JPS6181424A - Thermosetting composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having high rate of cure and excellent heat-resistance, heat-deterioration resistance and impact resistance, and useful as a paint, etc., economically, by compounding a specific epoxy resin, an aminobenzylamine, and a specific antimony compound. CONSTITUTION:The objective composition can be produced by compounding (A) an epoxy resin composed of (i) 100-30 (wt)% epoxy resin having >=3 epoxy groups in one molecule and (ii) 0-70% epoxy resin having >=2 epoxy groups in one molecule, with (B) an aminobenzylamine compound and (C) antimony trioxide. Preferably, (D) a rubber, is used in place of the compound C or in addition to the components A-C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermosetting composition that provides a cured product with little odor, excellent curability at room temperature, and excellent heat resistance.

Conventional technology Epoxy resin compositions that cure at room temperature are used for paints, adhesives,
Widely used for 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 poor curing, and the resulting cured product has poor heat resistance. Because of this, its use was limited.

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 (U.S. Pat. No. 3,317,468), and this type of composition has a slow curing rate at room temperature and can be obtained. The disadvantage is that the heat resistance of the cured product is poor.

Problems to be Solved by the Invention Therefore, as a result of intensive study, the present inventors discovered bisphenol A.
100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule in place of diglycidyl ether;
By using 7-minobenzylamines as a curing agent together with an epoxy resin consisting of 0 to 70 wt 1 ν% epoxy resin having two or less epoxy groups in one molecule, -
1; It has been found that it is possible to obtain a thermosetting composition with improved curing speed at room temperature, and markedly improved thermal properties.

However, the cured product of the thermosetting composition obtained in this way may undergo thermal deterioration when exposed to high temperatures for a long period of time.
In addition, they had drawbacks such as not being able to withstand strong impacts.

As a result of various studies to eliminate these drawbacks, it has been found that the addition of antimony trioxide is effective in preventing thermal deterioration of the cured product, and the addition of rubber is effective in improving impact resistance.

The present invention was completed based on this knowledge.

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;
1. An epoxy resin comprising 0 to 70% by weight of an epoxy resin having 3 or less epoxy groups; (b) aminopencylamide/class (Q) antimony trioxide.

C2> (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
(b) aminobenzylamines; (b) aminobenzylamines;

(c) Rubber.

A thermosetting composition comprising:

(3) (a) 100-30% by weight of an epoxy resin having 3 or more epoxy groups in the molecule, 2% in 1 molecule
An epoxy resin consisting of 0 to 70% by weight of an epoxy resin having 1-3 epoxy groups, Cb) aminopencylamines, (c) antimony trioxide.

(d) A thermosetting composition characterized by containing the following.

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.

lit Amine-based epoxy resins, such as N, N, N'', N'-tetraglycidyldiaminodiphenylmethane, meta-N, N-diglycidyl di!reaminophenyl glycidyl ether, N, N, N', N
It is synthesized from a compound having an amino group or an amide group, such as '-tetraglycidyl terephthalamide, and shrimp helohydrin, such as epichlorohydrin, methylepichlorohydrin, and epibromhydrin.

Specific examples of compounds having amine 7 groups include diaminodiphenylmethane, meta-xylylene diamine, para-xylylene diamine, meta-aminobenzylamine, para-aminobenzylamine, 1,3-bisaminomethylcyclohexane, 1,4-bis Aminomethylcyclohexane,■
, 3-diaminocyclohexane, 1,4-diaminocyclohexane, metaphenylenediamine, paraphenylenediamine, benzylamine, diaminodiphenylsulfone, diaminodiphenyl ether, diamino, /phenyl sulfite / aminonaphtol, naphthalene diamine aniline toluidino, Examples include meta-aminophenol, para-aminophenol, and aminonaphthol.

Further, specific examples of compounds having an amide group include phthalamide, inphthalamide, terephthalamide I, -\
/suamito, toluamide, parahydroquinopenamite, Jterhydroquinone, and so on.

A compound with a double amino group (or an amide group)
In the proboscis, amine groups or amino□ (external hydrocilia,
When a compound has a group that is anti-corrosive to rohitrin, part or all of it may be substituted with an epihalohydrin group and may be substituted with an epoquine group.

ii゛ Phenolic epoxy resin hisphenol henglysosyl ether, Epotote Y
It can be synthesized from a phenolic compound and epihalohydrin, such as D CN-220 (product of Tobu Kasei Co., Ltd.).

Specific examples of phenolic compounds include Fair'-al,
Cresol, butylphenol, octylphenol,
hecumylphenol, cumylphenol, naphthol,
Hydroquinone, catechol, renrunono, hisphenol A and suphenol F, bisphenol sulfono,
Examples include visualized bisphere/-A, nophoranc resin, cresol nophora, resin, tetraphenylethane, triphenylethane, and the like.

11D Alcohol-based epoxy resin trimethylolpropane triglycidyl ether Can be synthesized from an alcohol-based compound and epi/\glycidyl ether, such as neopentyl glycol glycidyl ether.

Specific examples of alcohol compounds include monohydric alcohols such as butyl alcohol and 2-ethylhexyl alcohol, ethylene glycol, nitethylene glycol, triethylene glycol, ethylene glycol, propylene glycol, and dibropylene/glycol 1 polypropylene. Noglycol 1,4-butaneol, l,6-
Hexano-7ol Neobenol glycol Trimethylolpropane, Glycerin, Pentaerythritol Polyprolactone, Polytetramethylene ether glycol, Polybutadiene glycol, Hydrogenated hisphenol A, Ngol, Ngol, Bisphene, −
Lehe〇Ethire/-Sekishitei size addition, hisphenol,
Examples include polyester polyols made from A. propylene oxide, polyalcohols, and polyester polyols made from these polyalcohols and polycarboxylic acids.

iV) Epoxidized products of unsaturated compounds - clopenotadiene epoxy i epoxy/chemical 7 (v: oil epoxidized polybutane/, vinylcyclo△, oxidized/.../epoxide, styrene ogyishito Yujisai no car 7, product name of ide juice E RL-4221, ERL -4234, E RL
Examples include epoxidized products of unsaturated compounds known as -4299 and the like.

, v) Can be synthesized from carbonic acid, Ebihalo, and Torino, such as glycidyl ester-based epoxy resin, glycidyl ester of aromatic acid, and diglycidyl ester of tetrahydrophthalate.

Specific examples of carboxylic acids include ammonium, 0. Monocarphonic acids such as folic acid, paraoxic benzoic acid, butyl benzoic acid,
Ampic acid, mono-tinic acid, dodecanedicarboxylic acid, meric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, -11, toric acid, pear, acid,
Maleic acid, fumaric acid, trimellitic acid, he, ncenotetracarboxylic acid, butanetetracarboxylic acid, penzophenonotetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-tuclohexene -1,
Examples include polysulfonate acids such as 2-carboxylic heptaic acids.

(2) It can be synthesized from urethane epoxy resin + iF7 mentioned polyhydric alcohol, diisonanate, and wayohi glycidol.

7.Specific examples of innoanates include tolylene isoneanate, nphenylmethano-4,4'-fincyanate, methylene'noisonoanato, isophoro/
Examples include diisocyanate, quinolyl isocyanate, and naphthalene soisocyanate.

Shrine Other epoxy trees [) h Tris-evokipropylison annulate, Glinonol (
Examples include meth)acrylate copolymers, and modified resins of the above-mentioned epoxy resins with diisonanate, dicarpho/acid, polyhydric phenol, and the like.

In addition, from the point of view of curing speed and thermal properties, epoxy #! has three epoxy groups. i4 fat is especially flft-like,
As the type of epoxy resin, amine epoxy resins and phenol epoxy resins are particularly preferred.

In the present invention, epoxy resins can be used singly or in combination of two or more.

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 has three or more epoxy groups in one molecule. It must be made of epoxy resin. If the amount of epoxy resin having three or more epoxy groups is less than 30%, 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, aminohensylamines, that is, mainly para-aminobenzylamines, meta-aminopencylamines, and mixtures thereof, are used as curing agents for epoxy resins. These seven ducts 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.

Furthermore, this adduct may be a separate adduct, an endogenous adduct, or a mixture of both.
Even if these benzylamines contain the ortho form that is usually produced as 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 may be used as is without purification as long as it is a small amount. do not have.

In the composition of the present invention, the ratio of each component used is usually 0.5 to 1.5. Preferably, they are used in a ratio of 0.8 to 1.2.

Further, the ratio of the combined use of para-aminopencylamines and meta-aminopencylamines can be as high as iii 4 [the melting point of the mixture can be lowered].

According to Tatoe, the melting point of meta-aminobenzylamine is approximately 40.
°C, but when half of both are used, the melting point is approximately 1
The temperature drops to 5°C. Therefore, reactivity is improved, curing time is shortened, and heat resistance is also improved.

Next, by adding antimony trioxide (Sb20i) to the thermosetting composition, the heat deterioration resistance of the cured product is greatly improved. The added sulfur is preferably 5 to 50 parts by weight per 100 parts by weight of the epoxy resin. If the added amount 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. 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 J silicone rubber, for example, Japanese Patent Application No. 1983-
No. 180831.

Examples of conjugated diene rubber include:

It can be produced by polymerizing or copolymerizing monomers such as 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, and chloroprene, and commercially available products can be used.

The usage fee for rubber is 100 parts of epoxy resin.
The amount is 5 to 40 parts by weight, preferably 12 to 35 parts by weight.

The comb may be dissolved or dispersed in the epoxy resin. Alternatively, it may be dissolved in an epoxy resin and precipitated as particles upon curing.

Alternatively, a polymer may be used instead of a graft of epoxy/wood.

The composition of the present invention contains xylylene diamine, inphoroncyamini/1,3-bisaminomethylcyclohexane as a curing agent and curing accelerator.

Diaminodiphenylmethane, polyamide resin, triethylamine, dimethylbenzylamine, imidazoles,
Aminos 7 such as trisdimethylaminomethylphenol, phenol, Fresol, trifluoroboron amine salts, etc. can be used in part in combination as long as they do not impair the effects of the present invention.

Also, solvents, silane and titanium coupling agents, pigments, organic and inorganic fillers, =r plastics, liquid rubber, thixotropic agents, leveling agents, antifoaming agents, tars, 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 in paints, adhesives, casting agents, sealants, molding materials, processing agents for fibers, 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 and percentages in each of the following 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., main component has 3 epoxy groups in one molecule) 92 parts, aminopencylamine (2.
Roughly 23 parts of antimony trioxide was added to 23 parts of a mixture of 8% M, 48.3% m, and 48.5% p, mixed well, and left at room temperature. After 180 minutes, it became almost sticky. It disappeared and hardened. Thereafter, after being left at room temperature for one week, the tensile shear strength at 20° C. was measured to check for thermal deterioration. The results are summarized in Table 1.

Table 1 Example 2 The following rubber components were synthesized.

Phenolic epoxy resin made from phenol novolac resin and epichlorohydrin (trade name, Epicote 152. Yuka-Nel Eboxy Co., Ltd., the main component has 2 epoxy groups in one molecule) sooi, 9 parts of acrylic acid,
Add 1 part of triethylamine and raise the temperature to 110°C.
By reacting for 8 hours, 509 parts of epoxy resin into which acrylic acid residues were introduced was produced.

Next, 370 parts of butyl acrylate, 1 part of azobisdimethyl yashironitrile, and 2 parts of azobisisobutyronitrile were added to this, and a polymerization reaction was carried out at 70°C for 3 hours and further at 90°C for 1 hour. A graft polymer of epoxy resin and acrylic ester was produced. (It is referred to as At.) The following experiment was conducted with the following composition.

Epoto) YH-4344 3 parts Vinyl cyclohexene gepoxide 5 parts A1
33 parts Aminobenzylamine 18.2 parts (2.8% in one piece, 48.3% in one meter, 48.5% in one piece) JISK6855 IC, impact strength (test piece material JISG4051-SIOC) was measured. , 12
．． It was 5 kg @cm/cm'. On the other hand, in the case of Example 1 which does not contain rubber, the weight is 6.0 kg cm/am',
A considerable improvement in impact strength was observed.

Example 3. Comparative example 1 rubber component Diglycidyl ether of bisphenol F Bo.

Add 12 parts of acrylic acid and 1 part of triethylamine to
By raising the temperature to 110°C and reacting for 5 hours,
Next, 15 parts of hydroquine ethyl acrylate and 1 part of anhisisobutyronitrile were added to 613 parts of epoxy resin into which acrylic acid residues had been introduced, and polymerization was carried out at 70°C for 3 hours and then at 80°C for 1 hour. The reaction was carried out.

Next, methoxyno is added to the molecule (Toray Silicone Co., Ltd., product DC-3037) 7
0 parts, add 0.3gl1 of dibutyltin dilaurate,
The reaction was carried out at 150°C for 1 hour. The latter 30 minutes of the reaction was carried out under reduced pressure of 20 mmHH in order to distill off the methanol produced. In this way, a graft polymer of a modified epoxy resin and a silicone compound was produced.

This is Shin-Etsu Chemical's product Shin-Etsu Silicone KE-120.
300 parts of silicone rubber consisting of a 1 part 1 mixture of KE-4A and KE-1204H were added and reacted for 2 hours with vigorous stirring to produce an epoxy resin in which silicone rubber was dispersed. (This is referred to as A2.) Impact strength was measured using the following composition.

Example 3 Comparative Example 1 Evoto YH-43443fl
43 parts Vinylcyclohexenone epoxy 1 5 parts 5 parts A2 33 parts 0 parts Ami/benzylamine 16 parts 13 parts Izont impact strength 12.0 parts 6.5 parts (JISK8855,
Material of test piece: JIS G4051-SIOC) 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. Furthermore, since the aminobenzylamine used as a curing agent can be used as an m-1p-1 mixture, the economic effect is extremely large.

Claims (3)

[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, (b) aminobenzylamines; (c) antimony trioxide. A thermosetting composition comprising: (b) aminobenzylamines; (c) antimony trioxide. (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, 1. A thermosetting composition comprising: (b) an aminobenzylamine; (c) a rubber. (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, A thermosetting composition comprising: (b) aminobenzylamines, (c) antimony trioxide, and (d) rubber.