JPH0241558B2 - - Google Patents

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, cushion floors, cork tiles, or rubber tiles. Conventionally, rubber latex-based adhesives or solution polymerized vinyl acetate-based adhesives have been used as adhesives for this type of flooring sheet or tile. Although it does not contain solvents and has excellent initial adhesion or adhesion, it has the disadvantage of water resistance because it is an emulsion type, so it is suitable for places where water resistance is required, such as washrooms. On the other hand, although solution-polymerized vinyl acetate adhesives have excellent initial tackiness, they contain a large amount of solvent and are therefore toxic and pose a fire hazard, and have low resistance to water. As with other systems, 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. It consists of Part A, which is added as a tackifier and also contains an inorganic filler, and Part B, which contains a dimer acid-based polyamide resin and an inorganic filler. However, in such adhesives, the vinyl acetate polymer contained in Part A and the polyamide resin contained in Part B have poor compatibility, so the mixture of these two parts tends to thicken and separate. This has the disadvantage that coating workability is poor. However, as a result of intensive research aimed at particularly improving the coating workability, the present inventors found that instead of the dimer acid-based polyamide resin contained in the B agent, aliphatic polyamines, aromatic polyamines, or these It was discovered that by using an amine adduct of It is only about the same level, and it cannot be said that it is still satisfactory for applications that require high adhesive strength. Therefore, with the aim of further improving this adhesive property, as a result of further intensive studies, the present invention was able to achieve a significant improvement in adhesive property compared to conventional adhesives. I have come to complete it. That is, the present invention provides A containing as essential components an epoxy resin (a-1) containing at least two epoxy groups and a solution-type polymer of vinyl acetate (a-2).
and a B agent containing an aliphatic polyamine, an aromatic polyamine, or an amine adduct thereof as an essential component, and at least one of the A agent or B agent may further contain a thermoplastic elastomer. The present invention provides a cold-curable two-component adhesive organic solvent solution composition having the following characteristics. Here, the epoxy resin (a-1) includes diglycidyl ether of polyhydric phenol represented by bisphenol A; diglycidyl ether of polyhydric alcohol represented by glycerin or propylene glycol; diglycidyl phthalate or adipine Typical examples include epoxy esters of polybasic acids such as diglycidyl acid; or glycidyl ethers of novolac type phenolic resins from phenols or cresols. In addition, the above-mentioned solution type polymer of vinyl acetate (a
-2) refers to a polymer having a degree of polymerization of 60 to 200 obtained by polymerizing a vinyl acetate monomer in a solvent such as methanol or ethyl acetate in the presence of a polymerization catalyst. Furthermore, representative aliphatic polyamines include N-aminoethylpiperazine, xylylene diamine, isophorone diamine, or aminoethylbenzylamine, and representative aromatic polyamines include diaminodiphenylmethane. Typical amine adducts include adducts of the various polyamines and epoxy group-containing compounds as described above, Mannitz reaction products of the polyamines, formalin, and phenols, and the polyamines. and Michael reaction products with acrylonitrile or acrylic acid ester. Typical thermoplastic elastomers include thermoplastic polyurethane, liquid polybutadiene, liquid polyisoprene, and polydicyclopentadiene. Although the addition ratio of these essential components of the composition of the present invention varies somewhat depending on the purpose, roughly speaking,
It is desirable that the ratio is as shown below. Furthermore, the above-mentioned compounding ratio of the A agent and the B agent is based on the theoretical number of epoxy equivalents of the epoxy resin contained in the A agent and the number of active hydrogen equivalents in the so-called curing agent component contained in the B agent. Although it can be determined by combining the two, an equivalent ratio in the range of 0.5:1 to 1:2 is usually 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. . Part A Epoxy resin (a-1) 5-40% by weight Solution type polymer of vinyl acetate (a-2)
5-30 〃 (based on 40% by weight of solids) Inorganic filler 80-20 〃 Thermoplastic elastomer 0.25-20 〃 B agent Aliphatic or aromatic polyamine
5 to 50% by weight or amine adduct Inorganic filler 95 to 50 Here, the above addition ratio indicates one embodiment of the present invention, and in particular, the method of adding the thermoplastic elastomer to the B agent is If it is possible, this does not preclude addition to both A and B, but generally it is sufficient to add it to at least one of A or B, so if it is added to B. Even in the case where it is added, the addition ratio may be roughly the same as that described above. However, when it is added to both agents A and B, it goes without saying that the total amount should be approximately at the above-mentioned addition ratio. In addition, if the addition ratio of the epoxy resin (a-1), aliphatic or aromatic polyamine, or their amine adduct is smaller than the above range, the water resistance of the resulting adhesive composition may decrease. On the other hand, if the addition ratio of the vinyl acetate solution type polymer (a-2) is smaller than the above range, the initial adhesive strength of the resulting composition will decrease significantly. , both are unfavorable. In obtaining the composition of the present invention, for example, for use in floor sheets or tiles, for the purpose of reducing costs and improving workability, as mentioned above, commonly used Various fillers can also be contained, typical examples of such fillers include calcium carbonate, talc, asbestos, zinc oxide, silica, titanium oxide, and inorganic fillers such as Bengara or silica sand. However, of course, this does not in any way preclude the use of conventional organic fillers as long as they suit the purpose of the present invention. For the composition of the present invention thus obtained,
Depending on the purpose, various additives such as well-known and commonly used solvents, plasticizers, colorants, and curing accelerators for epoxy resins can be added. The composition of the present invention is an epoch-making composition that can satisfy all of the requirements for adhesives for floor sheets or tiles, such as adhesion, application workability, and initial tackiness. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts refer to parts by weight unless otherwise specified. Example 1 50 parts of "Pandex T5000" (urethane elastomer manufactured by Dainippon Ink & Chemicals Co., Ltd.) was dissolved in 50 parts of toluene to obtain a mixture. Then,
7 parts of this mixture, 23 parts of "Epicron 855" (Epi-bis type epoxy resin manufactured by the same company), 20 parts of "Fintertuc HD-8049" (solution type vinyl acetate polymer manufactured by the same company), and calcium carbonate. 17 parts of asbestos powder, 8 parts of toluene, and 8 parts of butylcellosolve were uniformly mixed to prepare Part A. On the other hand, "Epicron 850" (Epi-bis type epoxy resin manufactured by the same company) was added to 70 parts of isophorone diamine.
30 parts of the solution was added dropwise at a temperature of 100°C, and after the completion of the addition, the reaction was continued 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
1 part and 5 parts of silicon oxide are uniformly mixed to form B.
It was used as a drug. Next, both agents A and B were mixed at a weight ratio of 1:1 to obtain the intended adhesive composition. For the composition thus obtained, initial tackiness,
Tests were conducted on each item of coating workability and adhesion, and the results shown in Table 1 were obtained. Example 2 A mixture was obtained by dissolving 50 parts of "Hiker CTBN1300x8" (polybutadiene, manufactured by Gutdrich, USA) in 50 parts of toluene. 7 of this mixture
Department, “Epicron 850” (Dainippon Ink and Chemicals Co., Ltd.)
18 parts of ``Epi-bis type epoxy resin'' manufactured by the same company, 5 parts of ``Epicron 520'' (a reactive diluent manufactured by the same company), 15 parts of ``Fintertuc HD-8049'', ``Nicanol''
5 parts of "HP-30" (xylene resin manufactured by Mitsubishi Gas Chemical Co., Ltd.), 17 parts of calcium carbonate, 15 parts of clay, 2 parts of silicon oxide, and 16 parts of methanol were uniformly mixed to make agent A. . Separately, to 70 parts of N-aminoethylpiperazine,
30 parts of "Epicron 850" was added dropwise at 100°C, and after the dropwise addition was completed, the reaction was continued at the same temperature for 2 hours to obtain an amine adduct. 20 parts of this adduct and "Hisol SAS295"
(Aromatic hydrocarbon diluent manufactured by Nisseki Chemical Co., Ltd.)
10 parts of talc, 20 parts of talc, 30 parts of asbestos powder, and 15 parts of butyl cellosolve were uniformly mixed to prepare agent B. Next, both agents A and B were mixed at a weight ratio of 1:1 to obtain the desired adhesive composition. This composition was also subjected to the same tests as in Example 1, and the results shown in Table 1 were obtained. Comparative example 1 50 parts of "Pandex T5000" and toluene
The total amount (7 parts) of the mixture with 50 parts of
A comparative composition was obtained in the same manner as in Example 1, except that the total amount of "Epicron 855" was changed to 30 parts by replacing it with "Epicron 855", and then performance evaluation was performed. The results are summarized in Table 1. Comparative Example 2 The entire amount (7 parts) of a mixture of 50 parts of "Hiker CTBN1300 x 8" and 50 parts of toluol was replaced with "Epicron 850", and this "Epicron 850"
A comparative composition was obtained in the same manner as in Example 2, except that the total amount was 25 parts, and then performance evaluation was performed. The results are summarized in Table 1.

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Claims (1)

[Claims] 1 Solution type polymer of epoxy resin (a-1) containing at least two epoxy groups and vinyl acetate (a
-2) is an essential component, and a B agent is an aliphatic polyamine, an aromatic polyamine, or an amine adduct thereof. 1. A room temperature-curable two-component adhesive organic solvent solution composition, characterized in that at least one of the components contains a thermoplastic elastomer.