JP2668972B2 - Adhesion method between metal and NBR - Google Patents

Description

The present invention relates to a method for adhering a metal and NBR. More specifically, it relates to a method for adhering a metal and NBR that gives a vulcanized adhesive having excellent resistance to hot water immersion.

[Prior Art] and [Problems to be Solved by the Invention] Conventionally, a phenol resin-based adhesive has been used as an adhesive between metal and NBR. Hot water, salt water, water-glycol liquid (mixture of water and ethylene glycol)
There is a defect that the adhesive surface peels off when immersed in.

It has become clear that the cause of such peeling in an aqueous environment is the hydrogen bonding force between the metal surface and the phenol resin and the crosslink density of the phenol resin.

An object of the present invention is to provide a bonding method for a metal and an NBR that gives a vulcanized adhesive having excellent resistance to hot water immersion, taking into consideration such a cause of peeling in an aqueous environment.

[Means for solving the problem]

The bonding between the metal and NBR to achieve the above object is performed by applying a vulcanization bonding primer containing a resol-type phenol aldehyde resin derived from an epoxy resin and a monohydric phenol onto the metal and performing a baking treatment on the NBR. It is carried out by applying a phenol resin adhesive for use, bonding an unvulcanized compound of NBR thereto, and vulcanizing under pressure at the vulcanizing temperature of NBR.

As the epoxy resin which is one component of the vulcanization adhesion primer, a bisphenol A type epoxy resin having an average molecular weight of about 10,000 to 10,000 is preferably used. In addition, the resole type phenol aldehyde resin, which is another essential component, is capable of reducing phenolic hydroxyl groups such as phenol, p-cresol, p-tert-butylphenol, p-phenylphenol, m-cresol and 3,5-xylenol. Two or three at the -position and / or p-position
Monohydric phenols having one hydrogen atom capable of substituting with formaldehyde, ammonia, alkali hydroxide,
It is obtained by a condensation reaction in the presence of an alkali catalyst such as magnesium hydroxide. In the present invention, those having an average of 2 to 8 phenol skeletons in the molecular chain are used.

These epoxy resins and the resole-type phenol aldehyde resin derived from monohydric phenol are about by weight ratio.
It is used in a ratio of 9: 1 to 4: 6, preferably about 8: 2 to 5: 5, and constitutes a vulcanized adhesive primer. This vulcanized adhesive primer is generally prepared and used in the form of an organic solvent solution,
As the organic solvent, any solvent can be used as long as it can dissolve each of these components. For example, a ketone such as methyl ethyl ketone or a ketone-aromatic hydrocarbon-
Alcohol mixed solution is preferably used.

At the time of bonding, the organic solvent solution of this vulcanized adhesive primer is mild steel, stainless steel, aluminum,
It is applied on a metal such as aluminum die cast, brass, zinc, etc., and after it is heated and dried at about 50-80 ℃, about 12
The baking treatment is first performed by heating at 0 to 220 ° C. for about 5 to 30 minutes.

Then, a phenolic resin adhesive for NBR is applied to the baked surface. Examples of such an adhesive include an alkylphenol resole type compounded with a small amount of chlorinated rubber (trade name: Chemlok 205, Metaloc P, etc.), a resorcinol-based phenol resin (trade name: typly
BN) or novolac alkylphenol resin (trade name Chemlock LJ201, Sixon 715, etc.) etc. are used.

Once the NBR phenolic resin-based adhesive has been applied, place the unvulcanized NBR compound on the mold or inject it to bring it into contact with the metal at the NBR vulcanization temperature. Adhesion is achieved by pressure vulcanization at some 160-300 ° C.

Examples of NBR unvulcanized compounds include the following.

NBR (Nippon 1041 manufactured by Zeon Corporation) 100 parts by weight SRF carbon black 40 Zinc oxide 5 Stearic acid 1 Dioctylphthalate 5 Sulfur 1 Tetramethylthiuram disulfide 2 [Action] and [Effect of the invention] NBR and metal adhered by the method of the present invention The vulcanized adhesive product of and has a remarkable effect that no peeling of the adhesive is observed even when it is immersed in hot water of about 120 ° C. or lower (pressurized water at 100 ° C. or higher) or warm water.

This is because a vulcanization adhesive primer containing a resole-type phenol aldehyde resin derived from epoxy resin and monohydric phenol is used as a base material for a phenolic resin-based adhesive for NBR, so that the phenol resin can be separated from the metal surface. It is believed that the hydrogen bond strength of the NBR is increased and the phenol resin is made to have a high crosslink density, which in turn enhances the adhesion between the metal and NBR.

〔Example〕

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

Example 1 From 40 parts (weight, the same applies hereinafter) of an epoxy resin (AER669 manufactured by Asahi Kasei), 10 parts of a resol-type phenol aldehyde resin (Hitanol 4010 manufactured by Hitachi Chemical), and 100 parts of a mixed solvent of equivalent amounts of methyl isobutyl ketone-xylene-n-butanol. The following vulcanization adhesion primer solution was applied onto a mild steel plate that had been shot blasted and washed with trichloroethane, dried at 50 ° C for 10 minutes, and then baked at 180 ° C for 10 minutes.

After applying a commercially available phenolic resin adhesive (Sixson 715) to the baked surface and drying, the NBR unvulcanized compound of the above formulation example is bonded in accordance with JIS K-6301 8.3, paragraph 90, 90 ° peeling method. Then, pressure vulcanization was performed at 180 ° C. for 4 minutes using the mold.

Example 2 In Example 1, the amount of epoxy resin was changed to 60 parts, and the amount of resol-type phenol aldehyde resin was changed to 40 minutes.

Example 3 In Example 1, the amount of epoxy resin was changed to 50 parts and the amount of resol-type phenol aldehyde resin was changed to 50 minutes.

Comparative Example 1 In Example 3, chlorosulfonated polyethylene (Chemlock 252 manufactured by Lord Co.) was used instead of the commercially available phenol resin adhesive.

Comparative Example 2 In Example 1, a commercially available phenol resin-based adhesive (Chemlock 205 manufactured by Lord Co., Ltd.) was used instead of the primer solution for vulcanization adhesion, and the NBR unvulcanized compound was bonded thereto.

The vulcanized adhesives obtained in the above Examples and Comparative Examples were subjected to a hot water immersion test at 120 ° C. for 70 hours, and the peeling force (unit: kg / cm) and the remaining rubber area (unit:%) were determined. Each was measured. The results obtained are shown in the following table.

Claims (1)

(57) [Claims] 1. A vulcanization adhesive primer containing a resol-type phenol aldehyde resin derived from an epoxy resin and a monohydric phenol is applied on a metal, baked, and then a phenol resin adhesive for NBR is applied. A method for adhering a metal and NBR, which comprises bonding an unvulcanized compound of NBR thereto and pressurizing at a vulcanizing temperature of NBR.