JP2676380B2 - Adhesive composition for glass tensile member for belt - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an adhesive composition of a glass tensile member for a rubber for belts, and particularly to a good adhesive property suitable for a rubber for organic peroxide vulcanized belts, The present invention relates to an adhesive composition having bending fatigue resistance.

[Conventional technology]

Conventionally, a toothed belt having teeth formed on one side or both sides has been widely used as a power transmission means. This toothed belt generally comprises a tooth-shaped surface protective layer, a rubber layer and a tensile body.

As a tensile body, glass fiber is widely used from the viewpoint of tensile strength, flexibility, adhesiveness with a rubber layer, and the like.

When embedding a glass tensile member in rubber for a belt, an adhesive is used to strengthen the adhesion between the two, but conventionally, the widely used adhesive is a resorcinol-formaldehyde resin. It was a conjugated diene-based monomer (latex) containing.

On the other hand, it is a common theory that the rubber used for the belt is a sulfur vulcanization system in order to establish vulcanization adhesion with the glass tensile member, and is widely used as industrial and automobile belts.

[Problems to be Solved by the Invention] However, with the recent advent of high-performance engines, high-performance machine tools, and the like, belts are required to have higher heat resistance, which is superior to conventional sulfur-vulcanized rubber. Rubber materials are desired. Organic peroxide-vulcanized rubber is a rubber that has better heat resistance than sulfur-vulcanized rubber, but conventional adhesive methods are not compatible with organic peroxide-vulcanized rubber, and it is a necessary condition for the belt. It had a drawback that the bending fatigue property was deteriorated, and an improvement was necessary.

Therefore, an object of the present invention is to provide good adhesion to an organic peroxide vulcanized rubber excellent in heat resistance than a conventional sulfur vulcanized rubber while maintaining sufficient bending fatigue resistance as a belt. It is intended to provide an adhesive composition for a glass tensile member for a belt, which has resistance to bending fatigue.

[Means for solving the problem]

As a result of earnest research in view of the above object, the present inventors have found that organic peroxides can be added by complex addition of chlorinated rubber, chlorinated paraffin and silica powder to conjugated diene rubber, ethylene-propylene rubber or hydrogenated acrylonitrile-butadiene rubber. It was discovered that an adhesive composition for a glass tensile member having excellent adhesive strength and flex fatigue resistance to a material vulcanized rubber can be obtained, and the present invention has been completed.

That is, the adhesive composition of the glass tension member for an organic peroxide vulcanizing belt of the present invention is a conjugated diene rubber, ethylene-propylene rubber or hydrogenated acrylonitrile-butadiene rubber 100 parts by weight, and chlorinated rubber 1 to 200. 1 part by weight, 1 to 200 parts by weight of chlorinated paraffin, and 1 to 100 parts by weight of silica powder having an average particle size of 50 mμ or less.

 The present invention will be described in detail below.

The conjugated diene rubber is a rubber consisting of a conjugated diene alone or a rubber obtained by copolymerizing a conjugated diene with another component or two or more components, for example, styrene-butadiene rubber,
Acrylonitrile-butadiene rubber, butadiene rubber,
Examples thereof include isoprene rubber and natural rubber.

The ethylene-propylene rubber and hydrogenated acrylonitrile-butadiene rubber preferably have a saturation of 90% or more.

Chlorinated rubber is obtained by reacting rubber with chlorine gas, and the chlorine content is preferably 50% or more.

Paraffin chloride is a liquid substance obtained by chlorinating paraffin oil, and the chlorine content is preferably 40% or more.

The silica powder needs to have an average particle size of 50 mμ or less.
When the average particle size exceeds 50 mμ, the reinforcing effect in the adhesive layer is reduced.

The above-mentioned chlorinated rubber, chlorinated paraffin, and silica powder do not exhibit the intended effect of the present invention until they are added in combination.
Generally, conjugated diene rubber, ethylene-propylene rubber or hydrogenated acrylonitrile-butadiene rubber 100 parts by weight, the proportion of chlorinated rubber is 1 to 200 parts by weight, the proportion of chlorinated paraffin is 1 to 200 parts by weight, and silica powder. Is 1 to 100 parts by weight.

If the chlorinated rubber content is less than 1 part by weight, the adhesive strength will be insufficient and
Even if it exceeds 0 part by weight, the adhesive strength is lowered, which is not preferable.
The preferred content of chlorinated rubber is 10 to 80 parts by weight.

If the amount of chlorinated paraffin is less than 5 parts by weight, the adhesive strength will be insufficient, and if it exceeds 200 parts by weight, the adhesive strength will decrease, which is not preferable. The preferred content of chlorinated paraffin is 10 to 80 parts by weight.

When the amount of silica powder is less than 1 part by weight, the adhesive strength is lowered due to insufficient strength of the adhesive layer, and when it exceeds 100 parts by weight, application to a glass expander becomes difficult, which is not preferable. The preferred content of silica powder is 20 to 60 parts by weight.

The adhesive composition of the present invention usually contains an organic solvent so that it can be uniformly applied to a glass tensile member. Any organic solvent may be used as long as it can dissolve the above components, but one having 3 to 9 carbon atoms, for example, acetone,
Methyl ethyl ketone, methyl isobutyl ketone and the like are preferable. The content of the organic solvent can be appropriately selected so as to obtain a desired composition viscosity, but from the viewpoint of coating workability, it is preferably about 80 to 95% by weight of the entire composition.

The adhesive composition of the present invention may further contain a vulcanizing agent, a vulcanization aid, a vulcanization modifier, an antioxidant, an antioxidant, etc., if necessary.

 An organic peroxide or the like can be used as the vulcanizing agent.

The vulcanization modifier is used in combination with the vulcanizing agent to adjust the vulcanization, and includes mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), and 2-mercaptobenzothiazole zinc salt (ZnMBT). Thiazoles, N
-Sulfenamides such as cyclohexyl-2-benzothiazole sulfenamide (CBS), tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiulaudisulfide (TETD), tetrabutylthiuram disulfide ( TB
TD), dipetamethylene thiuram tetrasulfide (DPT
It is possible to use thiurams such as T).

 The vulcanization aid is a metal oxide such as zinc oxide.

The anti-aging agent is for preventing aging phenomena such as curing, softening, cracking, and loss of elasticity after vulcanization from occurring.
Mercaptobenzimidazole zinc salt (MBZ), 2,2,4-
Trimethyl-1,2-dihydroquinoline polymer (TMDQ),
N, N'-diphenyl-p-phenylenediamine (DPP
D) and p-phenylenediamines are effective.

The adhesive composition of the present invention adjusted to have an appropriate viscosity by adding an organic solvent is applied to the surface of the glass tensile member by a method such as a dipping method, a spray method or a brush coating method. After drying, the glass tensile member is embedded in a rubber material, and vulcanized and molded to produce a belt such as a desired toothed belt.

The glass tensile member coated with the adhesive composition of the present invention is characterized by being suitable for an organic peroxide vulcanized rubber. As the organic peroxide, for example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tert-butyl peroxypivalate, etc. The peroxides of can be used.

A vulcanizing agent, a vulcanization aid, a vulcanization modifier, an antioxidant, an antioxidant, a reinforcing agent and the like are appropriately added to the rubber material for the belt. The vulcanizing agent, vulcanization aid, vulcanization modifier, and antioxidant may be the same as above. The reinforcing agent improves the mechanical properties (tensile strength, hardness, tear strength, etc.) of the vulcanized rubber, and carbon black is preferable.

An example of manufacturing a toothed belt using a glass tensile member will be described.

First, a rubber material is molded by, for example, a mold having a tooth profile of a predetermined shape and size as shown in FIG. The mold comprises a lower mold 1 having a tooth-shaped surface and an upper mold 2 having a flat surface. When forming an endless toothed belt, it is preferable that the lower mold has a cylindrical shape and the upper mold has a diaphragm. A surface layer 3 such as canvas or a film is provided on the tooth profile, a rubber sheet is placed on the surface layer, and the mold is tightened while heating. As a result, the rubber layer 4 deformed into a tooth shape as shown in FIG. Is formed. At this time, the surface layer 3 is also deformed along the tooth profile, but in the case of a film, it may be deformed in advance. Next, a tensile strength cord 5 made of glass fiber is wound around the obtained belt tooth portion, a back rubber layer is provided, and then the upper mold 2 is tightened again for vulcanization. In this way, the toothed belt shown in FIG. 2 is obtained. Vulcanization temperature is generally 140-1
The temperature is 80 ° C, and the vulcanization time is 15 to 50 minutes.

[Action]

Since the adhesive composition of the present invention is obtained by adding chlorinated rubber, chlorinated paraffin and silica powder to rubber, it does not become so hard even when crosslinked, and at the same time, the adhesive layer obtained is moderately reinforced. Therefore, it is considered that the adhesiveness is excellent and the bending fatigue resistance is also excellent.

〔Example〕

 The present invention is described in more detail by the following examples.

Example 1 An adhesive composition having the following composition was prepared.

Zp2000 ⁽¹⁾ 100 parts by weight Zn (MAA) ⁽²⁾ 3 parts by weight MBZ ⁽³⁾ 1 part by weight Naugard445 ⁽⁴⁾ 1 part by weight CR-20 ⁽⁵⁾ 40 parts by weight ClParaffin # 70 ⁽⁶⁾ 40 parts by weight Carplex # 67 ⁽⁷⁾ 40 parts by weight Park Mill D-40 ⁽⁸⁾ 10 parts by weight Parroximon F-40 ⁽⁹⁾ 5 parts by weight Colloidal sulfur ⁽¹⁰⁾ 0.3 parts by weight TMTD ⁽¹¹⁾ 1 part by weight MBT ⁽¹²⁾ 0.5 parts by weight Organic solvent ⁽¹³⁾ 1400 parts by weight Note: (1) Nippon Zeon Co., Ltd. hydrogenated acrylonitrile-butadiene rubber (butadiene content 65% by weight, saturation
98%).

(2) Zinc methacrylate manufactured by Asada Chemical Co., Ltd. (3) Antiaging agent (2-mercaptobenzimidazole zinc salt) manufactured by Kawaguchi Chemical Co., Ltd.

(4) Anti-aging agent (4,4 ') manufactured by Uniroyal Chemical Co., Ltd.-
(Α, α-dimethylbenzyl) diphenylamine).

(5) Asahi Denka Kogyo Co., Ltd. chlorinated rubber (64% chlorine or more) (6) Ajinomoto Co., Inc. chlorinated paraffin (70% chlorine) (7) Shionogi Pharmaceutical Co., Ltd. silica powder (average particle size 20 m
μ) (8) Organic fat-based vulcanizing agent manufactured by NOF CORPORATION (40% by weight of organic peroxide (dicumyl peroxide), CaCO ₃ 60)
weight%).

(9) Organic peroxide-based vulcanizing agent manufactured by NOF CORPORATION (organic peroxide (α, α′-bis (t-butylperoxy-m-
Isopropyl) benzene) 40% by weight, CaCO ₃ 60% by weight).

(10) Vulcanization modifier manufactured by Hosoi Chemical Co., Ltd.

(11) Tetramethylthiuram disulfide vulcanization modifier manufactured by Kawaguchi Chemical Co., Ltd.

(12) Kawaguchi Chemical Co., Ltd. mercaptobenzothiazole vulcanization modifier.

(13) Methyl ethyl ketone The above adhesive composition was uniformly applied to a glass tensile member, sufficiently dried, sandwiched between rubber materials having the following composition, and vulcanized and molded at 160 ° C.

ZP2020 ⁽¹⁴⁾ 100 parts by weight ZnO ⁽¹⁵⁾ 10 parts by weight MBZ 1.0 parts by weight Naugard445 1.0 parts by weight Parkmill D-40 4.0 parts by weight Parroximon F-40 2.0 parts by weight HAF carbon black 40 parts by weight (Note): (14) Japan Zeon Co., Ltd. hydrogenated acrylonitrile-butadiene rubber (butadiene content 65% by weight,
90% saturation).

(15) Sakai Chemical Co., Ltd. zinc oxide vulcanization aid.

With respect to the obtained vulcanized sample, the tensile strength, the pull-out strength of the glass tensile member and the flex fatigue resistance were measured. The tensile strength was determined by performing a tensile test on the sample after the adhesive composition was applied. The pull-out strength was determined by measuring the force at which the glass tensile member pulled out of the rubber, using a sample vulcanized with one end of the glass tensile member protruding from the rubber material. In addition, flex fatigue resistance is determined by using a vulcanized sample in which a rubber material is adhered around the glass tensile member, and repeatedly performing a flex test while applying a tension of 11 kg to the sample until the sample is cut. It was determined by counting the number of cycles. The results are shown in Table 1.

Comparative Example 1 Each sample was prepared in the same manner as in Example 1 except that a commercially available resorcinol-formaldehyde resin-containing latex adhesive was used, and the same test was performed. The results are shown in Table 1.

From the above results, by using the adhesive composition of the present invention, the adhesive strength between the glass tensile member and the rubber material is good, and the bending fatigue resistance when bonded to the organic peroxide vulcanized rubber It can be seen that is significantly improved.

〔The invention's effect〕

As described in detail above, the adhesive composition of the present invention has excellent adhesion to an organic peroxide vulcanized rubber and good flex fatigue resistance. This shows that it is extremely useful as an adhesive for glass tension members for belts. Further, since a highly heat-resistant toothed belt or the like is vulcanized by an organic peroxide, the adhesive composition of the present invention is particularly effective for producing a high-performance toothed belt or the like.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of molding a toothed rubber, and FIG. 2 is a sectional view showing a toothed belt obtained by the method of FIG. 1 ... Lower mold 2 ... Upper mold 3 ... Surface layer 4 ... Rubber layer 5 ... Glass tensile member

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 123: 28) (C09J 123/16 115: 02 123: 28) (72) Inventor Mitsuaki Furuya Saitama 219-6 Terao, Kawagoe City, Japan (72) Inventor Kisei Achiha 2-1-8 Honjo, Honjo City, Saitama Prefecture

Claims (1)

(57) [Claims] 1. A conjugated diene rubber, ethylene-propylene rubber or hydrogenated acrylonitrile-butadiene rubber 10
0 parts by weight, 1 to 200 parts by weight of chlorinated rubber, 1 to 200 parts by weight of chlorinated paraffin, and 1 to 200 parts by weight of silica powder having an average particle size of 50 mμ or less.
An adhesive composition for a glass tensile member for an organic peroxide vulcanizing belt, which comprises 100 parts by weight.