JPH0441523A - Curable polyepoxide composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of relatively low viscosity which can give a cured product excellent in toughness, impact resistance, peeling resistance, etc., by mixing a specified polyepoxide with a specified curing agent compound. CONSTITUTION:The title composition essentially consists of a polyepoxide having at least 1.5 glycidyl groups on the average per molecule (e.g. Araldite GY260, a product of Ciba-Geigy Co.) and a curing agent compound obtained by reacting by heating 1mol of an N-monoalkyl-alkylenediamine of formula I (wherein R1 is 1-4C alkyl; and (n) is 2-3) with 0.3-1.0 equivalent of a bis-p-{3- alkoxy-2-(2,3-epoxypropoxy)propoxy} phenyl] alkane of formula II (wherein R2 is R1; and R3 is 1-3C alkylene) and distilling off unreacted diamine.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application Polyepoxides having an oxirane ring in the molecule can be combined with various curing agent compounds and cured either at room temperature or by heating. The cured product has excellent adhesion to many substances, so it can be used for adhesives, paints, injections, impregnations, castings, etc.
We have many achievements in fields such as potting and molding.

This invention is directed to this polyepoxide resin related field,
The present invention provides a polyepoxide resin composition that exhibits excellent performance when cured at room temperature or by heating.

Prior Art and Problems Polyamine compounds are used in most cases as polyepoxide curing agent compounds that can be cured at room temperature or by heating. This takes advantage of the strong basicity of the nitrogen atoms in polyamines. There are a wide variety of polyamine curing agents that are actually used. These include not only simple polyamines but also various derivative substances, and their classifications and names are not clear.

In various applications that utilize epoxide-based cured products, the properties of the cured epoxy F-based resin are important. Generally, materials cured with polyamines are hard and brittle. In addition, there are many types of polyamines that have been derivatized by some method, or even those that have been cured by this method are still hard in nature.

Generally, excellent toughness, peel strength, and impact strength are often required as performances of cured epoxide products, and currently existing curing agents cannot fully satisfy these demands. Toughness here means that the cured product itself has both tensile strength and elongation in a tensile test, or one of them has strength above a certain level and the other has outstanding strength. It is interpreted as being present. Furthermore, one of the important properties of an epoxide-based cured product is impact strength. This property is also related to toughness, and in general, those with strong properties have excellent impact strength, and conversely, those with brittle properties have poor impact strength.

Some polyamines or polyamine derivatives can impart flexibility when cured to epoxide compounds, but in many cases they are simply soft,
There are few things that truly have excellent toughness. Also, among these, when the epoxide is similarly cured, there are some that show a certain value of tensile strength in the tensile test as a cured product, or these are simply because they are hard. There are few products that show sufficient values in elongation tests. When considering the performance of adhesives in various situations, the same can be said about the peel strength of adhesive properties, and many curing agent compounds are actually used as adhesives. However, there are few materials that truly have excellent peel strength.

As a very small number of examples, there are polyamine derivatives synthesized from natural rubber, synthetic rubber, and compounds, and of course, when used to cure epoxide, they exhibit excellent toughness. In other words, there are products that show sufficient strength and elongation as well as excellent impact strength in tensile tests, and excellent peel strength in adhesive tests, but these are extremely viscous in normal conditions. It is quite large and is quite inconvenient to handle. Given this current situation, it is recommended that the curing agent for polyepoxide has a relatively low viscosity, is easy to handle, and will harden at room temperature after being mixed with the epoxide, resulting in a cured product with excellent toughness and impact strength. There has been a strong desire for the development of a curing agent that can provide properties with excellent peel strength when tested as an adhesive, and for the existence of a polyepoxide composition based on this curing agent.

Means to solve the problem We are based on the current situation surrounding epoxide-related technology,
We have made our utmost efforts to solve this problem and have completed this invention. That is, the purpose of this invention is to develop a polyamine curing agent with a relatively low viscosity, and when polyepoxide is cured using this curing agent, it exhibits excellent toughness, that is, excellent tensile strength when tested in a tensile test. The object of the present invention is to provide a polyepoxide-based curable composition that has excellent elongation at break and impact strength, and also has excellent peel adhesion strength when tested as an adhesive. In more detail, component A: average within the molecule.
Polyepoxide having 1.5 or more glinosyl groups and component B represented by the following general formula % (in the formula, R1 is an alkyl group having 1 to 4 carbon atoms, and n represents 2 or 3) N- Monoalkyl alkylene diamine (component B) and the following general formula % formula % (in the formula, R5 is an aryl group having 1 to 4 carbon atoms, R3
represents an alkylene group having 1 to 3 carbon atoms) Bis[p-(3-alcokyne-2-(2,3-epoxypropoxy)propoxy)phenylcoalkane (component B!: hereinafter referred to as BAEP) Consisting of component B,
It consists of a curing agent compound synthesized by a method of reacting between 0.3 and 1.0 equivalents of component B with respect to 1 mole, and then removing component B by vacuum distillation, and component A and component B. Excellent toughness when mixed and cured.
That is, to provide a curable polyepoxide composition that has excellent tensile strength and elongation at break as well as impact strength when tested in a bow tension test, and also has excellent peel strength when tested as an adhesive. It is something.

The polyepoxides having an average of 15 or more glinonol groups in the molecule of component A constituting this invention are basically polyepoxides having 2 or more glycidyl groups in the molecule; It is possible to use a mixture of modiepoxides having one Grindyl group. Examples of these include the following:

Bisphenol A1 Bisphenol F1 Bisphenol S1 Hexahydrobisphenol A, Tetramethylbisphenol A1 Catechol, Resorcinol, Frebour Novolak, Tetrabromobisphenol A1 Trihydroquinobiphenyl, Benzophenone, Bisresol nonol, Bisphenol hexafluoroacetono, Hydroquinone, Tetramethylbisphenol A1 Tetramethylhisphenol F, triphenylmethane, tetraphenylecno, hikylnol, glino-lether obtained by reacting seven polyhydric phenols with epichlorohydrin, or glycerin, neobentyl glycol,
Obtained by reacting aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hekyl gelicol, boi ethylene glycol, i1 nobrobin 11:1-l and shrimp luchtrin. ) L ether, or glinonol ether ester obtained by reacting epichlorohydrin with a human quinocarpho/acid such as p-hydroquinobenchoic acid, 2-hydroquinonaphthoic acid, or phthalic acid, methylphthalic acid, isophthalic acid, etc. Polyglynonol esters obtained from polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, ettomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acids, some t)
3. Glycidylaminoglycidyl ether obtained from aminophenol, aminoalkylphenol, or glycidylaminoglycidyl ether obtained from aminobenzoic acid, or aniline, toluidine, tribromoaniline, xylylene diamine, cyclohexanediamine, bisaminomethylcyclohexane, 4. Grindyl amines obtained from 4°-diaminodiphenylmethane, 4°4′-diaminodiphenyl sulfone, and the like, as well as epoxidized polyolefins, and polyglycidyl ethers such as grindylhydantoin, glycidyl alkylhydantoin, and triglycidyl cyanurate. Also allyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, cyclohexyl glycidyl ether, methyl cyclohexyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, methyl benzoin. Monoglycidyl ethers such as acid glycidyl esters and styrene oquinide can also be mixed and used to adjust the viscosity and pot life.

N-monoalkylalkylene diamine represented by the following general formula % (in the formula, R1 is an alkyl group having 1 to 4 carbon atoms, and n represents 2 or 3), which is a raw material for component B constituting the invention. is a compound having primary and secondary amino groups in the molecule, examples of which include the following.

N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-butylethylenediamine, N-pentylethylenediamine, N-
These include hexylethylenediamine, N-methyltrimethylenediamine, N-ethyltrimethylenediamine, N-propyltrimethylenediamine, and N-butyltrimethylenediamine.

Among these, N-methyltrimethylenediamine is particularly preferred.

BAEP, which is the raw material of component B constituting the invention, is synthesized using a series of bisphenol compounds called bisphenol A, bisphenol F, and bisphenol AD, which are divalent phenol compounds, butyl glycidyl ether, and shrimp chlorhydrino as raw materials. It is a noepoquinodo with a diglynodyl group. Among these, diglyndyl diepoxide derived from bisphenol A is particularly preferred.

The curing agent compound of component B of the present invention is basically synthesized by the following composition and method. The reaction is carried out in a range of BAEPh<0.3 to IO equivalent per mole of N-monoalkylalkylenediamine. That is, B.A.E.
The N-monoalkylalkylene diamine is reacted in an amount of 1 mole or more per equivalent of P. This is because the purpose of the present invention is to synthesize a curing agent compound with a viscosity as low as possible, and for this purpose, the growth of molecular weight due to repeated addition polymerization of BAEP and N-alkyl alkylene diamine is suppressed. For this purpose, the greater the number of reacting moles of N-alkylalkylenezamine relative to BAEP, the better the result, but the economics of synthesis becomes an issue, and these relationships are determined by the raw material composition as described above. Preferably within the ratio.

During the synthesis of component B, the reaction was carried out using N-
For alkyl alkylene diamines, a method is adopted in which the diepoxide component is added in small amounts batchwise to avoid heat generation due to reaction. Although this reaction proceeds even at room temperature, it requires a long time, and heating is preferred in order to complete the reaction in a short time. At the end of the reaction, unreacted components of the N-monoalkylalkylenezamine are removed by vacuum distillation.

The mixing ratio of component A and component B is basically such that the epoxy equivalent of the epoxide and the active hydrogen equivalent of the curing agent compound are approximately similar. Therefore, these mixing ratios are influenced by the type of epoxide used and are not uniform. To express it roughly, the amount of curing agent compound is 30g for 100g of epoxide compound.
g to 130 g.

Other additives may be added to the curable epoxy composition according to the present invention, if necessary. Examples of such additives include alumina, silica, silica powder, talc, bentonite, calcium carbonate, inorganic material powder such as cement, asbestos, glass fiber, synthetic fiber, mica, metal powder, flame retardants, etc. Further examples include various thixotropy-imparting materials and similar materials. Further, a solvent, synthetic resins, or other organic compounds may be added to the composition of the present invention, if necessary.

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited to the scope of these examples.

Hardening agent compound production example 1 40 equipped with a nitrogen flow device, a stirring device, a thermometer, a reflux device with a trap for evaporation, a dropping funnel, and a pressure reduction device
In a flask, 176 g of N-methyltrimethylenediamine
(2 mol) and 100 g of toluene were charged. While nitrogen was introduced, the temperature was maintained at 80°C, and stirring was performed,
Bis[p-(3-butquin-2-(
2,3-epoxypropoxy)propoxy}phenylconomethylmethane (Evoquin compound XB manufactured by Ciba Geigy)
4122) 340g (1) and 100g toluene
was added dropwise little by little over about 2 hours. After this, the temperature was brought to 120° C. and maintained at this temperature for 2 hours. The temperature was then raised to 150° C. and the evaporating toluene was removed into the evaporator trap. A vacuum operation was applied at the end of the toluene removal step. When I cooled it down, took it out, and examined it, this thing was 4.
It was a viscous liquid with a viscosity of 4.7 Pa-s at 0°C and an amine value of 265.

Curing Agent Compound Production Example 2 Into the same apparatus as Curing Agent Compound Production Example 1, 176 g (2 moles) of N-ethylethylenediamine and 100 g of toluene were added.
I prepared it. While nitrogen was introduced, the temperature was maintained at 80°C, and stirring was performed, the bis[p-(
A mixture of 340 g (I equivalent) of 3-butoxy=2-(2,3epoquinopropoquine)propoquine)phenylconomethylmethane (Evoquino compound XB4122, manufactured by Ciba Geigy) and 100 g of toluene was added dropwise little by little over about 2 hours. After this, the temperature was brought to 120° C. and maintained at this temperature for 2 hours. The temperature was then raised to 150° C. and the evaporating toluene was removed into the evaporator trap. A vacuum operation was applied at the end of the toluene removal step. When they were cooled, taken out, and examined, they were found to be viscous liquids with a viscosity of 9.7 Pa-5 at 40°C and an amine value of 260.

Example]-12 Curing agent compounds The curing agent compounds synthesized in Production Examples 1 and 2 and various commercially available epoxides were combined and cured, and the tensile strength, elongation at break, Izot impact strength and The adhesion strength before T-shaped peeling was tested using a cold rolled steel plate. These results are shown in the table.

Reference Examples 1 to 6 Similarly to Examples, commercially available hardeners and various epoxides were combined and cured, and the bow strength, elongation at break, Izot impact strength, and cold-rolled steel plate were measured. Each of the T-shaped specimens was tested for adhesive strength before peeling. These results are shown in the table.

The commercially available engineering kits and curing agents used in Examples and Reference Examples are as follows.

Epoxy F' A Araldite G manufactured by Ciba Geigy
~ 260 Epoxy L” B Adekalenone PU manufactured by Asahi Denka Kogyo, r-f kit C Calenone EPO-20 manufactured by Shin Nihon Rika
E Epoxide D Evokin resin B41 manufactured by Ciba Geigy
22 Epoxide E, Yuka L Evokino Epicoat 871 Ebokinod F, Asahi Denka Kogyo Adeka Resin EP-400
0 Curing agent A, polyamino amide tomide #225-X manufactured by Fuji Chemical Industry Co., Ltd. Curing agent B Polyamino amide tomide #245 manufactured by Fuji Chemical Industry Co., Ltd. In addition, the various test methods adopted in the examples and reference examples are as follows. .

(1) Tensile strength and elongation A mixture of epoxide and a curing agent compound was poured into a tensile test mold conforming to the provisions of JIS K 6911, and the mixture was left at 23° C. for 10 days to cure. After being removed from the formwork, the tensile strength and elongation at break were tested using a tensile testing machine in the same room. The crosshead speed of the tensile tester was 5011 m/min.

(2) Izot impact strength A mixture of epoxide and a curing agent compound was poured into a mold for Izot test conforming to the provisions of JIS K 6911, and the mixture was left at 23° C. for 10 days to cure. After being removed from the formwork, an Izot impact test was conducted in the same room.

(3) T-type peel adhesion strength A cold-rolled steel plate for T-type peel adhesion test specified in JIS K 6850 was bonded with a mixture of epoxide and a curing agent compound. This material was heated to lO at 23°C.
It was left for several days to cure. Thereafter, a T-shaped pre-failure adhesion test was conducted in the same room using a tensile tester. The crosshead speed of the tensile tester is 50 mm/mi.
It was set as n.

Discussion of the results of Examples (1) Tensile strength and elongation at break 2 The curing agent systems shown in Table 1 thus produced in Curing Agent Production Examples 1 and 2 are the systems using commercially available curing agents. Both the tensile strength and elongation are large compared to the above.

(2) Izot impact strength As shown in the table, the curing agent systems made in Curing Agent Production Examples 1 and 2 do not break upon impact compared to systems using commercially available curing agents. , or the value of fracture energy is large.

(3) T-type peel adhesion strength 2 As shown in the table, the curing agent systems made in Curing Agent Production Examples 1 and 2 were generally superior to the systems using commercially available curing agents. Both the initial value and the stable value of peel adhesion strength are large, and all of the failure motes show cohesive failure, which is a feature that indicates excellent adhesive strength.

Effects of the Invention According to the above explanation, the present invention can provide a polyepochino resin composition which has a relatively low viscosity and has excellent toughness, impact strength and adhesive peel strength when cured. It is clear that there is.

Patent applicant: Fuji Kasei Kogyo Co., Ltd.

Claims (6)

[Claims] (1) Component A: Polyepoxide having an average of 1.5 or more glycidyl groups in the molecule Component B: The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 has a carbon number of 1 to 4. alkyl group, n
represents 2 or 3) N-monoalkyl alkylene diamine (component B_1) and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_2 is an alkyl group having 1 to 4 carbon atoms ,R
_3 represents an alkylene group having 1 to 3 carbon atoms) bis[p-{3-alkoxy-2-(2,3-epoxypropoxy)propoxy}phenyl]alkane (
Component B_2), which is synthesized by a method of heat-reacting Component B_2 in a range of 0.3 to 1.0 equivalents per 11 moles of Component B_2, and then removing unreacted components of B_1 by distillation. A curable polyepoxide composition basically consisting of a mixture of component A and component B. (2) The raw material bis[p-{3-alkoxy-2-(2,3-epoxypropoxy)propoxy}phenyl]alkane constituting component B is a diepoxide derived from bisphenol A, bisphenol F, and bisphenol AD. A curable polyepoxide composition according to claim 1. (3) Claim 1, wherein the raw material bis[p-{3-alkoxy-2-(2,3-epoxypropoxy)propoxy}phenyl]alkane constituting component B is a diepoxide derived from bisphenol A. The curable polyepoxide composition according to Items 1 and 2. (4) The raw material N-monoalkylalkylene diamine constituting component B is N-methyltrimethylene diamine, N
-Ethyltrimethylenediamine, N-propyltrimethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine and N-butylethylenediamine. (5) The curable polyepoxide composition according to claim 4, wherein the raw material N-monoalkylalkylene diamine constituting component B is N-methyltrimethylene diamine. (6) The curable polyepoxide composition according to claim 4, wherein the raw material N-monoalkylalkylenediamine constituting component B is N-ethylethylenediamine.