JPH08302323A - Vulcanizing adhesive composition - Google Patents

Abstract

PURPOSE: To obtain a vulcanizing adhesion compsn. effectively applicable to metallic members such as parts involving the problems of dimensional accuracy and fitting parts, and capable of exhibiting a good adhesion to NBR or hydrogenated NBR having a middle or lower nitrile unit content. CONSTITUTION: This compsn. comprises a resol phenolic resin, an epoxy-modified phenolic resin, an unvulcanized NBR or unvulcanized NBR blended with a vinyl chloride resin, and chlorinated polyethylene. It is pref. prepd. in soln. in an org. solvent. It is possible to obtain an adhesion product comprising a metal and a vulcanization product of NBR or hydrogenated NBR by, for example, applying the compsn. to a metal plate, air-drying at room temp. bollowed by drying under heating, bonding an unvulcanized NBR or hydrogenated NBR blend to the plate, and vulcanizing to product under pressure.

Description

Detailed Description of the Invention

[0001]

This invention relates to vulcanized adhesive compositions. More specifically, metal and NBR or hydrogenated NBR
The present invention relates to a vulcanized adhesive composition having excellent corrosion resistance, which is effectively used for adhesion with a vulcanized product.

[0002]

2. Description of the Related Art Conventionally, chlorinated rubber-based or novolac type phenol resin-based adhesives have been used to bond a metal to an NBR vulcanizate, but when these adhesives are used, at least A film thickness of 5 μm is required. For this reason, in the case of a component in which the dimensional accuracy of the metal member is a problem, a fitting component, or the like, there is a problem in workability, such as partial coating only on the rubber adhesive portion.

When these adhesives are used, good adhesion is exhibited with NBR vulcanizates having a high nitrile content of medium or high nitrile NBR, but good adhesiveness is obtained with a nitrile content of medium nitrile NBR or lower. However, there is a drawback that the value decreases sharply.

On the other hand, a method of adhering a metal and NBR using a resol type phenol resin as a component of a primer for vulcanization adhesion has been previously proposed by the present applicant (Japanese Patent Laid-Open No. 2-55782). In the adhesion method, a vulcanization adhesion primer containing an epoxy resin and a resol-type phenol resin is applied on a metal and baked, and then NB
A phenol resin vulcanizing adhesive for R is applied, an unvulcanized NBR compound is bonded thereto, and pressure vulcanization is performed at the vulcanizing temperature of NBR. This method is used. Epoxy resin and resol type phenolic resin are
It is just a primer application.

Further, the chlorinated rubber adhesives that have been conventionally used for this type of use also have a drawback that they have poor durability in hot water and salt water environments.

[0006]

SUMMARY OF THE INVENTION The object of the present invention can be effectively applied to metal members such as parts and fitting parts in which dimensional accuracy is a problem, and it has been said that conventional adhesion is difficult. A vulcanized adhesive composition effectively used for adhesion between a metal and an NBR or hydrogenated NBR vulcanizate, which exhibits good adhesiveness to NBR having a nitrile content equal to or less than the medium nitrile NBR or hydrogenated NBR. To provide.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
It is achieved by a vulcanized adhesive composition containing a resole type phenolic resin, an epoxy modified phenolic resin, an unvulcanized NBR or a vinyl chloride resin blend unvulcanized NBR and chlorinated polyethylene.

As the resol type phenol resin, those represented by the following general formula are used.

As the epoxy-modified phenol resin, a novolac type resin represented by the following general formula is used.

Unvulcanized NBR is a commercially available product having an extremely high nitrile content (nitrile content of 43% or more) and a high nitrile content.
(36 to 42% of the same), medium and high nitrile content (31 to 35% of the same), medium nitrile content (25 to 30% of the same), low nitrile content (24% or less of the same) can be optionally used. Generally, those having a medium to high nitrile content are preferably used from the viewpoint of compatibility with other components. In addition, vinyl chloride resin blend unvulcanized NB
As R, the vinyl chloride resin blending amount is about 15 to 50 weight
%, Preferably about 15-35% by weight of medium and high nitrile content NBR
Is preferred.

As the chlorinated polyethylene, one having a chlorine content of about 60 to 70% is preferably used.

Among the above components, the resol type phenol resin and the epoxy modified phenol resin are about 50
90% by weight, preferably about 70-85% by weight, the latter about 50-
It is used in a proportion of 10% by weight, preferably about 30-15% by weight. If the proportion of the epoxy-modified phenol resin is higher than this, the adhesiveness with NBR will decrease, while below this, the effect of improving corrosion resistance will not be seen.

Unvulcanized NBR or vinyl chloride resin blend Unvulcanized NBR is used in an amount of about 10 to 30 parts by weight, preferably about 15 to 25 parts by weight, per 100 parts by weight of the phenol resin of both. If it is used in a ratio higher than this, the curing speed of the adhesive may slow down, which may cause the adhesive layer to be washed away during vulcanization. Deteriorate.

The chlorinated polyethylene is used in an amount of about 5 to 20 parts by weight, preferably about 8 to 15 parts by weight, per 100 parts by weight of the above-mentioned phenol resins. If chlorinated polyethylene is used in excess of this amount, the adhesive layer will become brittle, and when the metal is caulked, the adhesive layer will crack and fall off, while if used in less than this amount, adhesion to the metal surface will be reduced. Will start to decline.

The vulcanized adhesive composition containing each of these components as essential components is prepared as an organic solvent solution. As the organic solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone or toluene, aromatic hydrocarbons such as xylene are preferably used, but from the viewpoint of solubility of each essential component, as a mixed solvent thereof, It is particularly preferable to use. When used as a mixed solvent, both ketones and aromatic hydrocarbons are used in a mixture of about 30 to 70% by weight, preferably about 40 to 60% by weight.

The adhesive composition as an organic solvent solution is prepared by first dissolving unvulcanized NBR or vinyl chloride resin blend unvulcanized NBR in an organic solvent, and then resol type phenol resin, epoxy modified phenol resin and chlorine. PEG is added and dissolved. Its solid content concentration is about 1 to 30% by weight, preferably about 3
It is adjusted to be ~ 15% by weight. When the solid content concentration is higher than this, the pot life of the adhesive becomes extremely short and it becomes unusable for practical use.

For adhesion, this vulcanized adhesive composition solution is applied to degreased and chemical-treated metal such as mild steel, stainless steel, aluminum, aluminum die cast, brass, zinc, etc., and air dried at room temperature. , About 150-230
C., preferably about 180 to 220.degree. C., for about 5 to 30 minutes, to which the unvulcanized NBR or hydrogenated NBR compound is bonded and cured at the vulcanization temperature of NBR or hydrogenated NBR. It is carried out by pressure vulcanization. The application of the vulcanized adhesive composition solution is carried out a plurality of times as necessary, but it may be applied once, and sufficient adhesive performance is exhibited even when the film thickness is about 5 μm.

As the unvulcanized NBR or hydrogenated NBR compound, for example, the following compound examples are used. (Formulation Example I) NBR (Chemical gum N715B manufactured by Goodyear Co., Ltd .; medium nitrile) 100 parts by weight SRF carbon black 40 talc 20 zinc oxide 5 stearic acid 1 dioctyl phthalate 5 N-phenyl-N'-isopropyl-p-phenylenediamine 2 sulfur 0.5 Tetramethylthiuram disulfide 2 2-Mercaptobenzothiazole 1 (Formulation Example II) NBR (Goodyear's product Chemigam N917; low nitrile) 100 parts by weight FEF carbon black 20 MT carbon black 40 zinc oxide 5 stearic acid 1 dioctyl sebacate 5 2, 2,4-Trimethyl-1,2-dihydroquinoline 1 Sulfur 1 Zinc dimethyldithiocarbamate 2 Di-2-benzothiazolyl disulfide 3 (Formulation example III) NBR (Chemical gum N615B manufactured by Goodyear Co., Ltd., medium-high nitrile) 100 parts by weight SRF Carbon black 40 Talc 20 Zinc oxide 5 Stearic acid 1 Di Octyl phthalate 5 N-Phenyl-N'-isopropyl-p-phenylenediamine 2 Sulfur 0.5 Tetramethylthiuram disulfide 22 2-Mercaptobenzothiazole 1 (Formulation Example IV) NBR (Goodyear product Chemigum N917; low nitrile) 100 parts by weight SRF Carbon black 80 MT Carbon black 20 Zinc oxide 5 Stearic acid 1 Dioctyl phthalate 6 2,2,4-Trimethyl-1,2-dihydroquinoline 1.5 Dicumyl peroxide 2 Triallyl isocyanurate 0.5 (Formulation example V) Hydrogenated NBR ( Zeon Corporation Zetpol 2020) 100 parts by weight SRF carbon black 50 Magnesium oxide 5 Stearic acid 1 Triallyl isocyanurate 1 1,3-Di-tert-butylperoxyisopropylbenzene 1.5

[0019]

INDUSTRIAL APPLICABILITY The vulcanized adhesive composition according to the present invention can be effectively used for adhesion of metal and NBR or hydrogenated NBR vulcanizate in a one-component coating, in which case dimensional accuracy is a problem. It can also be effectively applied to metal members such as parts and fitting parts. Moreover, except for the conventional chlorinated rubber adhesives, good adhesion is exhibited even for nitriles having a nitrile content of NBR or less, which has been considered to be difficult to bond. Excellent corrosion resistance is exhibited even in hot water or salt water, which has been a drawback when used.

[0020]

Next, the present invention will be described by way of examples.

Examples 1 to 5 80 parts by weight of resol type phenolic resin (Dainippon Ink and Chemicals product AF-2639) Epoxy modified phenolic resin 20 (Dainippon Ink and Chemicals product Epicron N695) Unvulcanized NBR (Chemi gum N615B) 18 Chlorinated polyethylene (Daiso Z-200) 10 Methyl ethyl ketone 600 Toluene 600 An adhesive composition solution prepared from each of the above components was applied onto a zinc phosphate-coated mild steel sheet and left at room temperature for 30 minutes. After that, a drying treatment was performed at 200 ° C. for 15 minutes, and the unvulcanized compounds of the above Formulation Examples I to V were bonded thereto, and at 180 ° C. for 10 minutes.
Pressure vulcanization for 1 minute was performed.

Examples 6 to 10 Resole type phenolic resin (AF-2639) 85 parts by weight Epoxy modified phenolic resin (Epiclon N695) 15 Vinyl chloride resin blend Unvulcanized NBR 15 (Nippon 1203JN manufactured by Zeon Corporation) Chlorinated polyethylene (Daiso) Product Z-200) 15 Methyl ethyl ketone 700 Toluene 800 The adhesive composition solution prepared from each of the above components was applied on a zinc phosphate-coated mild steel sheet and left at room temperature for 30 minutes, then at 190 ° C for 15 minutes. After performing a drying treatment for 10 minutes, the unvulcanized blends of the above Blend Examples I to V are bonded thereto, and the mixture is dried at 180 ° C for 10
Pressure vulcanization for 1 minute was performed.

Comparative Examples 1 to 5 In Examples 1 to 5, the amount of resole type phenolic resin was
The amount of the epoxy-modified phenolic resin was changed to 20 parts by weight, and the amount of the epoxy-modified phenolic resin was changed to 80 parts by weight.

Comparative Examples 6 to 10 In Examples 6 to 10, the amount of resol type phenol resin was 15 parts by weight and the amount of epoxy modified phenol resin was 85.
Changed to parts by weight.

Comparative Example 11 Unvulcanized NBR was not used in the adhesive composition solution of Example 2 applied to the unvulcanized formulation of Formulation II.

Comparative Example 12 No chlorinated polyethylene was used in the adhesive composition solution of Example 2 applied to the unvulcanized formulation of Formulation II.

Comparative Examples 13 to 14 A commercially available adhesive (primer: Chemlock 205 manufactured by Lord Co., cover coat: Chemlock 220 manufactured by the same company) was applied onto a mild steel sheet treated with a zinc phosphate coating, and the compounding example I was applied thereto.
Alternatively, the unvulcanized compound of II was joined and pressure-vulcanized at 180 ° C. for 10 minutes.

The adhesives obtained in the above Examples and Comparative Examples were subjected to a 90 ° peel test in accordance with JIS K-6301, and the peel force (unit: KN / mm) and the residual rubber area ratio (unit:
%) Respectively. In addition, a warm water immersion test (immersion in 80 ° C water for 168 hours) and a salt spray test (35% at 5% saline solution
After spraying for 68 hours, the same measurement was performed. Furthermore,
The presence or absence of cracks in the adhesive layer was observed by a 90 ° bending test of the adhesive-coated mild steel sheet. The results obtained are shown in the following table.

Table Test Before immersion in warm water After salt spray Bending Example Peeling force Remaining area Peeling force Remaining area Peeling force Remaining area Cracking Example 1 6.2 100 4.9 95 4.1 100 None 〃 2 5.4 〃 4.3 90 3.9 95 〃 3 7.3 〃 5.8 100 6.0 100 〃 〃 4 5.6 〃 4.7 95 4.0 95 〃 〃 5 8.6 〃 7.8 100 7.5 100 〃 〃 6 6.4 〃 4.8 100 4.2 95 〃 〃 5.9 〃 8 7.9 〃 8 7.9 〃 〃 9 5.4 〃 4.3 90 4.6 95 〃 〃 10 9.0 〃 8.2 95 8.0 90 〃 Comparative Example 1 1.2 20 0.6 10 0.2 0 None 〃 2 0.9 10 0.4 5 0.3 0 〃 〃 3 1.5 30 0.9 10 0.5 0 〃 〃 4 2.2 20 1.2 15 0.6 5 〃 〃 5 3.1 20 1.5 10 0.9 5 〃 〃 6 0.9 30 0.5 20 0.2 0 〃 〃 7 0.8 40 0.3 0 0.2 0 〃 〃 8 1.2 20 0.8 20 0.5 5 〃 〃 9 2.1 30 1.0 10 0.8 10 〃 〃 10 2.9 40 1.6 30 1.0 10 〃 〃 11 0.8 0-----〃 12 0.4 0-----〃 13 6.8 100 3.2 50 2.5 20 Yes 〃 14 5.5 100 2.1 40 1.8 20 〃

Claims (4)

[Claims] 1. A vulcanized adhesive composition comprising a resol type phenol resin, an epoxy modified phenol resin, an unvulcanized NBR or a vinyl chloride resin blend unvulcanized NBR and chlorinated polyethylene. 2. Resol type phenolic resin and epoxy modified phenolic resin are about 50 to 90% by weight and about 5% respectively.
The vulcanized adhesive composition according to claim 1, which is used in a proportion of 0 to 10% by weight. 3. The method according to claim 1, which is prepared as an organic solvent solution.
The vulcanized adhesive composition described. 4. The vulcanized adhesive composition according to claim 1, which is used for adhering a metal to an NBR or hydrogenated NBR vulcanizate.