JPH0336047B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a thermosetting composition that has little odor, has excellent curability at room temperature, and provides a cured product with excellent heat resistance. BACKGROUND OF THE INVENTION Room temperature curable epoxy resin compositions are widely used for paints, adhesives, casting, etc. However, conventionally used room-temperature curing epoxy resin compositions have a strong odor, absorb carbon dioxide gas in the air during curing, resulting in curing failure, and the resulting cured product has poor heat resistance. Its use was limited due to the lack of use. In order to solve these drawbacks, it has been proposed to increase the molecular weight of the curing agent or to use an aromatic amine compound as the curing agent, and some of these have been put into practical use. However, their use increases the viscosity of the resin composition, causing new problems in terms of workability, reducing the heat resistance of the cured product, and slowing down the curing speed. There is. For example, a composition consisting of meta-aminobenzylamine and bisphenol A diglycidyl ether has been proposed (US Pat. No. 3,317,468), but this type of composition has a slow curing rate at room temperature;
Another disadvantage is that the resulting cured product has poor heat resistance. Problems to be Solved by the Invention Therefore, as a result of intensive study, the present inventors changed to bisphenol A diglycidether, an epoxy resin having 3 or more epoxy groups in one molecule.
By using aminobenzylamine as a curing agent together with an epoxy resin consisting of ~30% by weight and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule, the above drawbacks are improved.
It has been found that a thermosetting composition can be obtained which has a fast curing speed at room temperature and has significantly improved heat resistance. However, the cured product of the thermosetting composition obtained in this manner has disadvantages such as thermal deterioration when exposed to high temperatures for a long period of time, or inability to withstand strong impact. As a result of various studies to eliminate these drawbacks, it has been found that addition of antimony trioxide is effective for preventing thermal deterioration of the cured product, and addition of rubber is effective for improving impact resistance. The present invention was completed based on this knowledge. Means/Action for Solving the Problems The present invention provides: (1)(a) 100 to 30% by weight of an epoxy resin having 3 or more epoxy groups in one molecule;
Epoxy resin with 0 or less epoxy groups
1. A thermosetting composition comprising: an epoxy resin containing up to 70% by weight, (b) aminobenzylamines, and (c) antimony trioxide. (2)(a) 100-30% by weight of epoxy resin having 3 or more epoxy groups in one molecule, 2% by weight in 1 molecule
Epoxy resin with 0 or less epoxy groups
70% by weight of an epoxy resin; (b) aminobenzylamines; (c) antimony trioxide; and (d) rubber. Hereinafter, the structure of the invention will be explained in detail together with its operation. Examples of the epoxy resin of the present invention include the following. () Amine-based epoxy resin

[Formula] An epoxy resin having a group, such as N, N, N', N'-tetraglycidyldiaminodiphenylmethane, meta-N, N
-Synthesized from a compound having an amino acid or amide group, such as diglycidylaminophenyl glycidyl ether, N,N,N',N'-tetraglycidyl terephthalamide, etc., and an epihadhydrin, such as epichlorohydrin, methylepichlorohydrin, epibromhydrin, etc. be done. Specific examples of compounds having an amino group include:
Diaminodiphenylmethane, meta-xylylene diamine, para-xylylene diamine, meta-aminobenzylamine, para-aminobenzylamine,
1,3-bisaminomethylcyclohexane,
1,4-bisaminomethylcyclohexane,
1,3-diaminocyclohexane, 1,4-diaminocyclohexane, metaphenylenediamine, paraphenylenediamine, benzylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl ketone, naphthalene diamine , aniline, toluidine, methanaminophenol, para-aminophenol, aminonaphthol and the like. Further, specific examples of compounds having an amide group include phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, parahydroxybenzamide, meta-hydroxybenzamide, and the like. When a compound having an amino group or an amide group has a group that reacts with epihalohydrin, such as a hydroxyl group, a carboxyl group, or a mercapto group other than the amino group or amide group, part or all of the group that reacts with epihalohydrin may react with epihalohydrin and be substituted with an epoxy group. () Phenol-based epoxy resin It can be synthesized from a phenol-based compound and epihalohydrin, such as bisphenol A diglycidyl ether and Epotote YDCN-220 (product of Toto Kasei Co., Ltd.). Specific examples of phenolic compounds include phenol, cresol, butylphenol, octylphenol, benzylphenol, cumylphenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, and brominated bisphenol. A, novolac resin, cresol novolac resin, tetraphenylethane, triphenylethane, and the like. () Alcohol-based epoxy resin Can be synthesized from alcohol-based compounds and epihalohydrin, such as trimethylolpropane triglycidyl ether and neopentyl glycol diglycidyl ether. Specific examples of alcohol compounds include monohydric alcohols such as butyl alcohol and 2-ethylhexy alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol 1,4-butane. diol, 1,
6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone, polytetramethylene ether glycol, polybutadiene glycol, hydrogenated bisphenol A,
Examples include polyhydric alcohols such as cyclohexanedimethanol, bisphenol A/ethylene oxide adduct, bisphenol A/propylene oxide adduct, and polyester polyols made from these polyhydric alcohols and polyhydric carboxylic acids. () Epoxidized unsaturated compounds Cyclopentadiene diepoxide, epoxidized soybean oil, epoxidized polybutodiene, vinylcyclohexene diepoxide, styrene oxide, Union Carbide product name ERL-
Examples include epoxidized products of unsaturated compounds known as 4221, ERL-4234, and ERL-4299. () Glycidyl ester-based epoxy resins such as benzoic acid glycidyl ester, tetrahydrophthalic acid diglycidyl ester, etc.
It can be synthesized from carboxylic acid and epihalohydrin. Specific examples of carboxylic acids include monocarboxylic acids such as benzoic acid, paraoxybenzoic acid, butylbenzoic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, tephthalic acid, and tetrahydrophthalic acid. , methyltetrahydrophthalic acid, hextrahydrophthalic acid, Hett's acid, nadic acid, maleic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, butanetetracarboxylic acid, benzophenonetetracarboxylic acid, 5-(2,5
-Dioxotetrahydrophyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid and other polyhydric carboxylic acids. () Urethane-based epoxy resin It can be synthesized from the above-mentioned polyhydric alcohol, diisocyanate, and glycidol. Specific examples of diisocyanates include tolylene diisoanate, diphenylmethane-4, 4'-
Examples include diisocyanate, hexamethylene diisocyanate, isophorone dicyanate, xylylene diisoanate, naphthalene diisocyanate, and the like. () Other epoxy resins Tris-epoxypropyl isocyanurate, glycidyl (meth)acrylate copolymers, and diisocyanates of the above-mentioned epoxy resins,
Examples include resins modified with dicarboxylic acids, polyhydric phenols, and the like. From the viewpoint of curing speed and heat resistance, epoxy resins having three or more epoxy groups are particularly preferred, and as types of epoxy resins, amine-based epoxy resins and phenol-based epoxy resins are particularly preferred. In the present invention, the epoxy resin alone is
Alternatively, two or more kinds can be used in combination. Specific examples of the epoxy resin used in the present invention have been listed above, but in the composition of the present invention, 100 to 30% by weight of the total epoxy resin is an epoxy resin having three or more epoxy groups in one molecule. It must be made into resin. If the amount of epoxy resin having three or more epoxy groups is less than 30% by weight, not only the curing speed of the composition of the present invention becomes slow, but also the heat resistance of the cured product decreases. In the composition of the present invention, aminobenzylamines, that is, mainly para-aminobenzylamine acid, meta-aminobenzylamines, and mixtures thereof, are used as curing agents for the epoxy resin. These adducts are included, which are products obtained by reacting benzylamine with the above-mentioned epoxy resin under conditions such that the active hydrogen in the amino group is in excess with respect to the epoxy group.
Further, this adduct may be a separate adduct, an internal adduct, or a mixture of both. Even if these benzylamines contain the ortho form, which is usually a by-product during the production of the para or meta form, as long as it does not impair the effects of the present invention, it can be used as is without purification if it is in a small amount. No problem. The proportion of each component used in the composition of the present invention is as follows:
For each epoxy group in the epoxy resin, the hydrogen of the amino group in the aminobenzylamino is usually
They are used in a ratio of 0.5 to 1.5, preferably 0.8 to 1.2. Further, as for the ratio of the combination of para-aminobenzylamines and meta-aminobenzylamines, the more the former is used, the lower the melting point of the mixture of both can be.
For example, the melting point of meta-aminobenzylamine is approximately 40°C, but when half of both are used, the melting point drops to approximately 15°C. Therefore, reactivity is improved, curing time is shortened, and heat resistance is also improved. Next, by adding antimony trioxide (Sb ₂ O ₃ ) to the above thermosetting composition, the heat deterioration resistance of the cured product is greatly improved. The amount added is preferably 5 to 50 parts by weight per 100 parts by weight of the epoxy resin.
If the amount added is less than 5 parts by weight, the effect will not be sufficiently expressed, and if it exceeds 50 parts by weight, the adhesive strength will decrease. In the present invention, in order to improve the toughness of the cured product, it is preferable to mix rubber. As rubber,
Examples include acrylic ester-based, silicone-based, conjugated diene-based, olefin-based, polyester-based, and urethane-based polymers, with acrylic ester-based, silicone-based, and conjugated diene-based polymers being particularly preferred. These may be used alone or in combination. Acrylic ester rubbers are disclosed, for example, in JP-A-55-16053 and JP-A-55-21432. Silicone rubbers are disclosed, for example, in Japanese Patent Application No. 180831/1983. In addition, examples of conjugated diene rubber include:
1,3-butane diene, 1,3-pentadiene,
It can be produced by polymerizing or copolymerizing monomers such as isoprene, 1,3-hexadiene, and chloroprene, and commercially available products can be used. The amount of rubber used is 5 to 40 parts by weight, preferably 12 to 35 parts by weight, based on 100 parts by weight of the epoxy resin. The rubber may be dissolved or dispersed in the epoxy resin. Alternatively, it may be dissolved in an epoxy resin and precipitated as particles upon curing. or,
A graft copolymer with an epoxy resin may also be used. The composition of the present invention includes xylylene diamine, isophorone diamine, 1,3-bisaminomethylcyclohexane, as a curing agent and a curing accelerator.
Aminos such as diaminodiphenylmethane, polyamide resin, triethylamine, dimethylbenzylamine, imidazoles, trisdimethylaminomethylphenol, phenol, cresol, boron trifluoride amine salt, etc. may be used as long as they do not impair the effects of the present invention. Can be used in combination in some cases. Also solvents, silane and titanium coupling agents, pigments, organic and inorganic fillers, plasticizers,
Liquid rubber, thixotropic agents, leveling agents, antifoaming agents, tar, non-reactive diluents, low molecular weight polymers, glass fibers, carbon fibers, metal fibers, ceramic fibers, etc. may also be added. The composition of the present invention can be used in paints, adhesives, casting agents, sealants, molding materials, processing agents for fibers, paper, and the like. Furthermore, the composition of the present invention usually has a
Can be cured at 200℃. The present invention will be explained in more detail below using examples. Note that parts and percentages in each of the following examples are expressed on a weight basis unless otherwise specified. Example 1 Amine-based epoxy resin made from meta-aminophenol and epichlorohydrin (trade name Epotote YDM-120, Toto Kasei Co., Ltd., main component has 3 epoxy groups in one molecule) 92 parts, aminobenzylamine (O-form 2.8%, m-form 48.3%, p-form 48.5
% mixture) and 23 parts of antimony trioxide were added to the mixture. Mix well and leave at room temperature.
After 180 minutes, the adhesiveness almost disappeared and it was cured. Thereafter, after being left at room temperature for one week, the sheet shear strength (Kgf/cm ² ) at 20° C. was measured to examine thermal deterioration properties.
The results are summarized in Table 1.

[Table] On the other hand, JISK6855 Izot impact velocity (test piece material JISG4051-
S10C) were measured and found to be 6.0Kgf・
cm/ ^cm2 . Example 2 The following rubber components were synthesized. Phenolic epoxy resin made from phenol novolac resin and epichlorohydrin (trade name: Epicote 152, Yuka Ciel Epoxy Co., Ltd.)
There are 2 epoxy groups in one molecule of the main component) 500 parts,
Add 9 parts of acrylic acid and 1 part of triethylamine,
Epoxy resin 509 with acrylic acid residue introduced by heating to 110℃ and reacting for 8 hours
The section was manufactured. Next, 370 parts of butyl acrylate, 1 part of azobisdimethylvaleronitrile, and 2 parts of azobisisobutynitrile were added to this, and the mixture was heated at 70°C for 3 hours and then at 90°C.
By carrying out a polymerization reaction for 1 hour, a graft polymer of epoxy resin and acrylic ester was produced. (This is referred to as A1.) Next, 92 parts of amine-based epoxy resin (trade name: Epototo YDM-120, Toto Kasei Co., Ltd., main component has 3 epoxy groups in one molecule), 45 parts of A1, aminobenzylamine (O-form 2.8%, m-form 48.3%, p-form
Further, 23 parts of antimony trioxide was added to 32 parts of the mixture (48.5% mixture), mixed well, and left to stand at room temperature. After 180 minutes, almost no stickiness was left and the mixture was cured. Thereafter, after being left at room temperature for one week, the sheet shear strength (Kgf/cm ² ) at 20° C. was measured to examine thermal deterioration properties. The result is when the holding time at 200℃ is 0 days.
It was 195 when it was 171 and 150 days. On the other hand, regarding the above composition, JISK6855 Izot impact strength (test piece material JISG4051-
S10G) was measured and found to be 13.0Kgf·cm/cm ² . Effects of the Invention As detailed above, the thermosetting composition of the present invention has a high curing speed and excellent heat resistance, heat deterioration resistance, and impact resistance, and the aminobenzylamine used as a curing agent is m -, p-, and can be used separately as a mixture, so the economic effect is also extremely large.

Claims (1)

[Scope of Claims] 1 (a) 100 to 30% by weight of an epoxy resin having 3 or more epoxy groups in one molecule, 2 to 30% by weight in one molecule;
Epoxy resin with 0 to 3 epoxy groups
1. A thermosetting composition comprising: 70% by weight of an epoxy resin; (b) aminobenzylamines; and (c) antimony trioxide. 2 (a) 100 to 30% by weight of epoxy resin having three or more epoxy groups in one molecule, two or more in one molecule.
Epoxy resin with 0 to 3 epoxy groups
1. A thermosetting composition comprising: 70% by weight of an epoxy resin; (b) aminobenzylamines; (c) antimony trioxide; and (d) rubber.