JPH07110929B2 - Vulcanization adhesion primer composition and adhesion method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vulcanizing adhesion primer composition and an adhesion method using the same. More specifically, it relates to a vulcanization adhesion primer composition used for adhesion of a metal and a peroxide vulcanizable rubber, and an adhesion method using the same.

[Conventional technology]

Conventionally, a chlorinated rubber adhesive or a phenol resin adhesive has been used to bond a metal and a nitrile rubber (NBR), but when these adhesives are used, a film thickness of at least 5 μm or more is obtained. It is necessary, and for this reason, in the case of parts and fitting parts where the dimensional accuracy of the metal member is a problem,
There were some surfaces that impaired workability, such as the need to partially coat only the rubber adhesion part. When using these adhesives, NBR containing peroxide vulcanizing agent
Adhesion may be unstable in formulations, and adhesives that exhibit stable adhesion are desired.

In addition, a chlorinated rubber adhesive is used when adhering ethylene / propylene copolymer rubber (EPDM) having a copolymerized diene component as a cross-linking point to a metal. When using this adhesive, In addition to the various problems associated with the film thickness as described above, there is a problem in that the adhesiveness is greatly reduced in an aqueous environment, for example, in warm water, and peeling of the adhesive occurs.

Furthermore, vinylidene fluoride-based, tetrafluoroethylene-
Fluorine rubber such as propylene type and phosphazene type (FK
Organosilane adhesives are mainly used for adhering M) to metals, but with FKM compounds containing peroxide vulcanizing agents, the adhesion may become unstable, resulting in stable adhesion. An adhesive is desired that is desired.

In addition, these adhesives may have unstable adhesion to non-ferrous metals such as aluminum and brass.
A stable adhesive is desired even for these non-ferrous metals.

[Problems to be solved by the invention]

The present inventors have previously made various investigations for a primer composition in which the adhesive film may be applied thinly, and moreover, these peroxide vulcanizable rubbers show stable adhesiveness.
It has been found that a primer composition containing methacryloxypropyltrimethoxysilane, an aqueous acid solution as a methoxy group hydrolysis accelerator of the methoxysilane compound, and an organic solvent as essential components sufficiently satisfies the above purpose ( Japanese Patent Application No. 62-45,146).

Adhesion between the metal and the peroxide vulcanizable rubber using such a vulcanizing adhesion primer composition is performed by applying the primer composition to a metal and then performing a baking treatment at about 130 to 200 ° C., Is contacted with a rubber compound containing a peroxide vulcanizing agent, and pressure vulcanization is performed at the rubber vulcanizing temperature.

The adhesion between the metal and the peroxide vulcanizable rubber thus performed is that the intended purpose has been achieved, but uneven coating easily occurs due to the presence of water in the primer composition, It was found that there is a point to be solved further, for example, the desired adhesiveness and film forming rate cannot be obtained without the baking treatment.

Therefore, the present inventors have sought a solution to these points,
It has been found that when an organic titanium compound or an organic zirconium compound is used instead of the aqueous acid solution used as the alkoxy group hydrolysis accelerator of the organic silane compound, it effectively acts as an adhesion promoter for the organic silane compound.

[Means for solving problems]

Therefore, the present invention relates to a vulcanization adhesion primer composition of a metal and a peroxide vulcanizable rubber, and this vulcanization adhesion primer composition is an organic silane compound having an unsaturated bond, and adhesion of the organic silane compound. An organic titanium compound or an organic zirconium compound as an accelerator and an organic solvent are contained as essential components.

The present invention also relates to a method for adhering a metal and a peroxide vulcanizable rubber using the vulcanizing adhesive primer composition, wherein the metal and the peroxide vulcanizable rubber are adhered to the metal by the above primer composition. After coating and drying at room temperature, a rubber compound containing a peroxide vulcanizing agent is brought into contact therewith, and pressure vulcanization is performed at the vulcanizing temperature of the rubber.

Examples of the organic silane compound having an unsaturated bond include γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, norbornyltrimethoxysilane, γ-diallylamino. Examples thereof include propyltrimethoxysilane, and preferably γ-methacryloxypropyltrimethoxysilane is used.

As the organic titanium compound as the adhesion promoter, for example, tetraisopropyl titanate, tetra n-butyl titanate, tetra-2-ethylhexyl titanate, titanium acetylacetonate, etc. are used. Similar effects can be obtained by using an organic zirconium compound such as zirconium butyrate or zirconium acetotyl acenate instead of the organic titanium compound.

Further, as the organic solvent, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, alcohols such as methanol, ethanol and isopropanol are used.

Each of the above components contains about 1 to about 5 parts by weight of the organosilane compound or the organotitanium compound.
10 parts by weight, preferably about 2 to 5 parts by weight, and an organic solvent in an amount of about 100 to 1000 parts by weight, preferably about 200 to 500 parts by weight, respectively. If the proportion of the organic titanium compound or the organic zirconium compound used is less than this range, the heat resistance will be poor, while if it is more than this range, the adhesion to rubber will be reduced.

Preparation of a composition using each of these components is performed by first adding an organic silane compound to an organic solvent, and then adding an organic titanium compound or an organic zirconium compound. At this time, if the order of addition is reversed, white turbidity occurs and the adhesiveness decreases.

When bonding metal and peroxide vulcanizable rubber,
Such a primer composition is first applied to a metal, air dried at room temperature for about 30 to 60 minutes, and then preferably dried at about 120 ° C. As the metal, mild steel, stainless steel, aluminum, aluminum die cast, brass, zinc, copper alloy and the like are used.

A rubber compound containing a peroxide vulcanizing agent is brought into contact therewith, and an example of the compounding formula of such a rubber compound is as follows. As the NBR, when γ-methacryloxypropyltrimethoxysilane is used, as shown in Examples below, either NBR having a low or high nitrile content or hydrogenated NBR can be used.

[Formulation Example I]

NBR (NIPPON DENON NIPPON DN206) 100 parts by weight FEF carbon black 40 Silica powder 20 Zinc flower 5 Stearic acid 1 Dioctylphthalate 5 Anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline) 1 Triallyl isocyanate Nurate (70%) 0.8 1,3-Bis (tertiary butylperoxyisopropyl) benzene 2.5 [Formulation example II] NBR (Nippon DN302 manufactured by Zeon Corporation) 100 parts by weight FEF carbon black 60 Zinc white 5 Stearic acid 1 Anti-aging agent (2,2,4-Trimethyl-1,2-dihydroquinoline) 1 Dioctyl phthalate 5 Triallyl isocyanurate (70%) 0.8 1,3-Bis (tert-butylperoxyisopropyl) benzene 2.5 [Formulation Example III] Water NBR (Nihon Nipol 1010) 100 parts by weight FEF carbon black 40 silica powder 20 zinc flower 5 stearic acid 1 dioctyl lid 5 Anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline) 1 Triallyl isocyanurate (70%) 2.5 1,3-bis (tertiary butylperoxyisopropyl) benzene 6 [Formulation example IV] EPDM (Mitsui Petrochemicals Mitsui EPT3070) 100 parts by weight FEF Carbon black 40 Zinc white 5 Stearic acid 0.5 Silica powder 30 1,3 Bis (3butylperoxyisopropyl) benzene
3 Triallyl isocyanurate (70%) 1.5 parts by weight [Formulation Example V] FKM (Daikin Industrial Product Daier Z91N) 100 parts by weight MT Carbon Black 40 1,3-bis (tertiary butylperoxyisopropyl) benzene 3 Triallyl isocyanate Nurate (70%) 1.5 parts by weight In addition to the compounding examples above, peroxide vulcanization of various peroxide vulcanizable rubbers such as silicone rubber, hydrin rubber, acrylic rubber, halogenated butyl rubber, chlorinated polyethylene, neoprene rubber, natural rubber, etc. For agent formulations,
The vulcanization adhesion primer composition of the present invention is effective.

Such a rubber compound containing a peroxide vulcanizing agent is placed on a metal which has been baked in a mold or brought into contact with the metal by contacting with the metal, and then the vulcanization temperature of the rubber used is about Adhesion is performed by pressure vulcanization at 150 to 200 ° C.

〔The invention's effect〕

The vulcanizing adhesive primer composition according to the present invention does not cause uneven coating because it does not use water, does not require baking at high temperature because the film forming rate is fast, and air-drying at room temperature is sufficient. In addition, it exhibits good adhesion to non-ferrous metals and inorganic substances, and the adhesive has an effect of improving heat resistance.

Therefore, the present invention provides various industrial rubber parts, such as oil seals, gaskets, packings, valves,
In particular, it can be effectively applied to adhesion to a metal in a complicated part having a hole and a groove.

〔Example〕

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

Example 1 5 parts of γ-methacryloxypropyltrimethoxysilane (weight, the same applies hereinafter), tetraisopropyl titanate 5
Part and a primer composition consisting of 250 parts of toluene,
Apply on degreased mild steel sheet, leave it at room temperature for 60 minutes to air dry, and then perform drying treatment at 120 ° C for 5 minutes,
Pressure vulcanization was performed at 180 ° C. for 6 minutes with the NBR formulations of Formulation Examples I-III.

Examples 2-3 In Example 1, the same amount of vinylmethoxysilane (Example 2) or vinyltris (2-methoxyethoxy) silane (Example 3) was used instead of γ-methacryloxypropyltrimethoxysilane. It was

Regarding the adhesive obtained in each of the above examples, JIS K-630
A 90 ° peel test was performed according to 1. The results obtained are
It is shown in Table 1 below.

From the above results, any alkoxy group-containing silane compound is effective for medium-high nitrile content (33%) NBR (formulation example I), but medium nitrile content (28%)
Only γ-methacryloxypropyltrimethoxysilane is substantially effective against NBR (Formulation Example II), and other than γ-methacryloxypropyltrimethoxysilane against hydrogenated NBR (Formulation Example III). The remaining rubber area is decreasing. That is, γ-methacryloxypropyltrimethoxysilane does not depend on the properties of the NBR used and always exhibits effective adhesiveness.

Example 4 In Example 1, the primer composition was applied on a degreased brass plate, and the above formulation example IV was used instead of the NBR formulation.
Pressure vulcanization was performed at 180 ° C. for 8 minutes using the EPDM compound of Example 1.

Comparative Example 1 In Example 4, a commercially available undercoat adhesive (Road fur
Chemlock 205 manufactured by Yeast Co., Ltd. and a vulcanization adhesive for commercial EPDM (Chemlock 252 manufactured by the same company) were applied on a degreased brass plate, and then pressure vulcanization was performed.

Example 5 In Example 4, a primer composition consisting of 5 parts of γ-methacryloxypropyltrimethoxysilane, 2 parts of zirconium butyrate and 250 parts of toluene was used.

Example 6 In Example 1, the primer composition was applied on a degreased aluminum plate, and the FKM compound of Formulation Example V was used instead of the NBR compound, and pressure vulcanization was performed at 180 ° C. for 6 minutes. I did.

Comparative Example 2 In Example 5, a commercial FKM adhesive (Chemlock 607 manufactured by Lord Far East Co., Ltd.) was applied on a degreased aluminum plate, and then pressure vulcanization was performed.

For the above Examples 4 to 6 and Comparative Examples 1 and 2, the same 90 ° peel test was carried out, and for Examples 4 to 5 and Comparative Example 1, after dipping in tap water at 80 ° C for 500 hours. A 90 ° peel test was performed. The results obtained are shown in Table 2 below.

Claims (4)

[Claims] 1. A metal and peroxide vulcanizable rubber containing an organic silane compound having an unsaturated bond, an organic titanium compound or an organic zirconium compound as an adhesion promoter for the organic silane compound, and an organic solvent as essential components. And a primer composition for vulcanization adhesion. 2. An organic silane compound having an unsaturated bond is γ
-The vulcanization adhesion primer composition according to claim 1, which is methacryloxypropyltrimethoxysilane. 3. The primer composition for vulcanization adhesion according to claim 1, wherein the peroxide vulcanizable rubber is nitrile rubber, ethylene / propylene copolymer rubber or fluororubber. 4. A primer composition comprising an organosilane compound having an unsaturated bond to a metal, an organotitanium compound as an adhesion promoter for the organosilane compound, and an organic solvent as essential components is applied and dried at room temperature. After that, a rubber compound containing a peroxide vulcanizing agent is brought into contact therewith, and pressure vulcanization is performed at a vulcanizing temperature of the rubber, and a method for adhering a metal and a peroxide vulcanizable rubber.