JPS59217779A - Adhesive composition of aqueous contact type - Google Patents

Abstract

PURPOSE:The titled adhesive composition having long adhesivity retention time, improved workability, high initial bond strength, obtained by blending a self- crosslinking acrylic dispersion with a phenolic resin dispersion, and a self-emulsifiable polyurethane dispersion in a specific ratio. CONSTITUTION:(A) 30-60wt% self-crosslinking acrylic dispersion (e.g., mixture of vinyl acetate and/or vinyl propionate with acrylonitrile and/or methacrylonitrile, etc.) is blended with (B) 20-50wt% phenolic resin dispersion, and (C) 20-50wt% (calculated as solid content) self-emulsifiable polyurethane dispersion (preferably one obtained by introducing amino group, etc. to polyurethane, emulsifying and dispersing it without using emulsifying agent), to give the desired adhesive composition. Since the component C will be agglomerated and separated by extreme change in pH, the pH of the components A and B is preferably made equal to that of the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based contact type 1 adhesive having a long adhesive retention time, excellent workability, and high initial adhesive strength.

(1"T) Since then, organic solvent-type polychloroprene adhesive h (has been widely used as a contact type 1 adhesive. This adhesive has excellent performance such as workability and initial adhesive strength. However, since it contains organic solvents, there is a risk of solvent toxicity and fire, and in addition, from the standpoint of environmental pollution and resource conservation, it is strongly recommended that adhesives be water-based or film-based. It is requested.

Examples of water-based contact adhesives include latex-type polychloroprene adhesives containing resins obtained by reacting polychloroprene latex with petroleum-based resins, heat-reactive alkylphenol resins, and/or rosin, and acrylic dispersion liquids. An adhesive ρ made of an enol resin dispersion is known.

However, these conventional water-based contact adhesives are different from organic solvent-based contact adhesives, such as organic solvent Q
Compared to Q polychloroprene adhesives, it not only has poor workability due to its short adhesion retention time, but also has shortcomings such as poor adhesive strength development and low initial adhesive strength.

The inventor of the present invention has conducted various studies in order to overcome the drawbacks of conventional contact type adhesives, to obtain a water-based contact type adhesive that has a long adhesive retention time, excellent workability, and excellent initial adhesive strength. An aqueous Konta/71-type 1g adhesive composition consisting of a specific mixing ratio of a self-crosslinking type Chikusil dispersion, a phenolic resin dispersion, and a self-emulsifying Polyurekne dispersion is extremely effective. This led to the completion of the present invention.

That is, the present invention consists of (Δ) a self-crosslinking acrylic dispersion, (r3) a phenolic resin dispersion, and (C) a self-emulsifying polyurethane dispersion, and (Δ), (B), and (
The mixing ratio of C) is 30 to 60% by weight, 20 to 50% by weight, and 20 to 50% by weight in terms of the solid type. The present invention relates to adhesive compositions.

The self-crosslinking acrylic dispersion used in the present invention is, for example, (T) a mixture of acid-resistant vinyl and/or vinyl propionate with acryloni-1-lyl and/or methacrylic[]-di-lyl, (IT) ethyl acrylate, n-butyl acrylate-1 to 2-ethyl to (meth)acrylate-1 such as 4-syl acrylate, (■
) (meth)acrylic acid, maleic anhydride, fumaric acid, etc., available unsaturated acids, (TV) glycidyl (meth)acrylate, (V) (meth)acrylamide, human 1-1 xyedyl (meth)acrylate, It is obtained by emulsion polymerization of a monomer mixture containing other polymerizable vinyl monomers such as N-medyloacrylamide and glycidyl (meth)acrylate in the presence of a surfactant. Commercially available products include, but are not limited to, ()CΔRLATEX 152, 153, and 154 of 1g# of carbon carbide, and 1-0-40 of Nippon Acrylic A-Rokeisou.

Phenol resin dispersions are those obtained by reacting phenols and aldehydes in the presence of catalysts, surfactants, and protective colloids, or those obtained by reacting solid phenol resins or solid phenol resins with epoxy resins in water, organic It is emulsified and dispersed in the presence of a coupling solvent, a surfactant, and a protective colloid. Commercially available products include BKU A-2260 and 2370 manufactured by Showa Union Gosei Co., Ltd.

Self-emulsifying polyurethane dispersion is polyol-L)
- A polar group, such as an amino group, is introduced into the polyurethane polymer obtained by reacting the compound with the isocyanate-1 compound, and the reaction is carried out at 21.degree. Using an emulsifying agent [1 emulsification and dispersion without 4! It's ours.

Commercially available products include Izerax S-1040 and S-4040 manufactured by Hodogaya Chemical (Mane 1).

The mixing ratio of the self-crosslinking acrylic dispersion, the phenol resin dispersion, and the self-emulsifying polyurethane dispersion that constitute the aqueous 1-tank 1-type adhesive composition of the present invention is 30 to 30, respectively, in terms of solid content. 60% by weight, 20-50% by weight and 20-50% by weight, /! Y is preferably 30-50
% weight, 25-40% hand hang and 25-40% by weight. Among these, the mixing ratio of self-crosslinking acrylic dispersion is 6011'! If the mixing ratio of the phenolic resin dispersion is less than 20% by weight, or if the mixing ratio of the self-emulsifying polyurethane dispersion is less than 20% by weight, the initial adhesive strength will decrease. On the other hand, when the mixing ratio of the self-crosslinking acrylic dispersion is less than 30ffi%, when the mixing ratio of the phenolic resin dispersion is more than 50% by weight, and when the mixing ratio of the self-emulsifying polyurethane dispersion is If the proportion is more than 50% by weight, it is not preferable because the adhesive retention time will be short.

Among the constituent components of the aqueous contact adhesive composition of the present invention, the self-emulsifying polyurethane dispersion has a significant P l-
The self-crosslinking acrylic resin mixed with this dispersion has the advantage that under one change, coagulation and separation occur, destroying the dispersion and reducing the adhesion performance of the water-based contact type 1 adhesive composition. system dispersion,) - "P of the nol resin dispersion
It is preferable that H is adjusted in advance to be approximately equal to Pl-1 of the self-emulsifying polyurethane dispersion.

If necessary, other compounding agents conventionally used in water-based contact adhesives may be added to the water-based contact adhesive composition of the present invention, such as polyvinyl alcohol and carboxylic acid. By adding methylcellulose, the desired viscosity can be achieved.

The water-based adhesive composition of the present invention has excellent workability and has a high initial contact force, so it is suitable for use with paper, shoulder 1, and water usage <7. Inkry J～OJ: Inorganic base material such as silicone board, poly T″f
Ren, Borip "1 pyrene, Borisjiren A5 and polyvinyl vinyl!, - which plastic material, aluminum Uno,
1) It is useful as an adhesive for any Kinkusaya shrine, and q
It can also be used as an adhesive for the interior of buildings and automobiles, for wood products, and in lightning-related fields.

Below, the present invention will be explained in detail using 11 actual examples.

Example 1 Phenol 45.! Fat dispersion [Showa Conion (1'4J
Made by Ne↑.

B KLI A-2370, solid content 44 times Mn]
100 (J), 25% ammonia water 0.39 was added to adjust Pl-1 to about 7. While gently stirring,
This is added to a self-emulsifying polyurethane dispersion oil [Chemical 1-Tani Kagaku (
11J? l'Fl, Izerax 3-4040
．． PH approx. 7. Solid content: 50 parts by weight%] Solid content: 60 parts by weight%
] 73.4 (1) was added with 25% ammonia water 0.49 to adjust the pH to about 7 and mixed uniformly to obtain a water-based contact type adhesive composition 261.7Q. The solid weight M ratio of the crosslinked dispersion, phenolic resin dispersion, and self-emulsifying polyurethane dispersion is 33.3/
It was 33.3/33.3% by weight.

Examples 2 to 4 and Comparative Examples 1 to 4 In Example 1, a phenolic resin dispersion, a self-emulsifying polyurethane dispersion, and a self-crosslinking acrylic dispersion were mixed in the proportions shown in Table 1. A water-based contact adhesive composition was prepared in exactly the same manner as in Example 1.

(blank below) Reference example Polychloroprene rubber manufactured by Showa Neoprene Hana Co., Ltd.

Neoprene A D] ]100] was made into 22 strands with a row, and then B)-IT2J, magnesium oxide 4o, I! Rubber compound [
111 g of A3 was obtained.

On the other hand, alkylphenol resin [CK M-1634, manufactured by Showa Union Gosei ■] 45Q was mixed with 15% of toluene.
6g.

It was dissolved in a mixed solvent consisting of 156 g of ethyl acetate and 156 g of n-hexane to obtain 513 g of resin liquid [B]. Dissolve the rubber compound [A] in this sap [8],
A conventional organic solvent type polychloroprene contact adhesive 62/Ig was obtained.

The weight ratio of polychloroprene rubber and alkylphenol resin is 100''45, and the heating residue of this adhesive (JIS K-6829, 10!i+2'C).

3 hours) was 25.1%.

Next, go to Example 1 in [--4. Using the adhesives of Comparative Examples 1 to 4 and Reference Example, the viscosity retention Il'7 was measured. Measuring method (not shown): Apply adhesive to the surface of the paper and glass board to a thickness of 100 microns each, and then cut the kraft paper into 1/2 inch width every 10 minutes.
, /, A method was adopted in which the adhesive layer of the glass plate was pressed with finger pressure and then peeled off straight away. At this time, the time between the final adhesion time 1) and the time when no adhesion occurred was defined as the adhesion retention time. Adhesion retention time was measured at 25°C, RI-I 65%
The test was carried out in an atmosphere and the results are shown in Table 2.

εr2 table name ξ middle name 1 temple 1? S1's Yasukawa Sada also,
Examples 1-4. Initial adhesive strength was measured using the adhesives of Comparative Examples 1 to 1 and Reference Examples.

To measure the initial adhesive strength, apply the adhesive to two sheets of lauan plywood.
- LJAS Class I, 3mmj7) 100g/each
m2, and after air drying for a certain period of time (usually called open time), 1k! J/C
Press bonding was performed at m2 for 2 seconds. Next, this test piece was incubated for 1 minute, and the tensile shear strength was measured. In addition,
For measuring shear strength, Tensilon tJTIVl-150
00 "Toyo Baldwin (manufactured by Shusha) was used, and the tensile speed was 50 mm/min.

The measurement results are shown in Table 3.

Table 3 Oki 1 constant of the first kyo 1 concubine force (shear 1 - analysis degree) (
kg, /” 2 5 x 2 5 mm2
11-) As is clear, the water-based one-touch adhesive silk composition of the present invention has a long adhesive retention time and high initial adhesive strength, and its characteristics are as follows: The results were comparable to those of the organic solvent type polychloroprene adhesive shown in the reference example.

Furthermore, while the conventional water-based contact type adhesive exhibited only one characteristic of initial adhesion strength (L < l), the water-based contact type adhesive of the present invention exhibited only one characteristic of initial adhesion strength.
Since the mold adhesive composition has these two contradictory properties, its workability is greatly improved and it can be used as an adhesive for a wide range of applications.

Further, Examples 1 to 4 and Comparative Examples 1 to /I were attached.

The coating speed was 100g/m2, and the coating interval was 30g/m2.
Wait a few minutes, then apply two coats of adhesive using A-Antime 30.
After a few minutes, the test piece was bonded using a 5ko hand roller. The measurement is 90' T-string Ml for canvas comrades.
, Canvas/''Aluminum plate 180° peeled Tensilon U
TM-T5000 [Toyo Baldwin (II?1IF
I] at a tensile speed of 50 mm/min. The measurement results are shown in Table 4.

Table 4 F=lJrlftUMl? Measurement (kg, /
25 rnm) Patent applicant Showa Union Gosei Co., Ltd. Agent Patent attorney Sei Kikuchi -14-

Claims (1)

[Claims] (△) Self-crosslinking A acrylic dispersion (r3) Phenol resin dispersion, OJ:Bi (C)
It consists of a self-emulsified 1'% + 7 polyurethane dispersion, and the mixing proportions of (A>, (B) and (C) are 30 to 60% by weight and 20 to 50% by weight, respectively, in terms of solid content). 1J' filtrate system characterized by Ichiharu% and 20-50%
1-type adhesive composition.