JPS6151072A - Non-mixing type two-rack acrylic adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled non-mixing type two pack adhesive which has improved workability and is freed from the problem of sticking, consisting of a soln. contg. chlorosulfonated polyethylene and a soln. contg. an acrylic polymer. CONSTITUTION:A non-mixing type two-pack acrylic adhesive compsn. consists of agent A and B which are used in such a manner that each of them is applied to each of adherend surfaces and the both surfaces are stuck to each other to effect bonding. The agent A is a mixture of 5-30pts.wt. chlorosulfonated polyethylene, 10-100pts.wt. at least one member (X) selected from (meth)acrylic acid, (meth)acrylate esters, di(meth)acrylates and polyfunctional (meth)acrylates, 0- 50pts.wt. diglycidyl ether type epoxy resin (Y), 1-50pts.wt. peroxide and 0- 5pts.wt. antioxidant. The agent B is a mixture of 5-50pts.wt. acrylic rubber and/or acrylic resin, 1-50pts.wt. polymn. promotor composed of an amine/ aldehyde condensate, 10-100pts.wt. said X, 0-50pts.wt. said Y, 0-5pts.wt. antioxidant and 0-5pts.wt. catalyst.

Description

Detailed Description of the Invention [Industrial Field of Application] The two-component non-mixable (Part A and Part B) acrylic adhesive composition of the present invention can be used as a structural and semi-structural adhesive, and Used for adhesion of various types of reinforcing plates (metal door reinforcement, elevator door reinforcement, etc.), adhesion of speaker parts, and adhesion of wood, concrete, plastic, and glass.

The purpose can be achieved by applying two parts, Part A and Part B, to both sides of the adherend and bonding them as is.

[Conventional technology]

A type of adhesive agent that completes curing by combining with agent A gold amine-aldehyde condensate shown in the claims is already commercially available (Diavin l-"5G-11 manufactured by Nogawa Chemical Company).゜5G-13 etc.).A
Regarding the agent, see JP-A-49-132119゜ JP-A-51-
7040 and JP-A No. 51-95438.

The curing mechanism of this adhesive is a system in which the filtered oxide contained in Agent A is decomposed by an amine-aldehyde condensate, and the acrylic monomer in Agent A is polymerized and cured by chain transfer of the generated radicals. be.

In addition, using an amine-aldehyde condensate as a catalyst, A
It has been recognized that the acrylic monomer graft polymerizes to the chlorosulfonated polyethylene in the agent A. Curing proceeds even in the absence of peroxide in the agent.

This adhesive has an A agent viscosity of 8,000 to 13,000 cp (S
G-11), it is a highly viscous liquid of 10,000 to 15,000 cp, whereas the viscosity of the amine-aldehyde condensate is z
The disadvantage is that workability is poor because the viscosity is low at less than OOOCP and the viscosity is too different. Furthermore, since the amine-aldehyde condensate does not directly participate in the reaction, but rather acts as a catalyst or accelerator, it has the disadvantage that when it is applied in excess, the protruding portion remains sticky.

[Problem that the invention seeks to solve]

The inventors of the present invention conducted research to solve all of the above-mentioned drawbacks, and found that if any small polymer substance is used as a binder for the amine-aldehyde condensate, it will be possible to adjust the viscosity and eliminate the overhanging part. We thought that it would be effective in resolving the problem of nine-pointers, and so we came up with the present invention.

All commercially available natural and synthetic rubbers and synthetic resins were examined in terms of test items necessary for adhesives, and among them, acrylic rubber and/or acrylic resin shown in Claim B was found to be very effective. I discovered something.

The conditions required for the polymeric substance used as a binder for the condensate are (1) good compatibility with chlorosulfonated polyethylene and acrylic polymer, which are the basic composition of agent A, and (2) agent B. When blended into the liquid, it has excellent storage stability and two-layer separation stability.

Acrylic rubber and acrylic resin are excellent binders that satisfy all of these conditions.

[Means of trying to solve the problem]

The two-component non-mixable entrainer composition of the present invention includes Part A (1) 5 to 30 parts by weight of chlorosulfonated ethylene (2) acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, 10 to 100 parts by weight of one or more acrylic resins selected from diacrylate, dimethacrylate, polyfunctional acrylate, and polyfunctional methacrylate (3) 0 to 50 parts by weight of diglycidyl ether type epoxy resin (4) Cumene hydroper Peroxide such as oxide ° 1 to 50 parts by weight (5) Anti-aging agent Q to 5 parts by weight Above (1), +21,
(31, obtained by mixing, stirring, and dissolving (4) and (5).

B agent (1) Acrylic rubber and/or acrylic resin 5~
50 parts by weight (2) Polymerization accelerator consisting of amine-aldehyde condensate 1 to 5.0 parts by weight (3) Acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, diacrylate and dimethacrylate, polyfunctional acrylate and 100 parts of l10N of one or more monomers selected from polyfunctional methacrylates (4) Diglycinol ether-type engineering 4xy resin 0~
50M parts (5) Anti-aging agent 0 to 5 parts (6)
Catalyst 0 to 5 parts by weight (1) above, (
2), (31, (4), (51) and (6) are mixed, stirred, and dissolved.

A two-component mixed acrylic adhesive composition in which the above components A and B are thoroughly stirred and dissolved, applied to both sides of the two-component adherend, and bonded as is to complete adhesion. It is.

Agent A is well known if you refer to the above-mentioned publication, so it will not be described here.

There are many types of commercially available acrylic rubbers and acrylic resins that will be described below as agent B, but all of them are shown in the claims, and acrylic rubbers with a Mooney viscosity of about 50 are preferred.

[Effect]

Agent A is described in the above-mentioned patent publication, and will be omitted here.

Let's talk about agent B. There are many commercially available acrylic rubbers and acrylic resins, but all of them are included in the claims.

Acrylic rubber having a Mooney viscosity of about 50 is preferred. A mixture of these and an amine-aldehyde condensate dissolved in an acrylic monomer and prepared homogeneously is stable at room temperature for three months or more.

The role of acrylic resin and acrylic resin in this B-agent system is to act as a binder for the amine-aldehyde condensate, and by adjusting the blend tt,
The viscosity of liquid B can be adjusted freely. Both the chlorsulfonated i-lyethylene and the acrylic polymer in the fcA agent are compatible and form a strong adhesive layer after curing.

Acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, diacrylate, dimethacrylate, polyfunctional acrylate, and polyfunctional methacrylate are so-called reactive acrylic sevenmers.
Through the catalytic action of the peroxide blended in Part A, polymerization is cured or graft polymerized to chlorosulfonated polyethylene, creating a mixed system with the acrylic rubber and acrylic resin described above, and reinforcing the acrylic rubber and acrylic resin layers. It is something to give.

The diglycidyl ether type epoxy resin serves as a storage viscosity stabilizer in this Part B system.

Although it is not a particularly necessary compounding agent in the B-component system, longer-term storage stability can be established by compounding it with certain acrylic rubbers and acrylic resins.

As with the epoxy resin, anti-aging agents are also added to ensure long-term storage stability.

As anti-aging agents, amine derivatives, diamino derivatives,
Reaction products of amines, phenol derivatives.

There are various types such as thiourea type and imidazole type, but phenol derivatives are particularly preferred in the B liquid type.

Phenol derivatives include 2,6 ditertiary butyl A lacresol, 2,2'methylenebis4methyl6tertiarybutylphenol, 4,4'-thiobister 7
Jarybutylphenol, 2,5 ivy-Jarybutylhydroquinone, styrenated phenol, 4
．． 4' butylidene bis 6 tertiary petit,.

lummetacresol, etc., and all of these exhibit excellent friend effects.

〔Example〕

Example 1 Comparison of storage stability between acrylic rubber and acrylic resin and other synthetic rubbers and synthetic resins l+ll 2 Performance test adhesive test piece; Steel piece mutual 10I+Iff+×1011
M uneven wrap adhesive heating aging test; 70°C x 7 days → Measured after cooling to room temperature Heat resistance test; 130°C x 20 minutes → Measured at the same temperature Water resistance test; Immersed in water for 7 days → Measured in wet state Note: Test piece Apply Parts A and B separately to both sides of the created adherend, immediately adhere by lightly rubbing them together, and fix and cure with clips.

All agents A used in the examples had the following formulations.

Chlorsulfonated polyethylene 35 parts by weight Methyl methacrylate 50 parts by weight methacrylic acid
10 fi parts ethylene dimethacrylate 1 part by weight epoxy resin
4 parts by weight peroxide
1 part by weight anti-aging agent 0.5 parts by weight [Effect] By applying the A and B agents gold to both sides of the adherend and bonding them as is, the viscosity can be adjusted and there is no stickiness in the protruding areas, as seen in the above example. As the shear strength is excellent, nine things can be obtained.

Claims (1)

[Claims] A two-component non-mixable acrylic adhesive composition of the type in which adhesion is completed by applying the following two components A and B to both sides of the adherend and bonding as is. , Part A (1) 5 to 30 parts by weight of chlorosulfonated polyethylene (2) selected from acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, diacrylate, dimethacrylate, polyfunctional acrylate, and polyfunctional methacrylate. 10 to 100 parts by weight of one or more acrylic resins (3) 0 to 50 parts by weight of diglycidyl ether type epoxy resins (4) 1 to 100 parts by weight of peroxides such as cumene hydroperoxide
50 parts by weight (5) Antioxidant 0 to 5 parts by weight What is obtained by mixing, stirring and dissolving the above (1), (2), (3), (4) and (5), Agent B (1 ) Acrylic rubber and/or acrylic resin 5-50
Part by weight (2) Polymerization accelerator 1 consisting of amine-aldehyde condensate
~50 parts by weight (3) 10 to 100 of one or more monomers selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, diacrylates and dimethacrylates, polyfunctional acrylates and polyfunctional methacrylates Part by weight (4) Diglycidyl ether type epoxy resin 0-50
Part by weight (5) Antioxidant 0 to 5 parts by weight (6) Catalyst 0 to 5 parts by weight Above (1), (2), (3), (4), (5) and (
6) obtained by mixing, stirring, and dissolving.