JP3057822B2 - Vulcanized adhesive compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to vulcanized adhesive formulations. More particularly, the present invention relates to a vulcanized adhesive composition effectively used for adhesion between rubber and various substrates.

[0002]

2. Description of the Related Art Conventionally, an isocyanate-based adhesive has been mainly used for bonding between a rubber and a synthetic resin molded product. However, when bonding is performed using this adhesive, urethane derived from isocyanate is used. Since the bond is easily eroded, there is a defect that durability against polar oil such as brake oil, acid, alkali and the like is poor.

[0003] Chloroprene latex-based adhesives have also been used in the same manner. However, at high temperatures, the cohesive force of chloroprene crystals is reduced due to the crystallization effect at high temperatures. Disadvantage.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a vulcanized adhesive composition of rubber and a synthetic resin molded article, and further to various substrates such as a metal plate, which has heat resistance, chemical resistance, oil resistance and the like. It is to provide something excellent.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
This is achieved by a vulcanized adhesive formulation containing a novolak type epoxy resin, a novolak type phenolic resin, a curing catalyst and chlorinated butyl rubber.

[0006] The novolak type epoxy resin which is a component effective for adhesion to various substrates is represented by the following general formula.

The novolak type epoxy resin is a component used for further improving the heat resistance, chemical resistance and adhesiveness of the adhesive, and is represented by epichlorohydrin in a novolak resin derived from p-unsubstituted phenol. Glycidyl etherification of phenolic hydroxyl groups.

The novolak-type phenol resin, which is a crosslinking component of the novolak-type epoxy resin, is represented by the following general formula.

As described above, a novolak-type phenol resin is obtained by reacting a phenol substituted or unsubstituted at the p-position with an alkyl, phenyl or p-isopropylphenol group with formaldehyde in the presence of an acid catalyst. And a pine or the like which is soluble in an organic solvent such as a ketone, and a curing agent such as an amine compound or a phosphorus compound is added thereto and heated to form an insoluble and infusible phenol resin. In the present invention,
Those having a melting point of about 100 to 150 ° C. and a molecular weight of about 1000 are used.

The following are used as the curing catalyst. Imidazole compounds: 2-methylimidazole, 2-ethyl
-4-methylimidazole, 2-undecylimidazole, 2
-Heptadecylimidazole, 2-phenylimidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole, 2,4-diamino-6- [2-methylimidazoline-
(1)]-Ethyl , s-triazine, etc. Lewis acid amine complex: BF ₃ monoethylamine complex, PF ₅
・ Monoethylamine complex, zinc bromide ・ p-phenylenediamine complex, etc. Acid hydrazide: o-tolylbiguanide, phenylbiguanide, biguanide Ni salt, etc.

These curing catalysts, particularly Lewis acid amine complexes and acid hydrazides, which act as initiators for the crosslinking reaction by epoxy groups, have a long pot life and are latent curing agents which cure rapidly by heating, Can be fixed to the substrate with a pot life of less and a short preheating time.

[0012] Each of these components contains novolak-type phenolic resin in an amount of about 10 to 100 parts by weight, preferably about 20 to 80 parts by weight, based on 100 parts by weight of novolak-type epoxy resin, and 100 parts by weight of novolak-type phenolic resin. Parts to about 0.1 to 5 parts by weight when the curing catalyst is, for example, an imidazole compound, and about 2 to 5 parts by weight when the curing catalyst is a Lewis acid amine complex.
To 20 parts by weight, and in the case of acid hydrazide, about 4 to 40 parts by weight. If the compounding ratio of the curing catalyst is less than this, curing of the resin is slow, heat resistance is inferior, and adhesion is reduced. Conversely, if the curing catalyst is used in a higher ratio, the stability of the organic solvent solution over time will be reduced.

The resin component comprising a novolak type epoxy resin and a novolak type phenol resin and the chlorinated butyl rubber are preferably about 10 to 60% by weight, preferably about 20 to 50% by weight.
%, And the latter is about 90-40% by weight, preferably about 80-50
Each is used in a proportion of% by weight. When the resin content is less than this, the adhesive strength with the adherend, particularly the synthetic resin adherend is reduced, while when the resin content is used at a higher ratio,
The adhesion to rubber is reduced, and the flexibility is also poor.

Further, when chlorosulfonated polyethylene or crystalline chloroprene (chloroprene having a high crystallization rate) is blended at a ratio of about 80 parts by weight or less, preferably about 60 parts by weight or less per 100 parts by weight of chlorinated butyl rubber, It is effective in preventing flow during sulfurization, shortening the baking time, and pre-lamination during lamination.

The vulcanized adhesive composition containing the above components as essential components is used as it is or after being prepared in the form of an organic solvent solution. Any organic solvent can be used as long as it can dissolve each of these components. When it is necessary to store the vulcanized adhesive composition for a long period of time, the curing catalyst is desirably formulated immediately before use.

The vulcanization bonding using these vulcanization adhesive compounds is carried out between rubber and various substrates such as synthetic resin molded articles and metal plates.

As the rubber, diene rubbers such as butyl rubber, chlorinated butyl rubber, styrene-butadiene rubber, nitrile rubber, chloroprene and the like are preferably used.

As the synthetic resin molded product, various molded products of a polar group-containing resin such as polyamide, polysulfone, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, and vinylidene chloride resin are used. In addition, as a metal plate, cast iron, mild steel, stainless steel, aluminum,
A plate-shaped body such as aluminum die-cast or brass, or a rubber-lined steel plate such as a brake shoe is used. Further, as the metal substrate, a processed product other than the plate-like body is also used.

Vulcanization adhesion involves applying the vulcanization adhesive formulation onto a substrate and treating at room temperature for about 30-60 minutes or about 70-150 ° C. for about 0.5 minute.
After drying for ~ 5 minutes, preferably at about 80-200 ° C for about 0.5
Heating for ~ 10 minutes to perform the baking process, and then put the unvulcanized compound of rubber on the mold in a mold or contact it with the substrate by injecting, etc., and pressurize at the vulcanization temperature of the rubber used. It is performed by vulcanization.

It is also possible to bond the applied surfaces together, preferably by heat and pressure, to bond and laminate the synthetic resin molded products, and to further laminate such a laminate with rubber.

[0021]

According to the present invention, when a rubber and various substrates are bonded using the vulcanized adhesive composition according to the present invention, the bonded product may peel off on the substrate surface even when subjected to a high temperature treatment. In particular, a stable effect is obtained in that almost no peeling occurs on metal surfaces such as aluminum, copper, and zinc, which are often peeled off in such a case.

Since an adhesive having not only such heat resistance but also excellent chemical resistance and oil resistance is formed, the vulcanized adhesive composition is used for an adhesive at a site where brake oil, a refrigeration fluid, or the like is used. It can also be used effectively.

[0023]

Next, the present invention will be described with reference to examples.

Example 1 Chlorinated butyl rubber (Japanese synthetic rubber product HT1066) 100 parts by weight Zinc oxide 5 Magnesium oxide 2 MT carbon black 50 Stearic acid 1 Sulfur 2 Vulcanization accelerator (DM) 1.5〃 (BZ) 1 Cresol novolak epoxy Resin 45 (Ciba-Geigy ECN 1299) Bisphenol A novolak resin 22.5 (Hi-Tech Polymer CMD 8452) 2-ethyl-4-methylimidazole 0.45

After kneading the above components with a kneader and a roll, 400 g of toluene was added to 100 g of the kneaded compound.
It was dissolved in a mixed solvent of tetrahydrofuran (1: 3) to prepare a vulcanized adhesive composition solution.

Example 2 In Example 1, the amount of novolak type epoxy resin was 23 parts by weight, the amount of novolak type phenol resin was 12 parts by weight,
The amount of 2-ethyl-4-methylimidazole was changed to 0.3 parts by weight.

Example 3 In Example 1, chlorosulfonated polyethylene was added.
30 parts by weight of Showa Denko / Hyperon 48 manufactured by DuPont were used.

Example 4 In Example 3, the same amount of 4,4'-dithio-bis-dimorpholine was used in place of sulfur, and vulcanization accelerator (DM)
The quantity was changed to 1 part by weight.

Example 5 In Example 3, the same amount of polydinitrosobenzene was used in place of sulfur, and the amount of the vulcanization accelerator (DM) was changed to 1 part by weight.

Example 6 In Example 1, novolak type phenol resin and
2-Ethyl-4-methylimidazole was dissolved in tetrahydrofuran, and the kneaded compound of each other component was dissolved in a mixed solvent, and these solutions were mixed before coating.

The vulcanized adhesive compound solution prepared in each of the above examples was applied to each of the following adherends, dried at 80 ° C. for 5 minutes, and baked at 160 ° C. for 2 minutes. (Vulcanization conditions: 160 ° C, 8 minutes + oven vulcanization 150 ° C, 1 hour), and subjected to various peel tests (unit kgf / cm) using strip-shaped test pieces described in JIS K-6301. went.

[Coating Material] A: Nylon 6 film (product of Ube Industries, 0.1 mm in thickness) B: Saponified ethylene-vinyl acetate copolymer film (Kuraray product EVAL F, 0.1 mm in thickness) C: Polyvinyl alcohol Film (Kuraray product vinylon film # 6500, thickness 65μ) D: Mild steel sheet treated with zinc phosphate coating (0.1mm thickness) [Rubber sheet compound] Butyl rubber (Exxon product butyl 365) 100 parts by weight MT carbon black 50 Zinc oxide 3 Sulfur 1.5 Vulcanization accelerator (TT) 1 〃 (DM) 0.5 [Test conditions] I: Peeling at room temperature II: Peeling at 160 ° C atmosphere III: Immersion in brake oil (DOT 4) at 100 ° C for 140 hours After peeling under room temperature conditions IV: After immersing in LLC-water (1: 1) mixed solution at 120 ° C for 140 hours,
Peeling at room temperature V: Baking time was changed from 2 minutes to 1 minute at the time of sample preparation, and peeled off at room temperature

The measurement results are shown in Tables 1 and 2 below. Comparative Example 1 used a chlorosulfonated polyethylene-isocyanate-based adhesive (Chemloc 402 manufactured by Lord Far East), and Comparative Example 2 used a chloroprene-based latex.
(Electrochemical product Denka LM-50, solid content concentration 50% by weight) are measured values.

Table 1 Test Conditions Example Adherend I II III IV V Example 1 A 2.50 1.20 2.70 1.90 1.70 B 2.30 1.10 2.50 1.80 1.60 C 1.40-1.70-1.00 D 4.50 2.00 4.80 4.50 2.70 Example 2 A 2.30 0.90 2.30 --B 2.10 0.85 2.20--C 1.30-1.40--D 3.30 1.40 3.40--Example 3 A 3.00 1.30 2.90 2.30 2.60 B 2.80 1.35 2.90 2.10 2.50 C 1.70-1.80-1.60 D 5.00 1.90 5.00 4.50 4.20 Example 4 A 3.20 1.50 2.90--B 2.90 1.45 2.70--C 1.70-1.80--D 5.00 1.85 4.80--Example 5 A 3.00 1.20 2.90--B 2.80 1.25 2.80--C 1.60-1.70--D 4.80 1.90 4.90- -Example 6 A 2.90 1.35 2.85 1.70-B 2.90 1.35 2.80 1.70-C-----D-----

Table 2Test condition An example Adherend I II III IV V  Comparative Example 1 A 2.70 1.80 0.30 0.25-B 3.90 1.60 0.30 0.20-C 1.40-> 0.15--D 5.20 2.50 0.35 0.45-Comparative Example 2 A 3.70 0.30 0.80 0.70 3.00 B 3.80 0.25 0.75 0.60 2.90 C 1.20-0.45-1.10 D 4.50 0.50 1.20 1.35 4.50

Example 7 100 parts by weight of chlorinated butyl rubber (HT1066) Zinc oxide 5 Hydrotalcite 0.5 MT carbon black 50 Stearic acid 1 Sulfur 1 Vulcanization accelerator (DM) 1〃 (TT) 1 Cresol novolak epoxy resin (ECN 1299) 30 bisphenol A novolac resin (CMD 8452) 15 BF ₃ · monoethylamine complex 3

After kneading the above components with a kneader and a roll, 400 g of xylene was mixed with 100 g of the kneaded compound.
It was dissolved in a mixed solvent of tetrahydrofuran (1: 3) to prepare a vulcanized adhesive composition solution.

Example 8 In Example 7, 4.5 parts by weight of salicylic acid hydrazide was used in place of the BF ₃ .monoethylamine complex.

Example 9 In Example 8, 2 parts by weight of EZ was used in place of the vulcanization accelerator TT, and 3 parts of brominated phenol formaldehyde resin (Tackilol 250, a product of Sumitomo Chemical Co., Ltd.) was used as a crosslinking agent.
Parts by weight were used.

Example 10 In Example 9, the amount of chlorinated butyl rubber was changed to 85 parts by weight, and instead of that, 15 parts by weight of neoprene (Neoprene AC manufactured by Showa Denko, DuPont) was used.

Each of the vulcanized adhesive compound solutions prepared in Examples 7 to 10 was applied on each of the following adherends, and
After drying at 1.5 ° C. for 1.5 minutes, baking treatment was performed at 170 ° C. for 1 minute, and various peel tests were similarly performed using the rubber sheet or the nylon 6 film (adhering material A). The measurement results are shown in Table 3 below.

Table 3Test condition An example Adherend Base material I II III  Example 7 A rubber sheet 3.2 1.2 3.0 B 〃 3.3 1.0 2.9 D 〃 1.2 0.7 1.0 Example 8 A 〃 3.0 1.0 3.2 B 〃 3.1 1.0 3.3 D 〃 1.0 0.6 0.8 Example 9 A 〃 3.6 1.3 3.0 B 〃 3.8 1.1 3.2 Example 10 A〃4.6 1.1 5.0 B〃4.4 1.0 4.8 B A film 2.0 0.6 2.1

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A vulcanized adhesive composition comprising a novolak type epoxy resin, a novolak type phenol resin, a curing catalyst and a chlorinated butyl rubber. 2. The vulcanized adhesive composition according to claim 1, further comprising chlorosulfonated polyethylene. 3. The composition according to claim 1, which is prepared in the form of an organic solvent solution.
Or a vulcanized adhesive composition according to 2.