it is considered to enable stable fixation even after a durability test. Therefore, according to the thermosetting resin composition of the present invention, a thermosetting resin composition having fast curing and excellent storage stability, and capable of stable fixation even after a durability test in the fixation of neodymium magnet The goods are provided. The present invention is not limited to the above mechanism.

  The details of the invention will now be described.

  The component (A) that can be used in the present invention is a compound having two or more epoxy groups in one molecule, and is a compound generally called an epoxy resin. The component (A) may be used alone or in combination of two or more. From the viewpoint of ease of handling, the component (A) is preferably liquid in an atmosphere at 25 ° C.

  Specific examples of epoxy resins include those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenol and polyhydric alcohols, and examples thereof include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, Glycidyl ethers such as bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolak type, phenol novolak type, ortho cresol novolac type, tris (hydroxyphenyl) methane type, tetraphenylol ethane type Type epoxy resin can be exemplified. In addition, glycidyl ester type epoxy resins obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids, glycidyl amine type epoxy resins obtained by reaction of epichlorohydrin with amines, cyanuric acids or hydantoins, di The epoxy resin which has alicyclic skeletons, such as a cyclopentadiene dimethanol type | mold, and also the epoxy resin modified | denatured by various methods are mentioned. However, it is not limited to these.

  Examples of commercially available epoxy resins include EP-4100, EP-4100E, EP-4088S, EP-4901, etc., manufactured by ADEKA Co., Ltd., 827, 828EL, etc., manufactured by Mitsubishi Chemical Corporation, manufactured by Dainippon Ink Industries Co., Ltd. EPICLON 830, EXA-835 LV etc. are mentioned. In addition, Epototo YD-128, YDF-170 and the like manufactured by Tohto Kasei Co., Ltd. may also be mentioned, but the invention is not limited thereto. In consideration of the price, epoxy resins having a bisphenol A skeleton or a bisphenol F skeleton are preferable.

In consideration of the resistance to the endurance test, epoxy resins having an alicyclic skeleton are particularly preferable. Note that “alicyclic skeleton” refers to a skeleton represented by the general formula C _t H _2t (t = 3 or more), and as a compound having an alicyclic skeleton, for example, a cyclic cyclo compound or a cyclic bicyclo compound, and Their fused rings and the like can be mentioned. Specific examples of the alicyclic skeleton include, but are not limited to, structures such as isobornyl, tricyclodecane, adamantane, dicyclopentadiene and the like.

  Furthermore, in order to further improve the effects of the present invention, epoxy resins having an alicyclic skeleton and an aromatic ring skeleton are preferable.

  The component (B) which can be used in the present invention is a compound having two or more cyanate ester groups in one molecule, and is a compound generally called cyanate ester resin. Although it does not specifically limit as cyanate ester resin, For example, the compound represented by the compound represented by the following general formula (1) and / or the following general formula (2) is mentioned. Moreover, the prepolymer in which a part of cyanate group of the compound represented by following General formula (1) or following General formula (2) forms the triazine ring can also be used as (A) component. As a prepolymer, what the trimmerization of all or one part of the compound represented by following General formula (1) is mentioned, for example is mentioned.

(In the above general formula (1), R ¹ is a divalent hydrocarbon group or a sulfur atom which is unsubstituted, substituted with a fluorine atom, or substituted with a cyanate group, and R ² and R ³ each represent Independently, it is a phenylene group which is unsubstituted or substituted by 1 to 4 alkyl groups.)

(In the above general formula (2), n is an integer of 1 or more, R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ is each independently It is a group selected from the groups represented by the following chemical formulas (B-1) to (B-9).)

(Here, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group which is unsubstituted or substituted with a fluorine atom, and m is an integer of 4 to 12.)
In the present specification, the "alkyl group" is a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec- A butyl group and a tert- butyl group are mentioned.

In General Formula (1) above, the divalent hydrocarbon group as R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group as R ¹ includes a linear, branched or cyclic hydrocarbon group, and includes, for example, an alkylene group, an arylene group, and an aralkylene group. More specifically, examples of divalent hydrocarbon groups include methylene, ethylene, methylmethylene, propylene, dimethylmethylene, methylethylene, butylene, pentylene, hexylene and cyclopentylene groups. And alkylene groups such as cyclohexylene group; arylene groups such as phenylene group, tolylene group and xylylene group; and aralkylene groups such as benzylene, β-phenylethylene, γ-tolylpropylene etc., but not limited thereto.

  In the general formula (2), the upper limit of n is preferably 10.

  Among the compounds represented by the above general formula (1), more preferable compounds are a compound represented by the following general formula (3), and prepolymers thereof.

(In the above general formula (3), R ⁵ is a group selected from the groups represented by the above chemical formulas (B-1) to (B-9), and R ⁸ is each independently a hydrogen atom or It is a methyl group which is unsubstituted or substituted by a fluorine atom.)
In order to further improve the effect of the present invention, in the above general formula (3), R ⁵ is preferably a group represented by (B-1). Further, R ⁸ is preferably a hydrogen atom. Furthermore, R ⁵ is a group represented by (B-1), and a form in which R ⁸ is a hydrogen atom is particularly preferable.

  More specifically, as the component (B), 4,4′-ethylidene bisphenylene cyanate, 2,2-bis (4-cyanatophenyl) propane, 1,1-bis (4-cyanatophenyl) ethane And bis (4-cyanato-3,5-dimethylphenyl) methane and the like are particularly preferred, but not limited thereto.

  The addition amount of the component (A) is 25 to 75% by mass, preferably 30 to 70% by mass, with respect to the total of the component (A) and the component (B). When the content is 25% by mass or more, sufficient curability is exhibited and peeling does not occur in the durability test. On the other hand, peeling does not generate | occur | produce in a durability test as it is 75 mass% or less.

  The component (C) that can be used in the present invention is a curing agent for curing the components (A) and (B), and includes two types of curing agents.

  The first curing agent which can be used in the present invention is a latent curing agent comprising the modified amine compound of component (C1) and a phenol resin. The modified amine compound as the component (C1) is a compound in which a polyamine compound and an epoxy compound are reacted, and the polyamine compound is one or more tertiary amino groups and one or more primary amino groups and It refers to a polyamine compound having at least one of the primary amino groups.

  The polyamine compound of the component (C1) used in the present invention is a compound represented by the following general formula (I), a compound represented by the following general formula (II), and a compound represented by the following general formula (III) Preferably, at least one selected from the group consisting of

(In the above general formula (I), each of R ²¹ and R ²² independently represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, which is substituted with a hydroxy group, a thiol group, or an amino group, R ²¹ and R ²² may be bonded to each other to form a ring, R ²³ is a (p + q) -valent hydrocarbon group, p is an integer of 1 or more, and q is 1 or 2. R ²⁴ is a hydrogen atom, or an unsubstituted or oxygen atom, a sulfur atom, or an alkyl group having 1 to 10 carbon atoms including a nitrogen atom.)

(In the above general formula (II), R ³¹ and R ³² are each independently an unsubstituted or an alkylene group containing an oxygen atom, a nitrogen atom or a sulfur atom. R ³³ is an alkyl having 1 to 10 carbon atoms And r is an integer of 1 or more.)

(In the above general formula (III), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently an unsubstituted or substituted C 1-10 alkyl substituted with a hydroxy group, a thiol group or an amino group And R ⁴¹ and R ⁴² or R ⁴³ and R ⁴⁴ may combine with each other to form a ring R ⁴⁵ and R ⁴⁶ each independently represent an unsubstituted or oxygen atom, nitrogen An atom or an alkylene group containing a sulfur atom, s is an integer of 1 or more.)
In the above general formula (I), R ²¹ and R ²² are preferably each independently an unsubstituted alkyl group of 1 to 5 carbon atoms. p is preferably an integer of 1 or more and 3 or less. R ²⁴ is preferably a hydrogen atom. In general formula (I), R ²¹ and R ²² are each independently an unsubstituted alkyl group of 1 to 5 carbon atoms, p is an integer of 1 or more and 3 or less, and R ²⁴ is hydrogen Particularly preferred is an atom. Furthermore, in general formula (I), R ²¹ and R ²² are each independently an unsubstituted alkyl group of 1 to 5 carbon atoms, p is an integer of 1 or more and 2 or less, and R ²⁴ is hydrogen Particularly preferred is an atom.

  In the above general formulas (II) and (III), the upper limit of r and s is preferably 10, respectively.

  Here, as the polyamine compound represented by the above general formula (I), for example, N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine N, N-benzylmethylaminoethylamine, N, N-dibenzylaminoethylamine, N, N-cyclohexylmethylaminoethylamine, N, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2 -Aminoethyl) piperidine, N- (2-aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N'-methylpiperazine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N Diisopropylaminopropylamine, N, N-diallylaminopropylamine, N, N-benzylmethylaminopropylamine, N, N-dibenzylaminopropylamine, N, N-cyclohexylmethylaminopropylamine, N, N-dicyclohexylamino Propylamine, N- (3-aminopropyl) pyrrolidine, N- (3-aminopropyl) piperidine, N- (3-aminopropyl) morpholine, N- (3-aminopropyl) piperazine, N- (3-aminopropyl ) -N'-methylpiperidine, 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N-diisopropylamino) benzylamine, N, N- Dimethyl isophorone diamine, N, N-dimethyl bis amino Chlorohexane, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethylethylenediamine, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethylpropanediamine, N ' Examples include, but are not limited to, -ethyl-N, N-dibenzylaminopropylamine and the like.

  Examples of polyamine compounds represented by the above general formula (II) include N, N- (bisaminopropyl) -N-methylamine, N, N-bisaminopropylethylamine, N, N-bisaminopropylpropylamine N, N-bisaminopropylbutylamine, N, N-bisaminopropylpentylamine, N, N-bisaminopropylhexylamine, N, N-bisaminopropyl-2-ethylhexylamine, N, N-bisaminopropyl Examples include, but are not limited to, cyclohexylamine, N, N-bisaminopropylbenzylamine, N, N-bisaminopropylallylamine and the like.

  Examples of polyamine compounds represented by the above general formula (III) include bis [3- (N, N-dimethylaminopropyl)] amine, bis [3- (N, N-diethylaminopropyl)] amine, bis [3 Examples include, but are not limited to, 3- (N, N-diisopropylaminopropyl)! Amine and bis [3- (N, N-dibutylaminopropyl)] amine.

  Among the polyamine compounds represented by the above general formula (I), particularly preferred are compounds represented by the following general formula (I-1). By using such a polyamine compound, it becomes a thermosetting resin composition which is excellent in the balance of curability and storage stability.

(In the above general formula (I-1), R ²¹ and R ²² each independently represent a non-substituted or alkyl group having 1 to 10 carbon atoms substituted with a hydroxy group, a thiol group, or an amino group, At this time, R ²¹ and R ²² may be bonded to each other to form a ring, and R ²⁵ is an alkylene group having 1 to 10 carbon atoms.)
In order to further improve the effect of the present invention, in the polyamine compound represented by the above general formula (I-1), R ²¹ and R ²² are each independently an unsubstituted or hydroxy group, a thiol group or an amino group It is preferable that it is a C1-C4 alkyl group substituted by these. R ²⁵ is preferably an alkylene group having 1 to 4 carbon atoms. Furthermore, it is particularly preferable that R ²¹ and R ²² each independently be an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ^{25 be} an alkylene group having 1 to 4 carbon atoms.

  Here, as the polyamine compound represented by the above general formula (I-1), for example, N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallyl Aminoethylamine, N, N-benzylmethylaminoethylamine, N, N-dibenzylaminoethylamine, N, N-cyclohexylmethylaminoethylamine, N, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2-Aminoethyl) piperidine, N- (2-Aminoethyl) morpholine, N- (2-Aminoethyl) piperazine, N- (2-Aminoethyl) -N'-methylpiperazine, N, N-dimethylaminopropyl Amine, N, N-diethylaminopropylamine, N N-diisopropylaminopropylamine, N, N-diallylaminopropylamine, N, N-benzylmethylaminopropylamine, N, N-dibenzylaminopropylamine, N, N-cyclohexylmethylaminopropylamine, N, N- Dicyclohexylaminopropylamine, N- (3-aminopropyl) pyrrolidine, N- (3-aminopropyl) piperidine, N- (3-aminopropyl) morpholine, N- (3-aminopropyl) piperazine, N- (3-aminopropyl) piperazine Examples include, but not limited to, aminopropyl) -N'-methylpiperidine and the like. Most preferably, N, N-dimethylaminopropylamine and N, N-diethylaminopropylamine are mentioned.

  As an epoxy compound to be reacted with the component (C1) used in the present invention, a compound having an epoxy group can be used without particular limitation, and an epoxy resin exemplified as the component (A) can also be used. Specific examples of the epoxy compound include, for example, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, sec-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, stearyl glycidyl ether, etc. Monoglycidyl ether compounds; monoglycidyl ester compounds such as versatic acid glycidyl ester; polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol ( Bisphenol F), methylene bis (ortho cresol), ethylidene bisphenol, isopropylidene Bisphenol (bisphenol A), isopropylidene bis (ortho cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho cresol novolak, ethylphenol novolac, Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as butylphenol novolak, octylphenol novolak, resorcinol novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol , Polyglycidyl ethers of polyhydric alcohols such as hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid Glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid And homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as endomethylene tetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidyl aniline, bis (4- ( Epoxy compounds having a glycidyl amino group such as N-methyl-N-glycidylamino) phenyl) methane and diglycidyl ortho toluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4 Epoxide compounds of cyclic olefin compounds such as epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxy Epoxidized conjugated diene (co) polymers such as activated polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate, but are also limited thereto Not. In particular, polyglycidyl ether compounds having two or more epoxy groups in the molecule are preferred. In particular, polyglycidyl ethers of bisphenol compounds such as methylene bisphenol (bisphenol F), methylene bis (ortho cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A) and isopropylidene bis (ortho cresol) are preferable.

  The modified polyamine compound used in the component (C1) is a compound obtained by reacting an epoxy compound in an amount of 0.5 to 2.0 equivalents of epoxy equivalent to an amount of 1 mol of polyamine compound. Is preferred. More preferably, they are modified polyamine compounds obtained by reacting an epoxy compound in such an amount that the epoxy equivalent is 0.8 to 1.5 equivalents, and even more preferably 1.0 to 1.3 equivalents. As a polyamine compound, it is also possible to use one kind or a combination of two or more kinds of different kinds of polyamine compounds.

  As a phenol resin contained in the 1st hardening | curing agent which comprises (C) component used for this invention, the phenol resin synthesize | combined from phenols and aldehydes is preferable. Examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone And one or more species such as 2,2-bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpene phenol, and phenolated dicyclopentadiene. Examples include, but are not limited to, formaldehyde. The synthesis method is not particularly limited, and known condensation reactions using an acid catalyst or an alkali catalyst can be employed.

  The number average molecular weight of the phenol resin used in the component (C) together with the component (C1) is preferably 750 to 1200, and particularly preferably 750 to 1000. If it is a number average molecular weight of this range, a thermosetting resin composition excellent in the balance between storage stability and curability can be obtained. The number average molecular weight of the phenol resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  It is preferable that 10 to 100 parts by mass of a phenol resin is contained in 100 parts by mass of the modified amine compound of the component (C1) in the first curing agent. More preferably, the content of the phenol resin is 20 to 60 parts by mass. When the content of the phenol resin is 10 parts by mass or more, sufficient curability is obtained, and when the content is 100 parts by mass or less, sufficient physical properties are developed in the cured product.

  The second curing agent which can be used in the present invention is a latent curing agent comprising the modified amine compound of component (C2) and a phenol resin. The modified amine compound as the component (C2) is a compound obtained by reacting a polyamine compound and an epoxy compound, and is a modified amine compound having one or more amino groups having active hydrogen in the molecule. The polyamine compound is a polyamine compound having no tertiary amino group in the molecule and having at least one of two primary amino groups and secondary amino groups having different reactivity, and a tertiary compound in the molecule. According to the structure having no amino group and at least one of two or more primary amino groups and secondary amino groups in the molecule, and the one amino group reacting with the epoxy group, the remaining amino groups and It refers to at least one of at least one polyamine compound selected from the group consisting of aromatic polyamines, alicyclic polyamines, and aliphatic polyamines having reduced reactivity with epoxy groups.

  Here, as a specific example of the epoxy compound used by (C2) component, since it is the same as that of the epoxy compound described by the said 1st hardening | curing agent, description is abbreviate | omitted here. The epoxy compounds used in the (C1) component and the (C2) component may be the same or different.

  Moreover, as a specific example of a phenol resin used by (C) component with (C2) component, since it is the same as that of the phenol resin described by the said 1st hardening | curing agent, description is abbreviate | omitted here. The phenolic resin used with the (C1) component and the phenolic resin used with the (C2) component may be the same or different.

  As a polyamine compound having at least one of two primary amino groups and secondary amino groups which do not have a tertiary amino group in the molecule used in the component (C2) and which have different reactivities, respectively, The polyamine compound which has a structure is mentioned. Specific examples thereof include, for example, isophorone diamine, p-menthan-1,8-diamine, 2,2,4-trimethylhexamethylene diamine, 1,2-diaminopropane and the like, but are not limited thereto. Absent.

  Component (C2) has no tertiary amino group in the molecule and at least one of two or more primary amino groups and secondary amino groups in the molecule, and the one amino group is epoxy As aromatic polyamines, alicyclic polyamines, and aliphatic polyamines, the reactivity of the remaining amino groups with epoxy groups is reduced due to the structure reacted with the groups, and polyamines having substituents that cause cyclic structure or steric hindrance. Compounds are mentioned. Specific examples thereof include, but are not limited to, for example, m-xylylene diamine, 1,3-bisaminomethyl cyclohexane and the like. As a polyamine compound, it is also possible to use singly or in combination of two or more different types of polyamine compounds.

  The modified polyamine compound used in the component (C2) is a compound obtained by reacting the epoxy compound in an amount of 0.5 to 2.0 equivalents of epoxy equivalent to the amount of 1 mol of polyamine compound. Is preferred. More preferably, they are modified polyamine compounds obtained by reacting an epoxy compound in such an amount that the epoxy equivalent is 0.8 to 1.5 equivalents, and even more preferably 1.0 to 1.3 equivalents. As a polyamine compound, it is also possible to use singly or in combination of two or more different types of polyamine compounds.

  The number average molecular weight of the phenol resin used in the component (C) together with the component (C2) is preferably 750 to 1200, and particularly preferably 750 to 1000. If it is a number average molecular weight of this range, a thermosetting resin composition excellent in the balance between storage stability and curability can be obtained.

  It is preferable that 10-100 mass parts of phenol resin is contained with respect to 100 mass parts of modified amine compounds of (C2) component in a 2nd hardening | curing agent. More preferably, the content of the phenol resin is 20 to 60 parts by mass. When the amount of the phenol resin is 10 parts by mass or more, sufficient curability is obtained, and when the amount is 100 parts by mass or less, sufficient physical properties are developed in the cured product.

  An epoxy-modified modified amine compound in which the primary amino group of the imidazole compound is epoxy-modified can also be used in combination with the (C2) component.

  The addition amount of the component (C) is preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). More preferably, it is 20-40 mass parts. When the amount of the component (C) is 10 parts by mass or more, curability is sufficiently developed. On the other hand, in the case of 50 parts by mass or less, storage stability is improved.

  The component (D) that can be used in the present invention is an organic filler. The organic filler may be an organic powder composed of rubber, elastomer, plastic, polymer (or copolymer) or the like. In addition, an organic filler having a multilayer structure such as a core-shell type may be used. As an average particle diameter of an organic filler, the range of 0.05-50 micrometers is preferable. From the viewpoint of improving the properties in durability test, a filler comprising a polymer or copolymer of an acrylic ester and / or a methacrylic ester ((meth) acrylic ester), or a polymer or copolymer of a styrene compound It is preferable to contain the filler which consists of coalescence.

  Although the following goods are mentioned as a specific example of (D) component, It is not limited to these. Specific examples of the butadiene rubber filler include Metabrene (registered trademark) E series manufactured by Mitsubishi Rayon Co., Ltd., and Metabrene (registered trademark) C series. Specific examples of the above acrylic rubber filler include MX series manufactured by Soken Chemical Co., Ltd., Metabrene (registered trademark) W series manufactured by Mitsubishi Rayon Co., Ltd., Zefiac series manufactured by Aika Kogyo Co., Ltd. Specific examples of styrene (polystyrene) fillers include SX series and SGP series manufactured by Soken Chemical Co., Ltd., ChromoSphere-T series manufactured by Thermo Fisher Scientific, Estapor (registered trademark) series manufactured by Merck Chimie, fine manufactured by Matsuura Co., Ltd. Pearl series etc. are mentioned.

  Moreover, you may use the organic filler disperse | distributed beforehand in the epoxy resin of (A) component. Specifically, rubber particles dispersed in an epoxy resin by a mixing / stirring apparatus such as a hyper or a homogenizer, or an organic filler synthesized by emulsion polymerization in the epoxy resin corresponds to this. The average particle diameter of the organic filler finally formed by the method by emulsion polymerization is preferably in the range of 0.05 to 0.5 μm. The use of rubber particles previously dispersed in an epoxy resin has the advantage that the handling of the components is simplified during the production of the thermosetting resin composition. In addition, since the epoxy resin sufficiently blends in with the organic filler, the viscosity change tends to decrease with time.

  It is preferable that 5-50 mass parts of (D) components are contained with respect to a total of 100 mass parts of (A) component and (B) component. More preferably, it is 10-40 mass parts. If the amount of the component (D) is less than 5 parts by mass, the durability to the durability test may be reduced. On the other hand, if the amount of the component (D) is more than 50 parts by mass, the viscosity becomes too high, which may cause coating problems such as stringing.

  The method for producing the thermosetting resin composition of the present invention is not particularly limited, and examples thereof include a method in which each component is mixed at one time, a method in which each component is sequentially added and mixed, and the like. Among them, it is preferable to add and mix the component (D) and the component (C) in this order after the component (A) and the component (B) are mixed, from the viewpoint of more uniformly curing later.

  In the thermosetting resin composition of the present invention, a monomer such as a monofunctional epoxy compound (reactive diluent), a pigment such as a pigment and a dye, a metal powder, calcium carbonate, etc. insofar as the characteristics of the present invention are not impaired. An appropriate amount of additives such as inorganic fillers such as fumed silica and aluminum hydroxide, flame retardants, plasticizers, antioxidants, antifoaming agents, silane coupling agents, leveling agents, rheology control agents may be added. . By adding these, a composition excellent in at least one of resin strength, adhesive strength, workability, storage property and the like and a cured product thereof can be obtained.

  The thermosetting resin composition of the present invention can be used particularly for fixing neodymium.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

[Examples 1 to 11, Comparative Examples 1 to 5]
The following components were prepared to prepare the thermosetting resin compositions of Examples 1 to 11 and Comparative Examples 1 to 5 (hereinafter, the thermosetting resin composition is simply referred to as a composition).

(A) Component: Epoxy resin-Preparation of epoxy resin In a flask, 400 g of bisphenol A epoxy resin (EP-4100E manufactured by ADEKA, epoxy equivalent 190) and dicyclopentadiene dimethanol type epoxy resin (EPK manufactured by ADEKA) 4088S, epoxy equivalent 170) 100 g was charged, and mixed for 0.5 hours at 60 ° C. to obtain an epoxy resin (hereinafter referred to as EP).

Component (B): cyanate ester resin 1,1-bis (4-cyanatophenyl) ethane (hereinafter referred to as CY).

Component (C): A first curing agent comprising the modified amine compound of component (C1) and a phenolic resin, and a second curing agent comprising the modified amine compound of component (C2) and a phenolic resin Preparation of First Curing Agent Containing Modified Amine Compound of Component (C1) and Phenolic Resin 130 g of N, N-dimethylaminopropylamine was charged into a flask and maintained at 80 ° C. 213 g ([Epoxy equivalent 1.12 of bisphenol A type epoxy resin to 1 mol of N, N-dimethylaminopropylamine]) of EP-4100E, manufactured by ADEKA Corporation, epoxy equivalent 190, was added little by little. After the bisphenol A epoxy resin was added, the temperature in the system was raised to 140 ° C., and reaction was performed for 1.5 hours to obtain a modified amine compound. To 100 g of the modified amine compound thus obtained, 30 g of a phenol resin (the product obtained by condensation reaction using phenol and formalin using an acid catalyst, number average molecular weight: 800) is charged, and 180 to 190 ° C., 4.0 to The solvent was removed at 5.3 kPa (30 to 40 Torr) for 1 hour to obtain a latent curing agent (first curing agent) (hereinafter referred to as EH-1).

-Preparation of a second curing agent comprising the modified amine compound of component (C2) and a phenolic resin 128 g of 1,2-diaminopropane is charged into a flask and heated to 60 ° C., and then a bisphenol A type epoxy resin (EPA-4100E manufactured by ADEKA, epoxy equivalent 190) 213 g ([Epoxy equivalent 1.12 of bisphenol A type epoxy resin to 1 mol of 1,2-diaminopropane]) is maintained at a system internal temperature of 100 to 110 ° C. I added it little by little to make it fall. After all of the bisphenol A epoxy resin was added, the temperature was raised to 140 ° C., and reaction was performed for 1.5 hours to obtain a modified polyamine. To 100 g of the modified polyamine obtained, 30 g of a phenol resin (one obtained by condensation reaction using an acid catalyst from phenol and formalin, number average molecular weight: 800) is charged, 180 to 190 ° C., 4.0 to 5 Desolvation was carried out at 30 kPa (30 to 40 Torr) for 1 hour to obtain a latent curing agent (second curing agent) (hereinafter referred to as EH-2).

Component (D): Organic filler · Acrylic rubber particles (average particle size 10 μm) (MX-1000 manufactured by Soken Chemical Co., Ltd.)
Polystyrene particles (average particle diameter 6 μm) (Fine Pearl PB-3006E manufactured by Matsuura Co., Ltd.).

  After stirring the said (A) component and (B) component for 15 minutes, (D) component was added and it stirred for further 15 minutes. Finally, component (C) was added and stirred for 30 minutes. The detailed preparation amounts are shown in Table 1 and all numerical values are expressed in parts by mass.

  With respect to the thermosetting resin compositions of Examples 1 to 11 and Comparative Examples 1 to 5, storage stability confirmation, 90 ° C. curing time measurement, tensile shear adhesion measurement, and heat cycle resistance confirmation were carried out. The results are summarized in Table 2 below.

[Confirmation of storage stability]
Storage stability is confirmed by viscosity measurement. A cone and plate rotational viscometer (E-type viscometer) whose cup is adjusted to 25 ° C. using a circulating constant temperature bath is used. After measuring the initial viscosity, it is left in an atmosphere at 25 ° C., and measurement is performed every 3 days, and the number of days until the viscosity reaches twice the initial viscosity is defined as “storage stability (day)”. Judgment is based on the following judgment criteria. In order to be able to use stably at the time of discharge, it is preferable that the viscosity doubles in an atmosphere at 25 ° C. for 15 days or more.

15 days or more: ○
Less than 15 days: x.

[90 ° C curing time measurement]
The composition is applied on a hot plate set at 90 ° C., and the time until the surface of the composition cures is measured. The time when the tackiness disappears on the surface of the composition is referred to as “90 ° C. curing time (seconds)”. Judgment is based on the following judgment criteria. It is preferable to cure in less than 20 seconds at 90 ° C. in order to shorten the curing time.

Less than 10 seconds: ◎
10 seconds or more and less than 20 seconds: ○
20 seconds or more: x.

[Measurement of tensile shear adhesion]
The adherend is made of SPCC-SD (Cold-rolled steel plate with dull finish) material of width 25 mm × length 100 mm × thickness 1.6 mm, and the composition of two sheets with a bonding area of 25 mm × 1.6 mm Stick together and fix with a clip. Thereafter, the composition is allowed to cure in a hot air drying oven at 90 ° C. for 1 hour to prepare a test piece. The tensile strength is measured at a tensile speed of 10 mm / min to measure the "tensile shear adhesion (MPa)". The details conform to JIS K 6850: 1999. Judgment is based on the following judgment criteria. In order to maintain stable adhesion, the initial adhesion is preferably 8 MPa or more.

8 MPa or more: ○
Less than 8 MPa: x.

[Heat cycle resistance confirmation]
The heat cycle resistance is confirmed by tensile shear adhesion measurement. The adherends are SPCC-SD (cold-rolled steel plate dull finish) 25 mm wide x 100 mm long x 1.6 mm thick and neodymium magnet (Ni plated) 25 mm wide x 100 mm long x 1.6 mm thick Using the two sheets of material with a bonding area of 25 mm × 1.6 mm according to the composition and fixing with a clip. Thereafter, the composition is allowed to cure in a hot air drying oven at 90 ° C. for 1 hour to prepare 10 test pieces. Measure the adhesion of the 5 test pieces under the same conditions as the tensile shear adhesion measurement described above, and load the remaining 5 test pieces into the heat cycle tester. As heat cycle conditions, 100 cycles are performed continuously, with 15 minutes in an atmosphere of 0 ° C. and 15 minutes in an atmosphere of 100 ° C. as one cycle. Take out after completion and measure adhesion. Calculate “Retention (%)” from (adhesion average after heat cycle) / (initial adhesion average) × 100. Judge from the following evaluation criteria. In order to stably fix the neodymium magnet, it is preferable that the holding ratio be 50% or more.

50% or more: ○
Less than 50%: x.

  When the amount of the component (A) is increased as in Comparative Example 1, the curing time at 90 ° C. is prolonged, and the rapid curing property is lowered. Moreover, heat cycle resistance falls in the comparative example 1 and the comparative example 5 which the (B) component increases. From the comparison between Examples and Comparative Examples 1 and 5, it is understood that the heat cycle resistance is affected by the ratio of the component (A) and the component (B). Further, as in Comparative Example 2, it is understood that the heat cycle resistance is lowered even in the composition to which the component (D) is not added. When Examples 8 and 9 and Comparative Examples 3 and 4 are compared, Examples 8 and 9 have better adhesion and resistance to heat cycles, and thus, the components (C1) and (C2) and the components (C2) and Both have to be added.

  Neodimagnets are widely used in various fields such as electric and electronic fields, in-vehicle fields, etc. Along with this, since the demand for adhesives and sealing agents for stably fixing neody magnets becomes high, as described in the present invention, the neody magnets are stably fixed even after the endurance test (heat cycle resistance test). Thermosetting resin compositions capable of curing may also be used in various applications.

  Furthermore, the present application is based on Japanese Patent Application No. 2013-252351 filed on Dec. 5, 2013, the disclosure of which is incorporated by reference in its entirety.

Claims (11)

A thermosetting resin composition containing the following components (A) to (D) and containing 25 to 75% by mass of the following component (A) based on the total of the following components (A) and (B):
Component (A): Epoxy Resin (B) Component: Cyanate Ester Resin (C) Component: First Curing Agent Containing Modified Amine Compound of the Following Component (C1) and Phenolic Resin, and Component (C2) modified amine compound and comprising a phenolic resin second curing agent component (C1): N, N-dimethyl aminopropyl amine, modified amine compounds obtained by reacting an epoxy compound (C2) component: 2 -Modified amine compound having one or more amino groups having active hydrogen in the molecule, which is obtained by reacting diaminopropane with an epoxy compound. Component (D): organic filler.   The thermosetting resin composition according to claim 1, wherein the component (A) comprises an epoxy resin having an alicyclic skeleton. The cyanate ester resin of the component (B) is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a prepolymer thereof The thermosetting resin composition according to claim 1 or 2, which is
(In the above general formula (1), R ¹ is a divalent hydrocarbon group which is unsubstituted, substituted by a fluorine atom or substituted by a cyanate group, or a sulfur atom, and R ² and R ³ are Each of them is independently a phenylene group which is unsubstituted or substituted by 1 to 4 alkyl groups.)
(In the above general formula (2), n is an integer of 1 or more, R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ is each independently It is a group selected from the groups represented by the following general formulas (B-1) to (B-9).
(Here, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group which is unsubstituted or substituted with a fluorine atom, and m is an integer of 4 to 12.) The thermosetting resin according to claim 3, wherein the cyanate ester resin of the component (B) is at least one selected from the group consisting of a compound represented by the following general formula (3), and prepolymers thereof: Resin composition.
(In the above general formula (3), R ⁵ is a group selected from the groups represented by the above general formulas (B-1) to (B-9), and R ⁸ is each independently hydrogen An atom or a methyl group which is unsubstituted or substituted by a fluorine atom) The thermosetting resin composition according to any one of claims 1 to 4 , wherein the epoxy compound used in the component (C) is a polyglycidyl ether compound having two or more epoxy groups in the molecule. The epoxy compound is reacted in such an amount that the epoxy equivalent becomes 0.5 to 2.0 equivalents with respect to the amount that the modified amine compound of the component (C1) becomes 1 mole of the N, N-dimethylaminopropylamine. The thermosetting resin composition according to any one of claims 1 to 5 , which is obtained by The modified amine compound of the component (C2) is obtained by reacting the epoxy compound in such an amount that the epoxy equivalent becomes 0.5 to 2.0 equivalents with respect to the amount that the 1,2-diaminopropane becomes 1 mole. The thermosetting resin composition according to any one of claims 1 to 6, which is The thermosetting resin composition according to any one of claims 1 to 7 , wherein the number average molecular weight of the phenol resin used in the component (C) is 750 to 1200. With respect to the component (C1) or said (C2) variations of the components A amine compound to 100 parts by mass, the amount of phenolic resin used in the component (C) is 10 to 100 parts by weight, claim 1 The thermosetting resin composition according to any one of to 8 . The component (D), (meth) polymer or copolymer of acrylic acid ester, or a filler composed of a polymer or copolymer of a styrene compound, according to any one of claims 1-9 Thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 10 , which is used to fix a neodymium magnet.