JPH0565421A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a thermosetting resin composition excellent in adhesion and mechanical strength not only at ordinary temperatures but high temperatures, low in metal corrosion, excellent in electrical insulation and especially suitable for electric and electronic components. CONSTITUTION:This invented thermosetting resin composition contains 100 pts.wt. polymer components containing 5-70wt.% copolymer obtained by emulsion polymerization of (a) 30-95wt.% thermosetting resin in the presence of (b) at least a nonionic surfactant as the emulsifier and containing a monomer unit containing at least a carboxylic group in amount of 1-20wt.% based on the copolymer and (c) 0.1-10 pts.wt. compounds of one or more kinds of metals selected from the II and III groups in the periodic table.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified thermosetting resin composition, more specifically, it has excellent adhesive strength, impact resistance, heat resistance and the like, and is used as an adhesive, a coating material, a sealant, and various other molding materials. The present invention relates to a thermosetting resin composition suitable for.

[0002]

2. Description of the Related Art Generally, epoxy resin has a small curing shrinkage, a large dimensional stability, a large mechanical strength, an excellent electrical property as an insulating material, and further has many properties such as heat resistance, water resistance and chemical resistance. When used as an adhesive, coating agent, etc., it has excellent adhesive strength, adhesion strength and mechanical strength to metal, porcelain, concrete, etc. and excellent shear strength and tensile strength. .. However, since epoxy resin is not sufficiently flexible, when used as an adhesive, coating agent, etc.,
It has a problem that the peel strength is very low and cracks and peeling are likely to occur. Further, when an epoxy resin is used as a molding material, there is a problem that the molded product is brittle and is easily broken by various impacts. Such problems were the same with thermosetting resins such as phenol resins and melamine resins in addition to epoxy resins.

As one of the methods for solving the above problems,
Generally, a method of adding an elastomer to an epoxy resin, a phenol resin, etc. is known and widely used. In particular, acrylonitrile-butadiene rubber (hereinafter abbreviated as NBR) that has excellent compatibility with epoxy resins and phenol resins.
Alternatively, an elastomer such as an acrylic ester rubber (hereinafter abbreviated as ACM) is used, and it is known that particularly excellent properties are exhibited by introducing a carboxyl group into these elastomers.

However, NBR and ACM containing a carboxyl group, which are usually commercially available, have a large content of various ionic components, and when they are used in the electric and electronic fields, in particular, the insulation resistance is lowered and the metal is corrosive. It was accompanied by problems such as an increase. On the other hand, the inventors of the present invention have disclosed in JP-A-61-161.
9827, 62-59660, 63-1255.
As disclosed in Japanese Patent Publication No. 89, by performing emulsion polymerization using a nonionic emulsifier and adding various elastomers obtained by heat coagulation in the presence of a metal-free electrolyte to a thermosetting resin, insulation Achieved an excellent modifying effect that suppresses a decrease in resistance and deterioration of metal corrosion.

[0005]

However, the above-mentioned JP-A-61-69827, JP-A-62-59660, and JP-A-6-69627.
When the thermosetting resin composition obtained by the method described in JP-A-3-125589 is used as an adhesive, the adhesive strength at room temperature and metal corrosion are excellent, but the adhesive strength at high temperature is The problem of being low has become apparent.

In view of the above situation, the present invention overcomes the conventional problems and has excellent adhesive force and mechanical strength not only at room temperature but also at high temperature, and also has a low metal corrosion property and an excellent electrical insulation property. Another object of the present invention is to provide a thermosetting resin composition suitable for electric / electronic parts.

[0007]

That is, the present invention is as follows.
(A) 30 to 95% by weight of a thermosetting resin, and (b) a monomer unit obtained by emulsion polymerization using at least a nonionic surfactant as an emulsifier, and containing at least a carboxyl group. Polymer component 10 containing 5 to 70% by weight of the copolymer, which is 1 to 20% by weight of the polymer.
0 to 10 parts by weight of (c) a compound of 0.1 to 10 of at least one metal selected from Group II or Group III of the periodic table.
The present invention provides a thermosetting resin composition characterized by containing parts by weight.

(Structure) The present invention will be described in detail below.

Component (a) The thermosetting resin which is the component (a) used in the present invention is appropriately selected according to its application, and various types can be used.

As the component (a), for example, phenol resin, epoxy resin, urea resin, melamine resin, polyimide resin, unsaturated polyester resin or the like can be used.

As the phenol resin, for example, novolac resin, resole resin, or modified products of these can be mentioned. Further, a composite with other materials such as phenol-modified melamine resin can also be used.

Examples of the epoxy resin include various epoxy resins such as bisphenol type epoxy resin, novolac type epoxy resin and alicyclic epoxy resin, as well as modified epoxy such as rubber modified epoxy resin, urethane modified epoxy resin and brominated epoxy resin. Resin etc. can be mentioned.

As the urea resin, various cationic, nonionic or anionic urea resins can be mentioned.

Examples of the melamine resin include urea-melamine resin, which is a modified urea resin, in addition to melamine resin alone.

Examples of the polyimide resin include a polyimide resin obtained by reacting a tetracarboxylic acid or its anhydride with a diamine, and a maleimide-modified epoxy resin.

Examples of unsaturated polyester resins include polyester resins having two or more unsaturated bonds per molecule such as diallyl phthalate, diallyl fumarate and divinyl phthalate.

These thermosetting resins can be used alone or in admixture of two or more.

Of these, the phenol resin, epoxy resin and unsaturated polyester resin are easy to process with a closed type kneader, an extruder, a roll or the like which is generally used for kneading rubber and other materials, The rubbery copolymer as the component) is preferably used because it can be easily finely dispersed.

More specifically, the epoxy resin may be, for example, a condensation product of epichlorohydrin and a polyhydric alcohol or a polyhydric phenol, a condensation product of epichlorohydrin and a phenol novolak, a novolak such as cresol novolac, or a cyclic product. Aliphatic epoxy compounds, glycidyl amine epoxy compounds, heterocyclic epoxy compounds, epoxy compounds derived from polyolefin polymers or copolymers, epoxy compounds obtained by (co) polymerization of glycidyl methacrylate, highly unsaturated fatty acids Examples thereof include epoxy compounds obtained from glyceride, polyalkylene ether type epoxy compounds, and nitrogen-containing or fluorine-containing epoxy compounds having an epoxy equivalent of about 6000 or less.

The curing agent and / or curing accelerator for the epoxy resin is selected according to the curing type of the modified epoxy composition, for example, two-component type, one-component type, thermosetting type, photo-curing type, and the like. Can be used. Examples of curing agents and / or curing accelerators for such epoxy resins include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4 -Amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,
Aliphatic polyamines such as 4,8,10-tetraoxaspiro (5,5) undecane and m-xylenediamine, aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diaminodiethyldiphenylmethane, benzyldimethylamine 2 -(Dimethylaminomethyl), phenol, 2,
4,6-tris (dimethylaminomethyl) phenol,
Secondary such as tetramethylguanidine, N, N'-dimethylpiperazine, triethylenediamine, 1,8-diazabiscyclo (5,4,0) undecene, triethanolamine, piperidine, hirolidine, polyamidoamine, boron fluoride monoethylamine complex Or tertiary amines, methyl nadic acid anhydride, dodecenyl succinic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcondomethylenetetrahydrophthalic anhydride,
Acid anhydrides such as chlorendic anhydride, ethylene glycol trimethylate anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole,
1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2
-Phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-
Undecyl imidazole, 1-cyanoethyl-2-methyl imidazole trimellitate, 1-cyanoethyl-2
-Phenylimidazole trimellitate, 2,4-diamino-6- {2'-methylimidazolyl- (1 ')}-
Ethyl-S-triazine, 2,4-diamino-6- {2
′ -Undecylimidazolyl- (1 ′)}-ethyl-S
-Triazine, 2,4-diamino-6- {2'-ethyl-4'-methylimidazolyl- (1 ')}-ethyl-S
-Triazine, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-
2-Undecylimidazole trimellitate, 1-dodecyl-2-methyl-3-benzimidazolium chloride, imidazole derivatives such as 1,3-dibenzyl-2-methylimidazolium chloride, dicyandiamide or its derivative, adipic dihydrazide, etc. Organic acid dihydrazide of 3- (p-chlorophenyl) -1,1
-Dimethylurea, 3- (3,4-dichlorophenyl)-
A urea derivative such as 1,1-dimethylurea, a polymercaptan curing agent, a methylol group-containing compound such as a phenol resin, a urea resin, and a melamine resin, a polyisocyanate, and an aromatic diazonium salt which is an ultraviolet curing catalyst,
A sulfonium salt or the like can be used.

When an epoxy resin curing agent and / or curing accelerator is used, the amount of the curing agent and / or curing accelerator is usually such that the active hydrogen group contained in these curing agents and / or curing accelerators is
It is an amount that is almost equivalent to the epoxy group of the component (a).

The phenol resin curing agent and curing accelerator are also not particularly limited. Usually, a polyamine such as hexamine, an epoxy resin, an isocyanate compound, a polyformaldehyde compound, etc. are used as necessary.

Component (b) Next, the copolymer as the component (b) will be described.

The constitutional unit of the emulsion-polymerized copolymer of the present invention comprises 1 to 20% by weight of a monomer unit containing a carboxyl group and another vinyl-based monomer unit 8 copolymerizable therewith.
0 to 99% by weight. If the monomer unit containing a carboxyl group is less than 1% by weight, the thermosetting resin composition of the present application is insufficient in terms of adhesive strength and strength. If it exceeds 20% weight,
The thermosetting resin composition has poor storage stability and adhesive strength,
There is a problem that both strength and strength decrease.

Examples of the carboxyl group-containing monomer used here include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, β- (meth) acryloxyethyl succinate, and β- (maleic acid. Examples of unsaturated acids include (meth) acryloxyethyl, β- (meth) acryloxyethyl phthalate, hexahydrophthalic acid, and β- (meth) acryloxyethyl. Also, maleic anhydride,
It is also possible to polymerize an unsaturated acid anhydride such as succinic anhydride and hydrolyze it to obtain a monomer containing a carboxyl group.

The following can be exemplified as other vinyl-based monomers copolymerizable therewith.

Conjugated dienes: butadiene, dimethyl butadiene, isoprene, chloroprene and their derivatives.

Vinyl cyanide: acrylonitrile, methacrylonitrile.

(Meth) acrylic acid ester: methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, (meth ) Reaction of ethoxyethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, diglycidyl ether of bisphenol A, diglycidyl ether of glycol, etc. with (meth) acrylic acid, hydroxyalkyl (meth) acrylate, etc. Epoxy (meth) acrylate obtained by the above, and urethane (meth) acrylate obtained by the reaction of hydroxyalkyl (meth) acrylate and polyisocyanate.

Unsaturated hydrocarbons other than the above: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-
Olefin such as pentene, aromatic vinyl such as styrene and methylstyrene. Compounds having a plurality of polymerizable double bonds in the molecule such as divinylbenzene, diallylphthalylate, ethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

It is also possible to copolymerize monomers having various functional groups other than the carboxyl group.

Examples of these monomers include glycidyl (meth) acrylate and (meth) acrylglycidyl ether when the functional group is an epoxy group, and dimethylaminomethyl (meth) when the functional group is an amino group. Acrylate, diethylaminoethyl (meth) acrylate and the like, when the functional group is an amide group, (meth) acrylamide, dimethyl (meth) acrylamide and the like, and when the functional group is a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate and the like, when the functional group is an isocyanate group, vinyl isocyanate, isocyanate ethyl (meth) acrylate, p-styryl isocyanate and the like, and when the functional group is a phosphoric acid group, (meth) acryloxyethyl Mention phosphates Door can be.

Various kinds of these monomers may be combined with the above-mentioned carboxyl group-containing monomer, if necessary, to obtain a copolymer.

Among the obtained copolymers, acrylonitrile / butadiene / (meth) acrylic acid copolymer, acrylonitrile / (meth) acrylic acid ester / (meth) acrylic acid copolymer, (meth) acrylic acid ester / ( A (meth) acrylic acid copolymer is preferable because it has excellent miscibility with an epoxy resin or a phenol resin.

The copolymer as the component (b) is disclosed in JP-A-63-
As disclosed in Japanese Patent No. 125589, after emulsion polymerization is performed using at least a nonionic surfactant, the resulting polymer latex is then added to a nonionic surfactant and optionally a metal-free electrolyte. It can be obtained by coagulating the rubbery copolymer by heating in the presence of

The emulsion polymerization applied to the production of the component (b) will be specifically described. First, a general polymerization agent is used in addition to the nonionic surfactant in the emulsion polymerization. It is preferable to use those containing no metal compound such as. However, since these drugs are used in a very small amount, there is no problem in practical use.

Polymerization is carried out using a peroxide, a redox compound, an azo compound, a persulfate, etc. as a polymerization initiator,
It may be carried out by a usual emulsion polymerization method.

In addition, a molecular weight modifier or the like may be used if necessary. Further, the kinds of the monomers are not limited to the above-mentioned ones, and any one can be applied as long as it is emulsion-polymerizable, and there is no limitation on the obtained molecular weight.

As the nonionic surfactant used as an essential component for the emulsion polymerization of the component (b), polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester,
Examples thereof include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block polymer, alkylsulfinyl alcohol, and fatty acid monoglyceride.

Among the surfactants that can be used as required during emulsion polymerization, examples of the anionic surfactant include soap, funnel oil, emulsion oil, alkylnaphthalene sulfonate, dodecylbenzene sulfonic acid. Salt, oleate, alkylbenzene sulfonate,
Dialkyl sulfosuccinate, lignin sulfonate,
Alcohol ethoxy sulfate, secondary alkane sulfonate, α-olefin sulfonic acid, tamol and the like, and as the cationic surfactant, for example, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl pyridinium salt, alkyl benzyl dimethyl ammonium salt and the like. Can be mentioned.

However, the nonionic surfactant is preferably used in an amount of 30% by weight or more, more preferably 50 to 100% by weight, based on the total amount of the surfactant. The surfactant is preferably 1 to 2 with respect to 100 parts by weight of the monomer.
0 part by weight, more preferably 2 to 12 parts by weight is used.

The emulsion polymerization is carried out in a reactor from which oxygen has been removed, at a temperature below the cloud point of a commonly used nonionic surfactant. Here, the cloud point means a temperature at which clouding occurs for the first time when the nonionic surfactant is heated, and is a phenomenon peculiar to the nonionic surfactant.

Monomers, nonionic surfactants, molecular weight regulators, polymerization initiators, etc. may be added in total amounts before the start of the reaction, or may be arbitrarily added after the start of the reaction. The conditions such as stirring can be arbitrarily changed.
However, it is necessary to keep the polymerization temperature at a temperature below the cloud point of the nonionic surfactant used.

The polymerization system may be either continuous or batch.

The polymer latex thus obtained is subjected to a conventional monomer recovery means such as distillation under reduced pressure or steam distillation to recover the monomer, and then the latex is heated to a temperature not lower than the cloud point of the nonionic surfactant. When heated to a temperature (solidification temperature), the nonionic surface active phase undergoes phase separation, and as a result, a polymer is instantaneously precipitated and the polymer can be separated. The heating may be performed batchwise in a container or continuously. If the solidification temperature exceeds 100 ° C,
In addition to the heating device, a pressure device is also required.

In this case, a metal-free electrolyte may be added to the latex to allow coagulation to occur at a lower temperature. Examples of such metal-free electrolytes include, but are not limited to, inorganic salts such as ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium nitrate or ammonium acetate.

The amount of the electrolyte used is preferably 5 per 100 parts by weight of the polymer component in the polymer latex.
-20 parts by weight, more preferably 7-15 parts by weight.
If the amount of the electrolyte used is less than 5 parts by weight, coagulation may be insufficient, while if it exceeds 20 parts by weight, it is uneconomical and the coagulation property hardly changes.

In this way, after the emulsion polymerization (further, after the monomer is recovered), the obtained polymer latex is subjected to the conventional method in the presence of a nonionic activator and a metal-free electrolyte. The polymer latex can be coagulated by simply heating the used metal compound such as calcium chloride or sodium chloride as a coagulant.

The heating temperature in this case is not particularly limited, and may be arbitrarily adjusted according to the type, amount and ratio of the nonionic surfactant / ionic surfactant used, the type and amount of the electrolyte used. However, usually 40 to
The temperature is adjusted to 150 ° C, preferably 60 to 120 ° C. If the heating temperature is lower than 40 ° C, the latex becomes unstable and there is a problem in production, while if it exceeds 150 ° C, gelation of the polymer may occur, which is not preferable.

The molecular weight of the component (b) which is a copolymer is not particularly limited, and it ranges from about 2000 to 100.
It is possible to use up to solids of up to 0,000.

Constituting the polymer component described above (a)
The ratio of the component to the component (b) is 30 to 95 for the component (a).
% By weight, preferably 40-90% by weight, 5% of component (b)
˜70% by weight, preferably 10 to 60% by weight.
When the content of the component (b) is less than 5% by weight, the flexibility of the thermosetting resin composition is insufficient and the peel strength and impact strength are poor, and when it exceeds 70% by weight, the thermosetting property is high. The dimensional stability, mechanical strength, and electrical insulation properties of the resin composition are insufficient.

Component (c) Next, the component (c) used in the present invention will be described.

The component (c) is a group II or III group of the periodic table.
At least one metal selected from the group, for example, calcium (Ca), magnesium (Mg), beryllium (B
e), a compound of at least one metal selected from zinc (Zn), strontium (Sr) and aluminum (Al), preferably a compound of Ca or Mg. More specifically, examples of the component (c) include organic sulfonates, organic carboxylates, organic phosphates, organic thiocyanates and hydrides of the respective metals, preferably organic sulfonates. Organic carboxylates and hydrides.

These organic metal salts or hydrides are
It is more difficult to dissociate than calcium chloride or sodium chloride, which are conventional coagulants, less likely to cause a decrease in insulation resistance and metal corrosion, and can significantly improve the adhesive strength at high temperatures. The component (c) can be used alone or in combination of a plurality of metal salts.

The ratio of the component (c) to the components (a) + (b) is 0.1 per 100 parts by weight of the components (a) + (b).
10 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

When the amount of the component (c) is less than 0.1 parts by weight, the adhesive strength and mechanical strength at high temperature, which are the features of the present invention, are poor, and when it exceeds 10 parts by weight, the thermosetting property obtained is obtained. The electrical insulation of the resin composition is reduced.

There is no particular limitation on the mixing method of the components (a), (b) and (c), and in addition to the conventional kneading using a closed type mixer, extruder, roll, etc., for example, To the latex as the component (b), the components (a), (c) or a latex obtained by previously emulsifying the component (a) with a surfactant is added, and the mixture is forcibly stirred under shearing force, and then the component (b) is coagulated. It is possible to use a method in which the solid content is separated from water and dried by the same procedure as described above.

When preparing the thermosetting resin composition of the present invention, if necessary, a resin curing agent, retarder, silica, clay, gypsum, calcium carbonate, quartz powder, talc, kaolin, mica, Various additives such as fillers such as titanium compounds and antimony compounds, pigments, antioxidants, ultraviolet absorbers and waxes can be added.

[0059]

EXAMPLES The present invention will be described in more detail below with reference to examples.

It should be noted that the present invention is not limited to these examples unless the gist thereof is exceeded.
In the following description, "part" and "%" are based on weight. Example 1 Using the emulsion polymerization formulation shown below, emulsion polymerization was carried out at 20 ° C. in an autoclave having an internal volume of 2.0 liters. (Emulsion polymerization formulation) Butadiene 65 parts Acrylonitrile 30 parts Methacrylic acid 5 parts Water 220 parts Polyoxyethylene 5 parts Nonylphenyl ether (Note 1) Tertiary dodecyl mercaptan 0.4 parts Ammonium persulfate 0.25 parts Cyanoethylated diethanolamine 0 15 parts Note 1: Emulgen 920 manufactured by Kao Soap Co., Ltd., cloud point 82 ° C. After the polymerization conversion rate reached 90%, 0.2 parts of hydroxylamine sulfate was added per 100 parts of the monomer to perform polymerization. Stopped. Then, after heating and recovering the residual monomer by steam distillation under reduced pressure at about 70 ° C., 1 part of alkylated phenol as an anti-aging agent was added, and then this polymer latex was put in a pressure can. The latex was coagulated by heating to 110 ° C. The generated crumb was taken out, washed with water, and then dried under reduced pressure at 50 ° C. to obtain a sample for evaluation.
The obtained copolymer is referred to as a copolymer (A).

Here, the amount of acrylonitrile contained in the obtained copolymer is NC-produced by Sumitomo Chemical Co., Ltd.
The amount of nitrogen contained was determined by using a 800 fully automatic nitrogen analyzer and calculated from this. The amount of methacrylic acid is obtained by quantitatively determining phenolphthalein according to a conventional method by using an alkali as an indicator. The amount of butadiene is obtained by obtaining the iodine value according to a conventional method and then calculating from this. Further, butyl acrylate is obtained by subtracting the amount of acrylonitrile, the amount of methacrylic acid, and the amount of butadiene from the total amount of copolymer.

Table 1 shows the above-mentioned polymerization formulation, polymer composition, Mooney viscosity ML _{1 + 4} (100 ° C.) of the polymer, and the amount of metal and chlorine in the polymer.

[Table 1] Using the obtained copolymer (A), an epoxy resin composition was obtained according to the following formulation.

(Formulation) Epoxy resin (Note 1) 85 parts Novolac resin (Note 2) 40 parts Copolymer (A) 15 parts Calcium dodecylbenzene sulfonate 1 part α-methylimidazole 0.75 parts Note 1: Product Name Summy Epoxy ESCN 220L Sumitomo Chemical Co., Ltd. Note 2: Trade name Tamanol 758 Arakawa Chemical Co., Ltd. These are kneaded at 80 ° C. using a closed mixer,
Further, press-molding was performed at 160 ° C., and the resulting molded plate was milled to obtain impact-resistant test pieces,
A bending strength test piece was prepared.

The bending strength test is performed according to JIS K 7203,
The impact resistance test was carried out by using an Izod impact tester at room temperature and using a notched test piece. The volume resistivity was measured using an electric resistance tester manufactured by Yokogawa Electric Corp. at 25 ° C. and a humidity of 40%. The above formulation and measurement results are shown in Tables 2 and 3.

[Table 2]

[Table 3] Examples 2-4, Comparative Examples 1-7 In accordance with the emulsion polymerization formulation shown in Example 1, as shown in Table 1, polymerization was performed by changing the type of emulsifier and the monomer composition, and copolymer (B)- (H) was obtained. Obtained copolymer (B)
~ (H) was used to prepare and evaluate a thermosetting resin composition in the same manner as in Example 1 except that the type and amount of the metal salt in the formulation shown in Example 1 were changed. It was
The results are shown in Tables 2 and 3. Example 5 Using the copolymer (A) shown in Table 1, an adhesive was prepared by the following formulation.

(Formulation) Epoxy resin 50 parts (Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) Copolymer (A) 50 parts Calcium dodecylbenzenesulfonate 2 parts 2-Methylimidazole 0.5 parts Methylethylketone 250 parts Dodecyl 2 parts calcium benzenesulfonate
The copolymer (A) was previously kneaded uniformly at 40 ° C. using a two-roll mill and then dissolved in methyl ethyl ketone. The obtained adhesive was applied to a polyimide film (trade name: Kapton manufactured by DuPont) so that the film thickness after drying would be 30 μm, and dried at 120 ° C. for 10 minutes. Next, a 35 μm thick copper foil (rolled copper foil BSH-35 manufactured by Mitsui Mining & Smelting Co., Ltd.) was applied to this adhesive layer for 10 minutes at 160 ° C. for 3 minutes.
It was pressure-bonded with a load of / cm ² and further heated at 120 ° C. for 60 minutes to prepare a flexible copper clad plate. The following characteristic evaluation was performed using this copper clad plate sample. The evaluation results are shown in Tables 4 and 5.

Peel Strength A copper-clad plate sample was punched out to a width of 1 cm, and a 180 ° peel test was conducted by an autograph using this, and the peel strength was obtained.

The peel strength is 2 at 25 ° C and 150 ° C.
The measurement was performed on two types of samples after standing for 4 hours.

Solder heat resistance The measurement was performed according to JIS C6481. At the time of measurement, 260 ℃, 30 seconds and 300 ℃, 20 seconds 2
It was carried out under different conditions.

Insulation Resistance Using the flexible copper clad plate, a comb-shaped pattern substrate having line / space = 0.2 / 0.2 (mm) was prepared at room temperature, and using this, a space between test pattern lines was formed. The insulation resistance value was measured with an electric resistance tester manufactured by Yokogawa Electric Co., Ltd.
The measurement was performed at 5 ° C. and a humidity of 40%.

Electrolytic property Using the same sample as used in the measurement of the insulation resistance, under the conditions of 85 ° C. and 85% relative humidity, 50
A voltage of V was applied, and the state change of the substrate after 50 hours was visually observed, and the insulation resistance value was measured.

[Table 4]

[Table 5] Examples 6 to 8 and Comparative Examples 8 to 14 Evaluations were performed in the same manner as in Example 5 except that the types and blending amounts of the copolymer and the metal salt were changed as shown in Tables 4 and 5. It was The results are shown in Tables 4 and 5.

From Tables 2 and 3 and Tables 4 and 5, the thermosetting resin composition according to the present invention has excellent mechanical strength, impact resistance, adhesive strength, insulation resistance, and adhesion at high temperature. It is clear that the composition is also excellent in strength and insulation resistance and has extremely small metal corrosiveness even under high temperature and high humidity.

[0072]

The thermosetting resin composition of the present invention is excellent in mechanical strength, adhesive strength and electrical characteristics not only at room temperature but also at high temperature, and is mainly used for electric and electronic parts. It can be widely used as a casting material, a sealing agent, an adhesive, a coating material, a paint, a lining material, a sealing material, etc., and is highly practical.

Claims (1)

[Claims] 1. (a) 30 to 95% by weight of thermosetting resin
And (b) a monomer unit containing at least a carboxyl group, which is obtained by emulsion polymerization using at least a nonionic surfactant as an emulsifier, and is 1 to 20 of a copolymer.
(C) at least one metal compound selected from Group II or Group III of the periodic table per 100 parts by weight of the polymer component containing 5 to 70% by weight of the copolymer. A thermosetting resin composition comprising 1 to 10 parts by weight.