JPH02117829A - Manufacture of composite body - Google Patents

Abstract

PURPOSE:To obtain sufficiently initial adhesive force and continuous adhesive force by performing a surface treatment on the surface of a vulcanized rubber article in use of treating agent containing a compound having a specific group in its molecule and polycarbodiimide compound as a required component, after that, laminating polyurethane resin on the treatment surface. CONSTITUTION:The surface of a vulcanized rubber article are given a surface treatment by a treatment agent containing a compound having a group represented by formula (I) (X denotes halogen in the formula) in molecule and polycarbodiimide compound as a required component, and then polyurethane resin is laminated on the treatment surface. As the compound having a group represented by a formula (I), halogenide of isocyanuric acid of trichloroisocyanuric acid, dichloroisocyanuric acid or the like, and N-haloimide of N-chlorosuccinic acid imide, N-bromosuccinic acid imide or the like are exemplified herein. It is preferable that these compounds are used by being dissolved in an organic solvent, and as the organic solvent, it is preferable that monobenzene is used jointly with acetone, ethyl acetate, methylethylketone or the like capable of raising the wettability of a vulcanized rubber article surface for sufficiently performing specially an effective component of the surface treatment agent.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a laminated sheet in which a thin film of polyurethane resin is laminated to a rubber sheet, a rubber hose, a rubber belt, etc. coated with polyurethane resin, and a rubber outsole coated with polyurethane resin. The present invention relates to a method for producing a rubber-polyurethane resin composite such as a shoe having a composite sole in which a mint sole is injected.

[Conventional technology]

Conventionally, when bonding vulcanized rubber and polyurethane resin, prior to bonding, the surface of the vulcanized rubber was coated with trichloroisocyanuric acid, N-chlorosuccinimide, N-bromosuccinimide, etc., with methyl ethyl ketone, acetone, or acetic acid. The surface was treated with a solution dissolved in an organic solvent such as ethyl.

[Problem to be solved by the invention]

However, in such conventional methods, hydrolysis of the polyester-based polyurethane resin in the polyurethane resin progresses significantly due to the influence of the surface treatment agent used, and the method cannot withstand long-term use. In order to eliminate this drawback, it has been proposed to wipe off excess trichloroisocyanuric acid remaining on the vulcanized rubber treated with ethyl acetate, etc., but this is not effective at all in preventing the hydrolysis of polyester polyurethane resins. was not found.

It has also been proposed to incorporate polycarbodiimide compounds into polyester-based polyurethane resins as hydrolysis inhibitors for compounds containing ester groups;
In order to exhibit the hydrolysis prevention function, 0.00% of the polycarbodiimide compound is usually added to 100 parts by weight of the polyurethane resin.
It requires 3 to 2.0 parts by weight, and as the amount added increases, it bleeds onto the rubber surface and becomes an oily substance that not only impairs the appearance but also tends to deteriorate physical properties and inhibit adhesion. was there.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventor found that
We have completed the present invention by discovering that a combination treatment agent of a halogenated compound such as trichloroisocyanuric acid and a polycarbodiimide compound is effective in securing adhesive strength and preventing hydrolysis.

That is, the present invention provides (1) a rubber product obtained by treating the surface of a vulcanized rubber article with a treatment agent containing a compound and a polycarbodiimide compound as essential components, and then laminating a polyurethane resin on the treated surface. A method for producing a polyurethane resin composite.

(2) A method for producing a rubber-polyurethane resin composite, characterized in that the polyurethane resin according to claim 1 is a polyester-based polyurethane resin.

(3) In the method for producing a rubber-polyurethane resin composite according to claim 1 or 2, the treating agent dissolves the compound and the polycarbodiimide compound in a solvent containing ethyl acetate and monochlorobenzene as main components. The gist of the present invention is a method for producing a rubber-polyurethane resin composite, characterized in that

Rubber components of the vulcanized rubber in the present invention include natural rubber, polybutadiene rubber, polyisoprene rubber, polychloroprene rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methacrylic acid-butadiene copolymer, Ethylene-propylene-diene terpolymer, isobutylene-isoprene copolymer, etc. can be used.

The vulcanized rubber in the present invention is obtained by vulcanizing these rubbers, and the vulcanization is performed by sulfur vulcanization using sulfur, which is the most common vulcanizing agent, as well as vulcanization using an organic sulfur compound. Examples include those obtained by peroxide vulcanization, quinoid vulcanization, resin vulcanization, metal salt vulcanization, metal oxide vulcanization, radiation vulcanization, and the like.

In addition to these vulcanizing agents, the rubber may also have fillers such as clay, calcium carbonate, diatomaceous earth, mica, silica, and carbon black, and softeners such as mineral oil and synthetic plasticizers, depending on the application and required properties. , anti-aging agents, processing aids, vulcanization accelerators, blowing agents and other conventional rubber compounding agents can be added.

In the present invention, the above-mentioned rubber compound is sufficiently kneaded using a kneading machine, etc., and then subjected to molding means such as rolling and injection, as well as vulcanization treatment, to form a desired article shape, and a surface treatment agent is applied to the surface of the rubber article. do.

The surface treatment agent in the present invention contains the following compounds and a polycarbodiimide compound as essential components.

Examples of the compound include halides of isocyanuric acid such as trichloroisocyanuric acid and dichloroisocyanuric acid, and N-halimides such as N-chlorosuccinimide and N-bromosuccinimide. It is preferable to use these compounds dissolved in an organic solvent. Examples of organic solvents that can be used include chlorinated hydrocarbons such as carbon tetrachloride, chloroform, and ethyl chloride, benzene, halogenated benzene, xylene, and toluene. aromatic hydrocarbons,
Aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, ethers such as dimethyl ether, diethyl ether, dioxane, and tetrahydrofuran, esters such as ethyl acetate, ketones such as acetone, cyclohexanone, and methyl ethyl ketone, ethanol, tertiary butyl alcohol, etc. Examples include alcohols.

These solvents can be used alone or in combination of two or more. In particular, it is preferable to use monochlorobenzene in combination with acetone, ethyl acetate, methyl ethyl ketone, etc. as a substance that can improve the wettability of the surface of vulcanized rubber articles in order to sufficiently develop the active ingredients of the surface treatment agent, especially ethyl acetate. and monochlorobenzene is an excellent combination, and in this case, it is possible to prevent dew condensation on the surface of the adherend due to latent heat of vaporization. In this combination, the ratio of ethyl acetate to monochlorobenzene is preferably in the range of ethyl acetate/monochlorobenzene - 80/20 to 9515, particularly preferably around 90/10.

The concentration of the treatment agent dissolved in the organic solvent is preferably in the range of 0.5 to 5% by weight, depending on the solubility of each essential component compound and treatment effect.

The treatment agent of the present invention can be applied to the surface of a vulcanized rubber article by any method commonly used for surface treatment, such as dipping in the treatment agent, coating the treatment agent, or spraying.

In the present invention, a polyurethane resin is laminated on the surface-treated side of a vulcanized rubber article that has been surface-treated in this way, but there are no restrictions on the polyurethane resin used, and polyester-based polyurethane resins, polyether-based polyurethane resins, polyether-based polyurethane resins, Any polyurethane resin such as polycarbonate-based polyurethane resin can be used, and this has the advantage of eliminating the inconvenience of changing the surface treatment agent depending on the type of polyurethane resin to be laminated. Furthermore, there are no particular restrictions on the lamination means, and any known means may be used.For example, a method may be used in which polyurethane resin is applied onto a vulcanized rubber sheet, or a vulcanized rubber article is placed in a part of the mold. Alternatively, the polyurethane resin may be laminated by injecting the polyurethane resin into the formed cavity.

〔Example〕

The present invention will be described in detail below based on Examples, but the present invention is not limited thereto.

Example 1 and Comparative Examples 1 to 2 <Example 1> The rubber compound shown below was injected into a shoe outsole forming mold using a kneading extruder and vulcanized to obtain an outsole. .

Rubber compounding Unit: Part by weight Styrene-butadiene copolymer rubber 100 (Niel 1502: manufactured by Nippon Zeon Co., Ltd.) 1.8 1.5 1.5 0.7 Tosozinc white sulfur stearic acid White Glossy Flower cc Dixie Craigie benzothiazyl disulfide Next, about 15 g/m'' of the treatment solution shown below was sprayed onto the formed wool, followed by diphenylguanidine, and dried at 0°C for 1 minute.

Treatment liquid formulation Unit: Part by weight Trichloroisocyanuric acid 1.0 Polycarboniimide compound 0.5 (Starbucks! = Bayer A, (4m) Ethyl acetate 90 Monochlorobenzene 9 Next, the surface-treated outsole is immediately removed. Place it on the bottom mold and
An injection molding void for the mint sole is formed using the bottom mold and the last covered with the insole material sewn together, and the side mold, and the foaming solution for the polyester polyurethane sole is injected into this void. It was foamed in the mold.

The initial adhesive strength of the rubber-polyurethane laminated sole of the obtained injection molded shoe and the adhesive strength after being left in an atmosphere of 70'C and relative humidity of 95% for 144 hours (hereinafter referred to as adhesive strength after jungle test) It was measured. The results are shown in Table 1.

<Comparative Example 1> A vulcanized outsole was first obtained in the same manner as in Example 1, and then surface treated and
In addition, the shoemaking process was carried out. Rubber of the obtained injection molded shoes
The strength of the polyurethane laminated sole was measured under the same conditions as in Example 1. The results are also shown in Table 1.

[Comparative Example 2] First, a vulcanized outsole was obtained in the same manner as in Example 1, and then the surface was treated with the same treatment liquid as in Comparative Example 1, and the treated surface was further wiped thoroughly with ethyl acetate. The same shoemaking process as in Example 1 was then carried out to obtain injection molded shoes.

The strength of the rubber-polyurethane laminated sole of the injection molded shoe obtained was measured under the same conditions as in Example 1. The results are also shown in Table 1.

As is clear from Table 1 below, it can be seen that the method of Example 1 had a good adhesive strength retention rate, while the method of Comparative Example 1.2 had an extremely poor adhesive strength retention rate.

〔Effect of the invention〕

As described above, according to the present invention, even when a polyester-based polyurethane resin is adhesively laminated to a vulcanized rubber article as a polyurethane resin, there is an advantage that sufficient initial adhesive strength and long-lasting adhesive strength can be obtained.

Claims (3)

[Claims] (1) The surface of the vulcanized rubber article is treated with a compound that has a ▲ mathematical formula, chemical formula, table, etc. in its molecule (X represents a halogen) and a treatment agent whose essential components are a polycarbodiimide compound. A method for producing a rubber-polyurethane resin composite, which comprises treating and then laminating a polyurethane resin on the treated surface. (2) A method for producing a rubber-polyurethane resin composite, characterized in that the polyurethane resin according to claim 1 is a polyester-based polyurethane resin. (3) In the method for producing a rubber-polyurethane resin composite according to claim 1 or 2, the processing agent has a ▲ mathematical formula, chemical formula, table, etc. ▼ group (X represents a halogen) in the molecule. 1. A method for producing a rubber-polyurethane resin composite, comprising dissolving a compound and a polycarbodiimide compound in a solvent containing ethyl acetate and monochlorobenzene as main components.