JPS58201868A - Adhesive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy adhesive composition suitable for adhering various floor sheets or tiles such as vinyl chloride sheets, vinyl chloride tiles, cush green floors, cork tiles or rubber tiles. .

Conventionally, rubber latex adhesives or solution polymerized vinyl acetate adhesives have been used as adhesives for this type of flooring sheets or tiles, but synthetic rubber latex adhesives were first used. Although the agent does not contain any solvents and has excellent initial tackiness or adhesion, it has problems with water resistance because it is an emulsion type, and water resistance is required in areas such as bathrooms, for example. On the other hand, although solution-polymerized vinyl acetate adhesives have excellent initial adhesion, they contain a large amount of solvent and are therefore toxic and pose a fire hazard, and have low resistance to water. As with the latex type, it is unsuitable for locations where water resistance is required.

For this reason, epoxy resin adhesives are mainly used as waterproof adhesives, and many of these types of adhesives currently on the market contain solution-type vinyl acetate polymers in epoxy resin. added as a tackifier, and
Part A contains an inorganic filler, and Part B contains a dimer acid-based polyamide resin and an inorganic filler.
It consists of a drug.

However, in such adhesives, the vinyl acetate polymer contained in Part A and the polyamide resin contained in Part B have poor compatibility, resulting in thickening and separation of the mixture of these gastric agents. This has the drawback of causing poor coating workability.

As an improvement method for this purpose, it is possible to reduce the amount of vinyl acetate polymer or to reduce the amount of polyamide resin and corresponding epoxy resin, but if the former method is used, sufficient initial tackiness may be cannot be expected, and the latter method has the disadvantage that it becomes difficult to obtain the good water resistance inherent to epoxy resins.

As described above, as far as conventional adhesives of this type are concerned, the current situation is that there are no satisfactory ones available.

However, as a result of intensive studies in view of these actual circumstances, the present inventors have discovered an adhesive composition that has superior initial tackiness, coating workability, and water resistance compared to conventional epoxy adhesives. The present invention has now been completed.

That is, the present invention provides a solution type polymer (a-1) of an epoxy resin (a-1) having two or more epoxy groups and vinyl acetate.
2) as an essential component, and this epoxy resin (
An adhesive composition comprising a B agent having a curing agent for a-1 as an essential component, and using an aliphatic polyamine or an aromatic polyamine or an amine adduct thereof as the curing agent. It is something that provides something.

Here, as the epoxy resin (a-1),
Diglycidyl ethers of polyhydric phenols such as bisphenol A; diglycidyl ethers of polyhydric alcohols such as glycerin or propylene glycol; epoxy esters of polybasic acids such as diglycidyl phthalate or diglycidyl adipate; or phenol or cresol. Typical examples include glycidyl ether of novolak-type phenolic resins from E.P. et al.

In addition, the solution type polymer (a-2) of vinyl acetate mentioned above refers to a polymer having a degree of polymerization of 60 to 200 obtained by polymerizing vinyl acetate monomer in a solvent such as methanol or ethyl acetate under a polymerization catalyst. It refers to something.

Further, representative aliphatic polyamines include N-aminoethylpiperazine, xylylene diamine, isophorone diamine, or aminoethylbenzylamine, and representative aromatic polyamines include diaminodiphenylmethane. Typical amine adducts include adducts of various polyamines and epoxy group-containing compounds as described above, Mannich reaction products of the polyamines, formalin, and phenols, or polyamines and acrylonitrile. Alternatively, there are Michael reaction products such as □ with acrylic acid esters.

Although the addition ratios of these essential components of the composition of the present invention vary somewhat depending on the purpose, it is generally desirable to have the following ratios.

Furthermore, the blending ratio of each agent A and agent B described above is
It can be determined by theoretically matching the number of epoxy equivalents of the epoxy resin contained in the agent and the number of active hydrogen equivalents in the so-called curing agent component contained in agent B, but usually 0.
．． Equivalence ratios in the range from 5jl to 1:2 are suitable.

However, it is understood that the above-mentioned addition ratio and compounding ratio do not limit the present invention in any way, and even if it deviates from such range, it is still within the scope of the present invention as long as it meets the purpose of the present invention. .

A agent.

Epoxy resin (a-1), 5-50 weight percent vinyl acetate solution polymer (p-2) 5-30
(In terms of solid content 40% by weight) Inorganic filler 90-20 Part B aliphatic or aromatic polyamine or amine adduct 5-50% by weight Inorganic filler 95-50 Here,
In order to impart improved water resistance and chemical resistance to the intended adhesive composition, the epoxy resin (a-1
) should be increased, and if it is desired to increase the initial tackiness, the ratio of the polymer (a-2) should be increased, but as long as it meets the purpose of the present invention, the above addition ratio It is possible to adjust and change.

Also, as a matter of course, when various additives other than the above-mentioned essential components and fillers are added, the ratio of the essential components becomes relatively small.

5-Furthermore, the addition ratio of the curing agent for the epoxy resin (a-1> described above is based on the theoretical embodiment described above for this epoxy resin (a-1), but for the epoxy resin (a-1) ), or when the addition ratio of aliphatic or aromatic polyamines or their amine adducts is smaller than the above-mentioned range, the water resistance of the resulting adhesive composition will be markedly reduced; If the addition ratio of the vinyl solution-type polymer (a-2) is smaller than the above-mentioned range, the initial adhesive strength of the resulting composition will be markedly reduced, which is not preferable.

In addition, the blending ratio of the A agent and the B agent described above is determined by the number of epoxy equivalents of the epoxy resin (a-1) contained in the A agent and the number of active hydrogen equivalents in the so-called curing agent component contained in the B agent. It can be determined by theoretically combining the
Equivalence ratios in the range 0.5:1 to 1:2 are suitable.

In preparing the composition of the present invention, improving adhesive strength,
In addition, in order to reduce the price, as mentioned above, various known and commonly used fillers can be included. Typical examples of such fillers include calcium carbonate, talc, asbestos, zinc white, Inorganic fillers such as silica, titanium oxide, Bengara, or silica sand are mentioned, but this does not in any way preclude the use of conventional organic fillers as long as they are compatible with the purpose of the present invention. .

Depending on the purpose, various additives such as a known and commonly used solvent, plasticizer, colorant, or curing accelerator for epoxy resins can be added to the composition of the present invention thus obtained.

In the composition of the present invention, the A component contains a tackifying component which is a vinyl acetate polymer, and the B component contains an aliphatic or aromatic polyamine or a curing agent component which is an amine adduct thereof. However, since the compatibility between these two components is better than that between vinyl acetate polymer and polyamide resin, which are used as conventional adhesives, the composition of the present invention has the following properties. It has features such as.

■ Due to its good fluidity, the coating workability with comb protection is good. ■ The performance of the tackifying agent (vinyl acetate polymer) itself is promoted by the polyamine curing agent. Since the addition ratio of the curing agent can be increased, initial adhesion can also be increased.In addition to these improvements, the adhesive of the present invention uses the polyamine-based curing agent, making it possible to increase the initial adhesion. It is possible to shorten the time required to develop adhesive strength at low temperatures, which was not possible with resin-based adhesives, and the water resistance is also improved.

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples, and in the following, parts mean parts by weight.

Example 1 30 parts of Ebicuron 855J (Ebi-bis type epoxy resin manufactured by Dainippon Ink & Chemicals), 20 parts of Finetac HD-□8049J (solution type vinyl acetate polymer manufactured by the same company), and calcium carbonate. 17 parts of asbestos powder, 8 parts of doluol, and 8 parts of butyl cellosolve were uniformly mixed to prepare a part A.

Separately, 70 parts of isophorone diamine was added with "Evicron 85".
0'' (shrimp bis type epoxy resin manufactured by the same company) was added dropwise at 100°C, and after the completion of the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours to obtain an amine adduct.

20 parts of this adduct, 20 parts of finely divided silica sand, 20 parts of calcium carbonate, 20 parts of talc, 15 parts of methanol and 5 parts of silicon oxide were uniformly mixed to prepare a B agent.

Next, both agents A and B were mixed at a weight ratio of 1:1 to prepare an adhesive composition.

This composition was tested in terms of coating workability, initial tackiness, and adhesion, and the results shown in Table 1 were obtained.

Example 2 25 parts of “Ebikuron 850”, [Ebikuron 520J
(reactive diluent made by the same company), 15 parts of Finetac+10-8049J, [Nicanol IIPi
Agent A was prepared by uniformly mixing 5 parts of OJ (Xyref resin manufactured by Mitsubishi Gas Chemical Company Ltd.), 17 parts of calcium carbonate, 15 parts of clay, 16 parts of methanol, and 2 parts of silicon oxide.

Separately, 30 parts of "Evicron 850" was added dropwise to 70 parts of N-aminoethylpiperazine at 100°C, and after the dropwise addition was completed, the mixture was allowed to react at the same temperature for 2 hours to obtain an amine adduct.

20 parts of this adduct and [Hysol 5AS295
10 parts of J (aromatic hydrocarbon diluent manufactured by Nisseki Chemical Co., Ltd.), 20 parts of talc, 30 parts of asbestos powder, and 15 parts of butyl cellosolve were uniformly mixed to prepare a B agent.

Both agents A and B were mixed at a weight ratio of 1=1 to obtain an adhesive composition.

The composition obtained here was also tested on the same items as in Example 1, and the results shown in Table 111 were obtained.

Example 3 25 parts of Ebikuron 830J (Dai Bhon Ink Kagaku Kogyo special made Ebi-bis type epoxy resin),
5 parts of El (reactive diluent manufactured by Shell, Switzerland), 20 parts of Finetac HD-8049J, Bremma GPJ (
10 parts of Nippon Oil & Fats ■ (responsive diluent), 20 parts of asbestos powder and
20 parts of Calcium Carbonate) were uniformly mixed to prepare Agent A.

Separately, 15 parts of Laccamite Wl+-340J (Dainippon Ink & Chemicals ■!ll1lII aliphatic polyamine adduct), 15 parts of Nicanol (Xyref resin manufactured by Mitsubishi Gas Chemical ■), 32 parts of asbestos powder, A B agent was prepared by uniformly mixing 20 parts of Cal NS-100J and 18 parts of methanol.

Next, these A and BW agents were mixed at a weight ratio of 1:1 to obtain an adhesive composition.

This composition was also tested on the same items as in Example 1, and the results shown in Table 1 were obtained.

Comparative Example 1 The same procedure as in Example 1 was used except that the same amount of [Tsukamite E^-233J (dimer acid-based liquid polyamide resin manufactured by Dainippon Ink & Chemicals) was used instead of isophorone diamine adduct. A comparative adhesive composition was prepared and then subjected to performance evaluation.

The results are summarized in Table 1.

10- Comparative Example 2 A comparative adhesive composition was prepared in the same manner as in Example 2, except that the same amount of Laccamite E^-240J (same as above) was used in place of the N-aminoethylpiperazine adduct. Then, performance evaluation was performed.

The results are summarized in Table 1.

Comparative Example 3 Except that the same amount of Laccamite TD-950J (same as above) was used in place of Ushikamite Wl+-340J,
A comparative adhesive composition was obtained in the same manner as in Example 3,
Next, performance evaluation was performed.

The results are summarized in Table 1.

Table 1 (Note) Test method (1) Coating workability---JIS A-553
According to 6.

(2) Adhesiveness --- In accordance with JIS^-5536.

(3) Initial adhesion - Approximately 250 g/po of the 11111 adhesive composition was applied onto a slate board, and a vinyl chloride tile specified in JIS^-5536 was attached to it, and the planar tensile strength was measured. did. This measurement was carried out at 0 minutes and 10 minutes after coating.

Patent applicant: Dainippon Ink and Chemicals Co., Ltd. 12-

Claims (1)

[Claims] Epoxy resin having two or more epoxy groups (a-1
) and a solution type polymer of vinyl acetate (a-2) as essential components, and B agent as an essential component a curing agent for epoxy resin (a-1). ,and,
A two-component adhesive composition that cures at room temperature, wherein the curing agent is an aliphatic polyamine, an aromatic polyamine, or an amine adduct thereof.