JPS61203186A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition exhibiting an excellent adhesion in bonding a rubber to a metal and no significant lowering in adhesion even after heat deterioration, by incorporating a dithiocarbamate and a petroleum resin in principal agent for adhesive comprising a chlorinated polymer as a main component. CONSTITUTION:In a main component comprising a chlorinated polymer such as a chlorinated polypropylene, a vinyl chloride elastomer, etc. are incorporated carbon black, a crosslinking agent, etc. to obtain a principal agent for adhesive. 100pts.wt. (on a solid basis) principal agent for adhesive is mixed with 2-20pts. wt. dithiocarbamate (e.g.: nickel dibutyldithiocarbamate or nickel di ethyldithiocarbamate) and 100pts.wt. or less petroleum resin to obtain an intended adhesive composition. The petroleum resin is an adhesive resin compris ing a polymer of styrene, vinyltoluene, etc., and containing an aromatic hydrocar bon and a polycyclic hydrocarbon as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to an adhesive composition for rubber, and particularly to an adhesive composition for rubber whose purpose is to improve adhesion to metals.

(Prior art) Conventionally, in order to bond rubber and metal, after applying a phenolic resin-based brimer and a chlorinated polymer-based cover coat to the bonding surface of the metal, A method is used in which vulcanized rubber or unvulcanized rubber is placed and bonded by pressure and heat treatment.

(Problems to be Solved by the Invention) However, depending on the composition of the rubber and its intended use, the adhesive strength of the above-mentioned brimer and cover coat may be insufficient, especially for industrial rubber products used in high-temperature atmospheres. In this case, the adhesion after thermal deterioration is likely to decrease, so an adhesive composition with stronger adhesion is desired.

With the aim of solving the above problems, the present inventors conducted repeated research on adhesive compositions for rubber, and as a result, they discovered an adhesive composition that can be used to bond rubber and metal and exhibits sufficient adhesion. , we have completed the present invention.

Structure of the Invention (Means for Solving Problems) That is, the present invention consists of a main adhesive agent mainly composed of a chlorinated polymer, a dithiocarbamate, and a petroleum resin, and the solid content of the main adhesive agent is 100% by weight. The above-mentioned problems were solved by devising an adhesive composition characterized in that the dithiocarbamate is blended in a ratio of 2 to 20 parts by weight and the petroleum resin is blended in a proportion of 100 parts by weight or less. By applying a cover coat made of a composition containing a dithiocarbamate as the main ingredient and a dithiocarbamate as the main ingredient, the rubber and metal are firmly bonded through this primer and cover coat. Adhesion is improved, especially after heat aging.

Furthermore, if a petroleum resin is blended into this cover coat, its adhesion will be further improved.

(Example) To explain the above adhesive composition more specifically, the main adhesive agent mainly composed of chlorinated polymer is chlorinated rubber,
This adhesive is mainly composed of chlorinated polypropylene, chlorinated ethylene-polypropylene, chloroprene, vinyl chloride elastomer, etc., with carbon black and a small amount of crosslinking agent added.

Furthermore, dithiocarbamates are metal salts of dialkyldithiocarbamic acids, such as nickel dibutyldithiocarbamate and nickel diethyldithiocarbamate, which are used as anti-aging agents and vulcanization accelerators.

The blending ratio of the main adhesive agent mainly composed of the above-mentioned chlorinated polymer and the dithiocarbamate is 10% of the solid content of the main adhesive agent.
It is preferable that the amount of dithiocarbamate is in the range of 2 to 20 parts by weight relative to 0 parts by weight, and if it exceeds 20 parts by weight, the adhesion will decrease.

Furthermore, petroleum resin is composed of polymers such as styrene, vinyltoluene, and indene, and is mainly composed of aromatic hydrocarbons and polycyclic hydrocarbons, has a softening point of 0°C to 120°C, and a solid carbon content of 15 to 30°C. % adhesive resin.

When blending this petroleum resin, the appropriate amount is 100 parts by weight or less based on 100 parts by weight of the solid content of the adhesive main agent, and if it exceeds 100 parts by weight, the adhesion strength decreases.

The method for preparing the adhesive composition is to mix the adhesive base agent and dithiocarbamate in a solvent appropriately mixed with an aromatic hydrocarbon such as toluene or xylene, a chlorine hydrocarbon such as chloroform, or carbon disulfide, or further It is sufficient to simply mix the petroleum resins in the above-mentioned predetermined proportions.

Next, a method for bonding rubber using the adhesive composition thus obtained will be briefly described.

First, a metal adhesion surface is pretreated by a conventional method, a metal primer is applied, and then the adhesive composition described above is applied.

The primer and adhesive composition may be applied by any conventional coating method.

Next, a base material of vulcanized rubber or unvulcanized rubber is placed on this, and the rubber base material is pressed and heated using a hot platen press or the like.

This pressurization and heat treatment causes a crosslinking reaction at the primer-adhesive composition-rubber base material interface, and the rubber base material and metal are firmly adhered to each other via the primer and adhesive composition.

Further, when an unvulcanized rubber base material is used, the vulcanization reaction also proceeds at the same time.

Next, the vulcanized rubber or unvulcanized rubber to which this adhesive composition is applied includes not only natural rubber (NR) but also various synthetic rubbers, such as chlorinated butyl rubber (CI-11R), chloroprene rubber (CR), etc. ), Hypalon (C3M), styrene-butadiene rubber (SBR), nitrile rubber (NB
R), ethylene-propylene-diene ternary copolymer rubber (
EPDM), ethylene-propylene copolymer rubber (EPM)
) etc., and most rubbers are subject to its application.

Hereinafter, detailed explanation will be given with reference to Examples, but the present invention is not limited to these Examples.

Example 1 An unvulcanized natural rubber (NR) compound having the composition shown in Table 1 was press-vulcanized at 160° C. for 15 minutes to prepare an NR rubber base material with a thickness of 5 mm.

Table-1 (All parts in the table are parts by weight.) *-1 Manufactured by Ohmukai Shinko Kagaku, product name "Sunnock" *-2 Product name "Tsukrank-224" Poly (2,2,4-) Dimethyl-1,2-dihydroquinoline) *-3〃Product name: “Tsukrak-81ONaJ N
-Phenyl-N-isopropyl-p-phenylenediamine*-4 N-cyclohexyl-2-benzothiazolyl sulfonamide On the other hand, after degreasing the adhesive surface of an approximately 311-thick iron plate with trichlorethylene, it was subjected to gridplast treatment. A primer was applied, and after drying at 50°C for 10 minutes, an adhesive composition was further applied.

The primer used was ``Chemlock-205J (product name, phenolic resin adhesive manufactured by Lord Co., Ltd.) (film thickness =
Approximately 10μ). In addition, the adhesive composition is “Chemlock-25
0J (trade name, chlorinated rubber adhesive manufactured by Lord Co., Ltd.) and “
Tsurank-NBCJ (trade name, nickel dibutyldithiocarbamate manufactured by Iriuchi Shinko Kagaku Co., Ltd.) and a mixture of Fucohol resin FR-LJ (trade name, petroleum-based aromatic hydrocarbon manufactured by Fuji Kosan Co., Ltd.) (film thickness = approximately 10μ) ) and
Table 3 shows the blending ratio.

Next, the NR rubber base material was sandwiched between the two iron plates, and the iron plates were pressed from both the upper and lower directions.

The pressing force at this time is such that the thickness of the rubber base material is reduced by 25%.

To illustrate this state, 1 is an iron plate, 2 is a rubber base material, and 3.
4 are a primer and an adhesive composition, respectively.

Next, while maintaining this state, this was placed in a constant temperature bath at 150° C. for 40 minutes to cause the adhesive composition to react, thereby bonding the rubber base material and the iron plate.

Example-2 Unvulcanized chlorinated butyl shim (Cf-
IIR) Press vulcanize the compound at 160°C for 15 minutes.
A C1-11R rubber base material of Tsuru thickness was prepared.

Table-2 *-1 Manufactured by Exxon Chemical Co., Ltd., product name [Chlorobutyl HT-
1t168J *-2 N,N'-diethylthiothiourea manufactured by Ohmukai Shinko Kagaku Thereafter, a Cl-11R rubber base material was bonded between two iron plates using the same procedure as in Example-1.

The same primer and adhesive composition as in Example-1 were used.

Next, using the samples obtained in Examples 1 and 2, the adhesion between the rubber base material and the iron plate was examined using the following method.

〔Test method〕

A tensile shear test and failure mode measurements were performed using an autograph on the samples of Examples 1 and 2 that had been left in a thermostat at 120° C. for 10 days to undergo thermal deterioration, and on the undegraded samples.

Tables 3 and 4 show the results of tests conducted with different mixing ratios of the components in the adhesive composition.

From the test results in Tables 3 and 4 above, it can be seen that by using the adhesive composition of the above example, the rubber base material and the steel plate adhered firmly, and even after thermal deterioration, sufficient adhesion was maintained. I know that there is.

Effects of the Invention As detailed above, the adhesive composition exhibits sufficient adhesion when used to bond rubber and metal, and exhibits the effect that there is little decrease in adhesion even after thermal deterioration. However, it is an excellent invention that can be used for a wide range of purposes.

[Brief explanation of drawings]

The figure is a sectional view showing a state in which rubber and a steel plate are bonded via the adhesive composition of the present invention. 1... Iron plate, 2... Rubber base material, 3... Adhesive composition. Patent applicant Toyoda Gosei Co., Ltd. agent
Patent attorney Hironobu Onda Voluntary procedure amendment dated March 13, 1985 1. Indication of the case 1985 Patent Application No. 43421 2. Name of the invention Adhesive composition 3. Person making the amendment Relationship to the case: Patent application Person Name: Toyoda Gosei Co., Ltd. (Name) 4. Agent address: 2-Hatazume-cho, Gikushi City, 500 <058
2>65-1810 (representative) Fax only <058
2> Contents of amendment in Column 6 of Detailed Description of the Invention in Specification 66-1339 (1) The description “chlorinated ethylene-polypropylene, chloroprene” on page 3, lines 18-19 of the specification has been changed to r-chlorinated. ``Ethylene-propylene rubber, chlorosulfonated polyethylene, chloroprene rubber.'' (2) The description of "solid carbon" on page 4, line 15 of the specification is amended to "fixed carbon." (3) The description of "Hypalon" on page 6, line 7 of the specification is amended to read "chlorosulfonated polyethylene." (4) “Kemuro Tsuku-25” on page 8, lines 6-7 of the specification
0" has been corrected to "Chemlotter-252." (5) “Chlorinated rubber adhesive” on page 8, lines 7-8 of the specification
"chlorosulfonated polyethylene adhesive"
and correct it. (6) “Kemuro Tsuku-2” in the margin of table-4 on page 11 of the specification
50'' was changed to ``Chemrotsuta-252 (solid content)'', and the description of ``Material destruction value R'' was changed to ``Material failure part R'', and ``
The description "interface destruction value RCO ratio" is corrected to "area ratio of interface destruction portion RC".

Claims (1)

[Claims] 1. Consisting of a main adhesive agent mainly composed of a chlorinated polymer, a dithiocarbamate salt, and a petroleum resin, with 2 to 20 parts by weight of the dithiocarbamate salt and a petroleum resin based on 100 parts by weight of the solid content of the main adhesive material. An adhesive composition characterized in that it is blended in a proportion of 100 parts by weight or less.