JPH04236282A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in adherability, coating workability and initial tackiness, suitable for bonding polyvinyl chloride sheets, tiles, etc., by incorporating a thermoplastic elastomer in an A-agent comprising an epoxy resin, solution-type polymer of vinyl acetate and oligoacrylate and/or B-agent comprising a polyamide resin. CONSTITUTION:The objective composition can be obtained by incorporating (A) an A-agent comprising (1) an epoxy resin having at least two epoxy groups (e.g. diglycidyl ether of polyhydric phenol), (2) a solution-type polymer of vinyl acetate (prepared by polymerizing vinyl acetate monomer in a solvent such as methanol) and (3) an oligoacrylate (e.g. urethane acrylate) and/or (B) a B- agent comprising a polyamide resin of <=350 in amine value with (C) a thermoplastic elastomer (e.g. thermoplastic polyurethane).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature curing epoxy adhesive composition suitable for bonding various floor sheets or tiles.

0002

[Prior Art] Adhesives used for flooring sheets or tiles such as vinyl chloride sheets, vinyl chloride tiles, direct adhesive floors, and cushion floors include rubber latex, solvent-polymerized vinyl acetate, and epoxy. Adhesives such as adhesives are used. However, adhesives other than epoxy adhesives have a drawback in water resistance, and epoxy resin adhesives are used where water resistance is required.

[0003] This type of epoxy resin adhesive has a component A in which a solvent-type vinyl acetate polymer is added as a tackifier to an epoxy resin, and an inorganic filler is mixed therein;
It consists of a B agent which is a mixture of a dimer acid-based polyamide resin and an inorganic filler. However, in this type of adhesive, the vinyl acetate polymer in Part A and the polyamide resin in Part B have poor compatibility, resulting in thickening and separation of the mixture of these two parts, resulting in the application process being difficult. It had the disadvantage of poor performance.

[0004] Therefore, the use of aliphatic amines or aromatic amines or amine adducts thereof in place of the dimer acid-based polyamide resin contained in the above-mentioned B agent has been considered, but in this case, Agent A and B
The tolerance range for the mixing ratio with the adhesive was narrow, making it unsuitable as an adhesive for on-site construction.

[0005]

[Problems to be Solved by the Invention] The present invention provides an epoxy resin adhesive with excellent water resistance, in which the mixture of the above-mentioned A and B agents does not thicken or separate, and the compounding ratio is To provide a flooring adhesive with a wide tolerance and excellent on-site workability.

[0006]

[Means for Solving the Problems] The present invention provides at least two
An epoxy resin containing epoxy groups (a-1), a solution polymer of vinyl acetate (a-2) and an oligoacrylate (
It is composed of a part A containing a-3) as an essential component, and a part B containing a polyamide resin with an amine value of 350 or less as an essential component, and at least one of the A part and B part further contains a thermoplastic elastomer. An adhesive composition characterized by containing:

[0007] Here, the epoxy resin (a-1
) include diglycidyl ethers of polyhydric phenols represented by bisphenol A; diglycidyl ethers of polyhydric alcohols represented by glycerin or propylene glycol; epoxy esters of polybasic acids such as diglycidyl phthalate or diglycidyl adipate;
Typical examples include glycidyl ether of novolac type phenolic resin made from phenol or cresol.

[0008] The solution-type vinyl acetate polymer (a-2) is obtained by polymerizing a vinyl acetate monomer in a solvent such as methanol or ethyl acetate under a polymerization catalyst and has a polymerization degree of 60 to 60. 2000.

[0009] Furthermore, the oligoacrylate (a-3)
is an oligomer having an acryloyl group at the end or side chain of the molecule, and refers to urethane acrylate (average molecular weight 1,000 to 20,000) having a polyurethane main chain. For example, polyester diol and diisocyanate having OH groups at both terminals are NCO:OH=1:
1 of acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester and its derivatives per 100 parts by weight (solid content) of the urethane obtained by reacting at a molar ratio of 0.65 to 0.95.
It can be obtained by polymerizing 50 to 150 parts by weight of the species or a mixture of two or more species.

[0010] The polyamide resin is produced by a condensation reaction of dimer acid and polyamine, and is a polyamide amine having reactive primary and secondary amino groups in the molecule, and has an amine value of 350 or less. Polyamide resin is suitable.

Typical thermoplastic elastomers include thermoplastic polyurethane, liquid polybutadiene, liquid polyisoprene, and polydicyclopentadiene.

[0012]Although the ratio of addition of these essential components of the composition of the present invention varies somewhat depending on the purpose, it is generally desirable to have the following ratios. 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. It can be determined by combining, but usually 0.5:1 to 1:2
An equivalent ratio within the following range is appropriate. 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. .

[0013] Agent A epoxy resin (a-1)
5-40% by weight Solution type polymer of vinyl acetate (a-2) 5-30
(based on solid content of 40% by weight) Oligoacrylate (a-3)
1-20 〃 Inorganic filler
80
~20 〃 Thermoplastic elastomer
0.25~20〃

B agent polyamide resin
5-50% by weight (amine value 350 or less) Inorganic filler
95~50〃

[0015]
Here, the above addition ratio indicates one embodiment of the present invention, and in particular, as for the method of adding the thermoplastic elastomer, if addition to agent B is possible, addition to both agents A and B is also prevented. Generally speaking, it is sufficient to add it to at least one of agent A or agent B, although it is not a
Even if it is added to the B agent, the addition ratio may be approximately the same as 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.

[0016] If the addition ratio of the epoxy resin (a-1) or the poamide resin 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 significantly reduced. Also,
If the oligoacrylate content is smaller than the above range, there will be no effect on improving the compatibility between the vinyl acetate solution polymer and the polyamide resin, and if it is larger, the water resistance will drop significantly. Therefore, neither is preferable.

[0017] 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 materials are used. Typical fillers include calcium carbonate, talc, asbestos, zinc white, silica, titanium oxide, and inorganic fillers such as Bengara or silica sand. However, this does not preclude the use of conventional organic fillers as long as they suit the purpose of the present invention. To the thus obtained composition of the present invention, various known and commonly used additives such as solvents, plasticizers, colorants, and curing accelerators for epoxy resins can be added, depending on the purpose.

The composition of the present invention is an epoch-making product that can satisfy all of the adhesion, application workability, and initial tack properties required of adhesives for floor sheets or tiles. 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.

[0019]

[Example] Example 1 28 parts of Epicoat 815 (manufactured by Yuka Shell Epoxy Co., Ltd., Epi-bis type epoxy resin), Finetac HD-
8049 (manufactured by Dainippon Ink and Chemicals Co., Ltd., solution-type vinyl acetate polymer) 14 parts, UV-2700B (manufactured by Nippon Gosei Chemical Co., Ltd., oligoacrylate) 1 part, calcium carbonate 38 parts, acetone 15 parts, 3 parts of toluene and 1 part of Hiker CTBN 1300X8 (polybutadiene manufactured by Goodrich) were uniformly mixed to prepare a part A. On the other hand, Versamide 115 (manufactured by Henkel Hakusui Chemical Co., Ltd., amine value 240)
A B agent was prepared by uniformly mixing 23 parts of polyamide resin, 53 parts of finely powdered silica sand, 17 parts of calcium carbonate, and 7 parts of methanol. Both agents A and B were mixed at a ratio of 1:1 to prepare a target adhesive composition.

Example 2 Epicoat 1001-X-75 (oiled shell epoxy (
Co., Ltd. epoxy resin) 5 parts, Epicoat 828 (epoxy resin made by the same company) 17 parts, Finetac HD-804
9, 1 part of UV-2700B, 30 parts of calcium carbonate, 13 parts of clay, 15 parts of acetone, and 5 parts of IPA were uniformly mixed to prepare Agent A. On the other hand, Tomide 215X
(Fuji Kasei Kogyo Co., Ltd. amine value 245 polyamide resin) 15 parts, 1 part of Hiker ATBN 1300 . Both agents A and B were mixed at a ratio of 1:1 to obtain a desired adhesive composition.

Comparative Example 1 In Example 1, by replacing one part of UV-2700B and one part of Hiker CTBN1300X8 with Epicote 815, the total amount of Epicote 815 was reduced to 21%.
It was used as a control in the same manner except that it was used as a control.

Comparative Example 2 In Example 2, 1 part of UV-2700B was replaced with Epicoat 828, so that the total amount of Epikot 828 was 18 parts. Also, hiker ATBN1300
A comparative sample was prepared in the same manner except that 1 part of X16 was replaced with Versamide 115, making the total amount of Versamide 115 16 parts.

[0023] Next, the compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were tested for each item of coating workability, initial adhesion, normal state, and water-resistant adhesion, and the results are shown in Table 1. . The test method is as follows. (1) Coating workability: Based on JIS A-5536. (2) Initial tackiness: Approximately 600 g/m2 of the adhesive composition is applied onto a slate board with a comb trowel, and the adhesive composition is applied to the floor for direct attachment (
A plane tensile test was conducted 5 minutes and 30 minutes after pasting (40 x 40 mm). (3) Adhesiveness: Approximately 600 g/m2 of the adhesive composition is applied onto a slate board using a comb trowel, a foamed rubber sheet with 40 mm width irregularities is attached, and a 90°C peel test is performed. Normal condition: Leave at 20°C for 7 days. Water resistance: Measured in a wet state after being left at 20°C for 7 days and immersed in water for 1 day. Upper row shows adhesive strength (kgf/40mm width) Lower row shows rubber sheet material breakage rate (%)

[0024]

[Table 1]

Claims (1)

[Claims] Claim 1: A solution-type polymer (a-1) of an epoxy resin containing at least two epoxy groups and vinyl acetate (a-1);
-2) and oligoacrylate (a-3) as essential components, and B agent as an essential component a polyamide resin with an amine value of 350 or less. An adhesive composition characterized in that at least one of the adhesive compositions contains a thermoplastic elastomer.