JPS6181423A - Thermosetting composition - Google Patents

Abstract

PURPOSE:The titled composition useful as a coating compound, etc., having a faint smell, normal temperature curing properties, low-temperature workability, providing a cured material having improved heat resistance, comprising an epoxy resin having plural epoxy groups in the molecule, an aminobenzylamine, and an aromatic diamine. CONSTITUTION:(A) (i) 100-30wt% epoxy resin (preferably amine type epoxy resin, etc.) containing >=3 epoxy groups in one molecule and (ii) 0-70wt% epoxy resin containing <=2 epoxy groups in one molecule are blended with (B) (i) 95-50pts.wt. aminobenzylamine (paraamino derivative alone or a mixture of it and metaamino derivative) and (ii) preferably 20-50pts.wt. aromatic diamine (e.g., 3,5-diethyltoluene-2,4-diamine, etc.) in a ratio of preferably 0.8-1.2H of NH2 group in the component B to one epoxy group in the component A, to give the aimed thermosetting composition. Addition of Sb2O3 and rubber improves more thermal aging resistance and toughness.

Description

[Detailed description of the invention]! Thermosetting compositions that produce cured products with low odor, curability at temperature, low l crystal workability, and excellent heat resistance. Regarding.

BACKGROUND OF THE INVENTION 1Q Temperature-curing epoxy resin compositions are widely used for paints, adhesives, casting, etc. However, conventionally used room-temperature curing epoxy resin compositions have strong odor, absorb carbon dioxide scum in the air during curing, resulting in poor curing, and the resulting cured product has poor thermal properties. Because of this, its use was limited.

In order to solve these drawbacks, it has been proposed to increase the molecular adhesion 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. It is occurring.

For example, a composition consisting of meta-aminobenzylamine and bisphenol A diglycidyl ether has been proposed (Kikuni Toku, I'l' 3, 317, 468), but this type of composition does not work well at room temperature. The drawbacks are that the curing speed is slow and the resulting cured product has poor thermal properties.

The problem that the invention aims to solve Therefore, as a result of intensive study, the inventor of the tree discovered bisphenol A.
100 to 30% by weight of an epoxy resin having three scene H epoxy groups in one molecule in place of diglycidyl ether;
By using an epoxy resin consisting of 0 to 70% polymerization of an epoxy resin having 2 or less epoxy groups in one molecule, the defect listed in L was improved, the room temperature curing speed was fast, and the heat resistance was also significantly improved. It has been found that a thermosetting composition can be obtained.

However, meta-aminobenzylamine, which is used as one of the curing agents, has a melting point of about 40°C, is solid at room temperature, and has poor uniformity in mixing into the composition. The reaction with the resin did not proceed uniformly and quickly, resulting in insufficient adhesion, paint adhesion, and molded product strength. Secondly, attempts have been made to use a suitable organic solvent, but this poses safety and pollution problems when volatilizing the organic solvent during curing, and also creates bubbles in the resin part, making it difficult to adhere to the paint. Deteriorates adhesion and molded product strength.

In addition, attempts have been made to modify meta-aminopencylamine and use it as a liquid adduct, but the conventional examples have had poor adhesion and have not been satisfactory.

Therefore, the present inventor found that the curability and heat resistance could be further improved by using para-aminobenzylamine alone or in combination with meta-aminopencylamine, and the present applicant filed an application earlier.

The present invention relates to a thermosetting composition that has further improved curability at room temperature, low-temperature workability, heat resistance of cured product, heat deterioration resistance, and toughness.

That is, 1. The present invention focuses on the fact that by mixing aromatic diamines in a certain proportion not only with aminobenzylamine in a meta-balanced mixture but also with meta-aminobenzylamine alone, the mixture becomes liquid at room temperature, adhesives, paints,
Tried to use it for cast products, etc. Although aromatic diamines do not show curing properties alone at room temperature, when mixed with aminobenzylamines, the reaction with epoxy resins proceeds uniformly and quickly, and the reaction is equivalent to or higher than that of aminobenzylamines. It is said to exhibit room temperature curability and heat resistance! I found out the truth.

Furthermore, we found that the addition of antimony trioxide is extremely effective in preventing thermal deterioration, and that the addition of acrylic, silicone, etc. rubbers is extremely effective in improving impact resistance. This completes the present invention.

Means and Effects for Solving the Problems The present invention provides: (1) (a) 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, two or more in one molecule;
An epoxy resin comprising 0 to 70% by weight of an epoxy resin having 3 or less epoxy groups, and (b) an amide/benzylamine and an aromatic diamine.

(2) (a) Epokinono with three scenes in one molecule,
(Epoxy resin 118,100-30% by weight, 0-30% epoxy resin having 2 or less epoxy groups in one molecule)
Epoxy resin consisting of 70% by weight.

A thermosetting composition comprising (b) aminopencylamines and aromatic cyamines, and (c) antimony trioxide.

(3) (a) 100 to 30% by weight of epoxy resin having 3 or more epoxy groups in one molecule, 2 to 30% by weight in 1 molecule
an epoxy resin consisting of an epoxy resin θ to 70% by weight, (b) aminobenzylamines and aromatic diamines, and (c) com.

A thermosetting composition comprising:

(4) (a) Epoxy resin having 3 or more epoxy groups in one molecule, 100-30% by weight, 2% in 1 molecule
(b) aminohairsylamines and aromatic diamines; (c>antimony trioxide; and (d) rubber.

A thermosetting composition characterized by containing the following.

The configuration of the first invention will be explained in detail below along with its operation.

Examples of the epoxy resin of the present invention include the following.

, i) Amine-based epoxy resins such as N, N, N', N'-tetraglycidylaminophenylmethane, meta-N, N-diglycidyl aminophenylglycinolether, N, N, N',
It is synthesized from a compound having an amide group or an amide group, such as N'-tetraglyndyl terephthalamide, and an epihalohydrin, such as epichlorohydrin, methylepichlorohydrin, or epibromohydrin.

Specific examples of compounds having an amine group include diaminodiphenylmethane, meta-xylylene diamine, para-xylylene diamine, meta-aminopencylamine, para-aminopencylamine, 1,3-saminomethylcyclohexano, 4-bisami/ Methylcyclohexane,
3-diaminocyclohexane, l,4-diaminocyclohexane metaphenylenediamine, paraphenylenediamine, hensylamine, diaminodiphenylsulfone, diami, nodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl ketone, naphthalene diamine, anili/, toluidino 2 meta-aminophenol , para-aminophenol, aminonaphthol, etc.

Further, specific examples of the compound having an amide group include phthalamide, inphthalamide, terephthalamide, benzamide, toluamide parahydroxy heptazamide, meta-hytroquine beptazamide, and the like.

When a compound having an amino group or an amide group has a group other than an amino group or an amide group that reacts with a hydrocyl group or a carboxyl group, a part or all of the group that reacts with epihalohydrin is epichlorohydrin. may be substituted with an epochine group.

, tii Phenolic epoxy resin bisphenol A diglycidyl ether, Epotote Y D C N-
It can be synthesized from a phenolic compound and epihalohydrin, such as 220 (product of Tobu Kasei Co., Ltd.).

Specific examples of phenolic compounds include phenol, cresol, butylphenol, octylphenol, benzylphenol, cumylphenol, naphtho-/butylphenol,
Hydroquinone, catechol, lenlucine, bisfe/
alcohol A1 hisphenol F, hisphenol sulfone,
Examples include brominated hisphenol A, noholac resin, kleinol no pora, resin, tetraphenylethane, triphenylethane, and the like.

., 110 Alcohol-based epoxy resins 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-ethylhexyl alcohol, ethylene glycol, diethylenoglycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1.4 -Butanediol, ■, 6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, penotaerythritol, polycaprolact/, polytetramethylenenoether glycol, polybutadiene glycol, hydrogenated bispheno-I
L, A, cyclohexane dimetatool, bisphenol A ethylene oxide adduct, bisphenol A
- Examples include polyhydric alcohols such as propylene oxide adducts, and polyester polyols made from these polyhydric alcohols and polyhydric carboxylic acids.

JV) Epoxides of unsaturated compounds Ngropentadiene diepoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexef diepoxide, styrene oxide, Union Carbide's trade name ERL-
Examples thereof include epoxidized products of unsaturated compounds known as ERL-4221, ERL-4234, ERL-4299, and the like.

(v) Glycidyl ester-based epoxy resin Can be synthesized from carbonic acid and epihalohydride, such as benzoic acid glycidyl ester and tetrahydrophthalic acid diglycidyl ester.

Specific examples of carboxylic acids include monocarboxylic acids such as ben9oic acid, paraoxybenzoic acid, butylbenzoic acid, adipic acid, cepatic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, and tetrahydrocarboxylic acid. Phthalic acid Methyltetrahydrophthalic acid, hexahydrophthalic acid, he/tonic acid, nadic acid, maleic acid, fumaric acid, trinoliftic acid, benzenetetracarboxylic acid, butanetetracarbo/s, benzophenonetetracarboxylic acid, 5- Examples include polycarboxylic acids such as (2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic acid.

; vO urethane epoxy resin The polyhydric alcohol and diisocyanate described above.

and glycidol.

Specific examples of diisocyanates include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xamethylene diisocyanate, isophorone diisocyanate, quinlylene diisocyanate, and naphthalene diisocyanate. It will be done.

■ Other epoxy resins such as tris-epoxypropyl isocyanurate, glycidyl (
Examples include meth)acrylate polymers, and resins modified with diisocyanates of epoxy resins, dicarboxylic acids, polyhydric phenols, etc., as indicated by +if.

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, epoxy resins can be used alone or in combination of two or more.

Specific examples of the epoxy resin used in the present invention have been listed above. In the composition of the present invention, 100 to 30% by weight of the total epoxy resin has three or more epoxy groups in one molecule. 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 will be slow, but also the heat resistance of the cured product will be low. Sexuality decreases.

In the composition of the present invention, aminohensylamines, that is, mainly para-aminobenzylamines, meta-aminobenzylamines, and mixtures thereof, are used as hardening agents for the epoxy resin. Varaminobenozylamine and an epoxy resin as described in ii.
Included are these adducts, which are products obtained by reacting under conditions such that there is an excess of active hydrogen in the group. In addition, this adduct may be a separated adduct, an endogenous adduct, or a mixture of the two.The ortho-reactive adduct that is usually produced as a by-product during the production of the para- and meta-isomers of these benzylamines Even if it is contained, as long as it does not impair the effects of the present invention, it may be used as is without purification as long as it does not impair the effects of the present invention.

Next, aromatic diamines used as curing agents for epoxy resins together with 7-minobenzylamines are represented by the following general formula.

However, Rr, Rz, and R3 refer to the same or different alkyl groups having 1 to 5 carbon atoms.

For example, 3.5-diethyltoluene-2,4-diamine or 3.5-diethyltoluene-2°6-diamine may be used alone or in combination.

Further, it is possible to use a mixture of 80 to 80% by weight of a compound in which R1 is a methyl group and R2 and R3 are an ethyl group, and 40 to 10% by weight of a compound in which R, , R2 is a methyl group, and R3 is a methyl group.

Aromatic diamines do not have room temperature curability even when used alone as curing agents for epoxy resins, and do not cure unless heated. Exhibits excellent room temperature curability when used in combination with aminobenzylamines.

Therefore, the mixing ratio of Ami-7 pendylamines and aromatic diamines is 5 to 50 parts by weight, preferably 2 parts by weight, of aromatic diamines to 95 to 50 parts by weight of aminohensylamines.
0 to 50 parts by weight are used. If the mixing ratio of aromatic diamine exceeds 50 parts by weight, the curing rate will be low, which is not preferable.

Furthermore, at the above mixing ratio, the melting point of the mixture is lowered and it liquefies at room temperature, so there is no need to heat and melt it when reacting with the epoxy resin, improving workability, improving heat resistance, and achieving a Tg of 10 to 20°C. will also rise.

In the composition of the present invention, the ratio of each component of the epoxy resin and curing agent is such that 1 epoxy group in the epoxy resin and 1 hydrogen group in the 7-mino group in the aminobenzylamines and aromatic diamines. It is usually used in a ratio of 0.5 to 1.5, preferably 0.8 to 1.2.

Next, by adding antimony antimony (Sb70i) 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. Addition amount is 51f
If the amount is less than L5j, the effect will not be sufficiently expressed, and 5
If it exceeds 0 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. Examples of the rubber 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.

As the acrylic ester rubber, for example, JP-A-55
-18053 or Japanese Patent Application Laid-Open No. 55-21432.

In addition, as for uricone rubber, for example, Japanese Patent Application No. 1982-
No. 180821.

In addition, examples of the conjugated diene rubber include 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3
It can be produced by polymerizing or copolymerizing hexaene, chloroprene, etc., and Ichisaka products can be used.

The amount of carbon used is 5 to 40 parts, preferably 12 to 35 parts per 100 parts of Epoquin 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 during curing.

Graft combination with mepoquine resin may also be used.

Uninvented compositions include quinrylene diamine, inphorone diamine, 13-bisamine methylcyclohexane, diaminodiphenylmethane, polyamide resins, triethylamine, dimethylhendylamine, imidazoles, trisdimethylaminomethylphenol as curing agents and accelerators. Heptamines such as phenol, cresol, trifluoroboron amine salt, etc. may be used in combination as long as they do not impair the effects of the present invention.

Also solvents, silane-based and titanium-based coupling agents, pigments, organic and inorganic fillers, if plastics.

Liquid rubber, thixotropic agent, leveling agent, antifoaming agent.

Tar, non-reactive diluents, low molecular weight polymers, glass fibers, carbon fibers, metal fibers, ceramic fibers, etc. can also be added and used.

The composition of the present invention can be used as a coating material, an adhesive, a casting agent, a sealant, a molding material, a processing agent for fiber Φ paper, and the like. Further, the composition of the present invention can be generally cured under conditions of 5 to 200°C.

The present invention will be explained in more detail below by way of examples.

Note that parts 1 or % in each item below are expressed on a weight basis unless otherwise specified.

Example 1 Amine-based epoxy resin made from meta-aminophenol and epichlorohydrin (trade name: Bototo YDM-
120, Tobu Kasei Co., Ltd., 32 parts of the main component (3 epoxy groups in one molecule), 13 parts of para-aminobenzylamine and 5 parts of 3,5-diethyltoluene 2,4-diamine were thoroughly mixed. When it was left to stand at room temperature, the adhesiveness almost disappeared and it cured after 170 minutes. After this cured product was left at room temperature for one week, a dynamic viscoelasticity test of the cured product was conducted using a Rheopybron tester. As a measure of the heat resistance of the cured product, the glass transition temperature was determined to be 175°C.

(The glass transition temperature was defined as the temperature at which Epa (loss modulus of elasticity) peaked. Hereinafter, the glass transition temperature will be used in this sense.

Example 2 Amine-based epoxy resin made from diaminodiphenylmethane and epichlorohydrin (trade name: Epotote Y)
H-434, Tobu Kasei Co., Ltd., phenolic epoxy resin made from bisphenol A and epichlorohydrin (product name: 4 epoxy groups in one molecule)
Epicote 828, Yuka Shell Epoxy Co., Ltd.; 2 epoxy groups in one molecule of the component) and aminobenzylamine and toluene 78% (3,5-diethyltoluene 2.4-diamine 78% and 3. A mixture of 5-diethyltoluene and 22% of 4-cyamine) shown in Table 1 was mixed, and the time until the adhesiveness disappeared was determined as the curing time. After curing, the material was allowed to stand at room temperature for 14 hours as in Example 1, and then the glass transition temperature was determined by a dynamic viscoelasticity test. The results are summarized in Table 1.

Example 3 Phenolic epoxy resin made from phenol novolank resin and epichlorohydrin (trade name, Epicote +54. Yuka Shell Epoki/Co., Ltd., main component has 3 epoxy groups in one molecule) 80 parts, bisphenol F diglycidyl ether (the main component has 2 epoxy groups in one molecule)
20 parts), and 19.8 parts of the atactant obtained by reacting 72.5 moles of meta-aminobenzylamide with 1 mole of ethylene glycol diglyndyl ether at 80°C for 2 hours.
parts and 3.5-diethyltoluene 2.4-cyami/8.5
The curing time and glass transition l temperature were determined in the same manner as in Example 1. Curing time is 230 minutes, glass transition temperature is 1
Example 4 A phenolic epoxy resin made from tetraphenylethane and epichlorohydrin (trade name: Epicor h
1031. Yuka shell epoxy C resin.

(4 epoxy groups in 1 molecule of the main component) 85 parts, 15 parts of vinylcyclohexene dieboxide (2 epoxy groups in 1 molecule), and 1 part of meta-aminobenzylamine
The curing time and glass transition temperature were determined in the same manner as in Example 1 using 3.1 parts of 3.5-diethyltoluene and 87 parts of 2.4-diamino. The curing time was 170 minutes and the glass transition temperature was 198°C.

Example 5 40 parts of Epicor) +031, 7 parts of vinylcyclohexene epoxide, 3 parts of Epotot YH-43453, 12.1 parts of meta-ami7 pendylamine, 6.5 parts of para-aminopencylamine, and 2 parts of 3.5-diethyltoluene.
．． The curing time and glass transition temperature were determined using 7.5 parts of 4-cyamine in the same manner as in Example 1. The curing time was 130 minutes, and the glass transition temperature was 209°C.

Example 6 An experiment similar to Example 1 was conducted using the following composition.

Evototo Y H-4344 3 parts Vinyl cyclohexene dieboxide 5 parts Aminopencylamine 8.9 g 1 t -A B
A 48.5% 3.5-diethyltoluene 2.4-diamine 95% and 3.5-diethyltoluene 2
, 6.0 parts of a mixture with 5% of 4-cyamine The curing speed was 110 minutes, and the glass transition temperature was 195°C.

Example 7 To the same amount of epoxy resin and curing agent as in Example 1, 23 parts of antimony pentatoxicity was further added and mixed well, and the mixture was left to stand at room temperature. After 170 minutes, almost no stickiness was left and the mixture was cured. After that, keep it in the air at 200°C for a long time, and
The tensile shear strength (8f according to JIS K8850) at ℃ was measured to investigate thermal deterioration. The results are summarized in Table 2.

The adherend is cold rolled steel plate (JISG3141) 5P(I
c-knee SD (1,6a+m thickness) was used.

Table 2: The tensile shear strength of the samples containing anti-7/trioxide is smaller than that of the samples containing no additive.

Example 8 A primary rubber component was synthesized.

Phenolic epoxy resin made from phenol novolac resin and shrimp glolhydrin (trade name, Epicote [52, Yuka Shell Epoxy Co., Ltd., main component has 2 epoxy groups in one molecule] 500 parts, acrylic acid 9 parts and 1 part of triethylamine were added, and the temperature was raised to 100°C.
By reacting for a period of time, 5011 parts of an epoxy resin into which acrylic acid residues were introduced was produced.

Next, 370 parts of butyl acrylate, 1 part of azobisdimethylvaleronitrile, and 2 parts of azobisisobutylonitrile were added to this, and a polymerization reaction was carried out at 70°C for 3 hours and then at SOoC for 1 hour, thereby combining the epoxy resin and acrylic resin. A graft polymer with an ester system was prepared. (Assumed to be Al.) The following experiment was conducted with the following composition.

Epotote YH-43443 parts vinylcyclohexene dieboxide 5811A1
33 parts Aminobenzylamine 13.8 parts (〇 2.8% 1m integral 48.3%, P 48.5%) 3.5-diethyltoluene 2.4-diamine 2.7 parts 3.5- Diethyltoluene 2.6-diamine 0.8 parts Jl5K6855 Izot impact strength (test piece material JIS G4051-SIOC> was measured, 12
．． It was 0 kgφcm/Crr['. On the other hand, in the case of Example 6, which did not contain rubber, the impact strength was 8.0 kg·cm/cm', and acceptable impact strength was observed.

Effects of the Invention As described in detail below, the thermosetting composition of the present invention has a high curing speed and excellent heat resistance, heat deterioration resistance, and impact resistance, and also has aminobenzylamine used as a curing agent. Since the m- and p-1 mixture can be used as is, the economical effect is extremely large.

Claims (4)

[Claims] (1) (a) An epoxy resin consisting of 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule, and (b) a thermosetting composition comprising aminobenzylamines and aromatic diamines. (2) (a) An epoxy resin consisting of 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule, (b) aminobenzylamines and aromatic diamines; and (c) antimony trioxide. A thermosetting composition comprising: (3) (a) An epoxy resin consisting of 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule, (b) aminobenzylamines and aromatic diamines; and (c) rubber. A thermosetting composition comprising: (b) aminobenzylamines and aromatic diamines; and (c) rubber. (4) (a) An epoxy resin consisting of 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule, A thermosetting composition comprising: (b) aminobenzylamines and aromatic diamines; (c) antimony trioxide; and (d) rubber.