JPH0366733A - Fiber-rubber composite material - Google Patents

Abstract

PURPOSE:To obtain a fiber-rubber composite having excellent adhesion between the fiber and the rubber by vulcanizing integrally fibers treated with a specific dip solution and an ethylene-propylene copolymer rubber composition vulcanizable with an organic peroxide. CONSTITUTION:The subject fiber-rubber composite is produced by vulcanizing integrally (A) fibers treated with a dipping solution containing an initial condensate from resorcin and formaldehyde and a chlorosulfonated polyethylene latex at a solid ratio of 5/100 to 35/100 and (B) a rubber composition containing B1: 100 parts.wt. of base rubber containing more than 75wt.% of ethylene- propylene copolymer rubber, and preferably 0 to 10wt.% of halogenated rubber, B2: 3 to 10 pts.wt. of 1,3-phenylenebis(2-oxazoline) and B3 1/10 mole to 1/300 mole of an organic peroxide vulcanizer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fiber-rubber composite having excellent heat-resistant adhesion between fiber and rubber.

<Prior art> Ethylene-propylene copolymer rubber compositions have heat resistance,
Because it has excellent weather resistance and ozone resistance, it is expected to be used in applications such as heat-resistant belts and heat-resistant hoses. In manufacturing rubber products, usually, in order to increase the strength, a plurality of layers made of a rubber composition are laminated, and a reinforcing layer made of fibers such as carbon fiber material is arranged between the layers. ．． However, ethylene/propylene copolymer rubber compositions have limited adhesion to fibers, so their uses are limited. In view of this drawback, various proposals have heretofore been made to ensure sufficient vulcanization adhesion between rubber compositions and organic fiber materials.

To give an example, a specific amount of dialkyl peroxide and di(meth)acrylates are blended into a rubber composition as disclosed in Japanese Patent Application No. 137376/1985! 1I
11 fibers are treated with a dipping liquid containing an initial condensate of resorcinol and formaldehyde and latex, and a method of using fibers treated with a co-cement solution of a rubber composition. Initial condensate of resorcin and formaldehyde, chlorosulfonated polyethylene, chlorosulfonated polypropylene, chlorosulfonated ethylene/vinyl acetate copolymer, chlorosulfonated ethylene/propylene/diene copolymer disclosed in Japanese Patent No. 105476 A method of using fibers treated with a dipping liquid containing a latex containing one or more polymers selected from chlorosulfonated ethylene/propylene copolymer, chlorosulfonated isobutylene/isoprene copolymer, and chlorosulfonated isobutylene/isoprene copolymer. The initial condensate of resorcinol and formaldehyde disclosed in Publication No. 40227, and polybutadiene latex and/or styrene-butadiene latex (however, the copolymerization amount of styrene is 10% by weight or less), or There is a method of using fibers treated with a dipping solution prepared by adding a condensate of a halogenated phenol compound such as p-chlorophenol, formaldehyde, and resorcinol to a mixed solution containing butadiene, styrene, and vinylpyridine latex.

<Problems to be Solved by the Invention> As mentioned above, a method has been proposed to ensure sufficient adhesive strength when vulcanizing and adhering fibers and an ethylene-propylene copolymer rubber composition. .

However, Japanese Patent Application No. 57-137376 and JP-A-57
Rubber products made by the method disclosed in Japanese Patent Publication No. 105476 and the method using 1a fibers treated with a co-cement solution of a rubber composition have improved normal adhesive strength between the rubber composition and the fibers. However, due to poor adhesion after heat aging, the product cannot be used in applications that take advantage of the heat resistance, which is a feature of ethylene-propylene copolymer rubber compositions.

In addition, rubber products made by the method disclosed in Japanese Patent Publication No. 63-40227 show little deterioration in adhesive properties due to heat aging, but their adhesive strength itself is not sufficient and their practical value is low. .

The present invention has been made in view of the above facts, and is a fiber-rubber composite in which fibers and an ethylene-propylene copolymer rubber composition are integrally vulcanized. The present invention aims to provide a fiber-rubber composite in which fibers and a rubber composition adhere with sufficient adhesive force even after aging or heat aging, and the rubber composition after vulcanization has sufficient rubber physical properties.

Means for Solving the Problems> The present invention provides a fiber treated with a dip-n-coat containing an initial condensate of resorcinol and formaldehyde (RF) and a chlorosulfonated polyethylene latex (L), and an ethylene-propylene-based fiber. Organic peroxide vulcanized ethylene/propylene copolymer rubber containing 3 to 10 parts by weight of 1,3-phenylenebis(2-oxazoline) per 100 parts by weight of raw material rubber containing 75 parts by weight or more of copolymer rubber. The present invention provides a fiber-rubber composite characterized in that the composition and the composition are integrally vulcanized.

The organic peroxide vulcanized ethylene/propylene copolymer rubber composition preferably contains halogenated rubber in an amount of 0 to 10 parts by weight based on 100 parts by weight of the raw rubber.

The present invention will be explained in detail below.

The fibers used in the m-fiber rubber composite of the present invention are normally used as reinforcing materials in rubber products such as belts, tires, and hoses. That is, aliphatic boriayodo fibers, polyester fibers, U fibers, regenerated cellulose fibers, polyvinyl alcohol synthetic fibers, polyolefin synthetic 1m fibers, aromatic polyamide fibers, and the like.

Aliphatic polyamide fiber is a polymer compound having an acid-acid bond and a straight saturated hydrocarbon portion in the molecule.

Specifically, nylon 6 fiber, nylon 66 fiber, nylon 46 fiber, etc. can be mentioned.

Polyester fiber is a polymer compound obtained by condensation polymerization of a polyhydric organic acid and a polyhydric alcohol, and polyethylene terephthalate fibers are usually used.

In addition, regenerated cellulose fibers include viscose rayon fibers, polyvinyl alcohol synthetic fibers include vinylon fibers, polyolefin synthetic fibers include polypropylene fibers, and aromatic boria fibers include poly(p-phenylene terephthalamide) ia. fibers etc. are used.

Note that the fibers used are woven fabrics, thread-like fibers, and cord-like fibers.

Such as dip-n-night for processing fibers,
In the present invention, a material containing an initial condensate (RF) of resorcin and formaldehyde and chlorosulfonated polyethylene latex (L) is used.

Here, RF refers to reacting resorcin and formaldehyde at a predetermined charging molar ratio in the presence of a basic catalyst, or reacting formaldehyde in an amount of 1 mol or less per 1 mol of resorcin with an acidic catalyst. This is a compound obtained by reacting in the presence of a basic catalyst and then adding formaldehyde later in the presence of a basic catalyst.

Commercially available products include Sumikanol 700 (manufactured by Sumitomo Chemical Industries, Ltd.) and Atover RF (manufactured by Hodogaya Chemical Industries, Ltd.), which are used as they are or after further reaction with formaldehyde.

What is chlorosulfonated polyethylene latex (L)?
A latex containing chlorosulfonated polyethylene in an amount of 50% by weight or more of the polymer in the latex.
Other polymers blended here include vinylpyridine-butadiene-styrene, terpolymer latex, styrene-butadiene copolymer latex, and the like. Furthermore, the reason why 50% by weight or more of the polymer in the chlorosulfonated polyethylene latex (L) is made of chlorosulfonated polyethylene is to increase the initial adhesive strength.

In addition, as a commercial product, C3M450 (Steel Chemical Industry Co., Ltd.
R) etc.

The quantitative ratio of the above-mentioned components is not particularly limited, but the molar ratio of resorcinol (R) and formaldehyde (F) is about 1:0.6 to 3.5, and the initial condensate (RF) of resorcinol and formaldehyde is and latex (L) at a solid content ratio of about 5+100 to 35:100, and a dry solid content of about 5 to 20%, the dipping liquid will not gel and the fibers will be immersed in the dipping liquid. The amount of pick-up at the time is appropriate, which is also favorable in terms of adhesive performance.

In addition, surfactants, plasticizers, thickeners, and the like may be added to the dip liquid used in the present invention as long as the gist of the present invention is not impaired.

The organic peroxide vulcanized ethylene/propylene copolymer rubber composition used in the present invention refers to ethylene/propylene copolymer rubber compositions containing ethylene/propylene as raw material rubber.
Propylene rubber (hereinafter referred to as EPM) and/or ethylene-propylene-diene terpolymer rubber (hereinafter referred to as
Contains 75% by weight or more of raw rubber (referred to as EPDM),
A rubber composition containing 3 to 10 parts by weight of 1,3-phenylenebis(2-oxazoline) based on 100 parts by weight of the raw material rubber, and further containing an organic peroxide-based vulcanizing agent as a vulcanizing agent. It is. Examples of the diene component of EPDM include methylene norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, methyltetrahydroindene, and the like.

Here, EPM and/or EPDM is 7% of the raw rubber.
The reason why it must be 5% by weight or more is because if it is less than 75% by weight, the characteristics of EPM and/or EPDM will not be fully expressed.

Other rubbers that may be blended with EPM and/or EPDM include chlorinated polyethylene, chlorinated EPM
, chlorinated EPDM, chlorinated butyl rubber, brominated butyl rubber, etc. However, when halogenated rubber such as chlorinated polyethylene is blended in a range of 0 to 10 parts by weight based on 100 parts by weight of raw material rubber, the adhesive strength with fibers increases. further improved,
preferable.

1.3-Phenylenebis(2-oxazoline) is represented by the following formula (1), and in the present invention, it can be combined with the fibers treated with the dip liquid without reducing the physical properties of the rubber after vulcanization. This is a component that improves heat-resistant adhesion after vulcanization with a peroxide-vulcanized ethylene/propylene copolymer rubber composition.

The organic peroxide vulcanized ethylene/propylene copolymer rubber composition used in the present invention includes 1,3-phenylene bis(2
-oxazoline) is contained in an amount of 3 to 101 parts by weight based on 100 parts by weight of the raw material rubber. If the amount is less than 3 parts by weight, sufficient heat-resistant adhesive properties will not be exhibited, while if it exceeds 10 parts by weight, the physical properties of the rubber after vulcanization of the rubber composition will deteriorate, which is not preferable.

Further, as the vulcanizing agent, an organic peroxide-based vulcanizing agent is used.
This is because when a sulfur-based vulcanizing agent is used, 1,3-phenylenebis(2-oxazoline) reacts with the amine-based vulcanization accelerator used in conjunction with the sulfur-based vulcanizing agent, which prevents vulcanization. This is because the rubber physical properties of the rubber composition after vulcanization are deteriorated.

Incidentally, it has been reported in an international publication that deterioration of polyester M can be prevented by adding 1,3-phenylenebis(2-oxazolicane) used in the present invention to a rubber composition containing an aion-based vulcanization accelerator. Patent WO39102908 (19
89,4゜6), the present invention applies 1,3-phenylenebis(2-oxacillin) to an organic peroxide compounded rubber composition that does not contain an amine vulcanization accelerator. , and the gist is different.

Examples of organic peroxide-based vulcanizing agents include dialkyl peroxides and peroxyketals. Dialkyl peroxides are preferred, and those with a decomposition temperature of 117°C or higher are more preferred.

More specifically, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-
t-Butylperoxyhexane, 2,5-dimethyl-2
,5-di-t-butylperoxyhexyne-3,1,3
-bis(t-butylperoxyisopropyl)benzene and the like.

The organic peroxide-based vulcanizing agent is preferably contained in an amount of 1/10 to 1/300 mol based on ioo parts by weight of the raw material rubber,
More preferably, it is contained in an amount of 1/20 to 1/150 mol. If it is less than 1/300 mole, sufficient vulcanization adhesion will not be achieved, while if it exceeds 1/10 mole, heat resistance will be impaired or scorch will occur easily.

The organic oxide vulcanized ethylene/propylene copolymer rubber composition used in the present invention contains the above raw material rubber, 1,3-phenylenebis(2-oxazoline), and an organic peroxide vulcanizing agent. In addition to these, a vulcanization aid, a plasticizer, a reinforcing agent, an anti-aging agent, etc. may be contained as necessary.

As shown in FIG. 1, the fiber-rubber composite of the present invention consists of fibers 1 treated with a dipping liquid, which are formed into an unvulcanized organic peroxide vulcanized ethylene-propylene copolymer and formed into a sheet shape or the like. The rubber composition 2 is laminated between the eyebrows and vulcanized. However, the number of flies is not limited.

Here, treatment of fibers with a dip liquid refers to immersing the fibers in the dip liquid, or applying the dip liquid to the fibers by brushing, spraying, etc., followed by drying, and if necessary, further heat treatment (baking). ), and usually drying is carried out at a temperature of 100 to 150℃ for 1 to 5 minutes.
Heat treatment (baking) for about 18,0~23 minutes
This is done for about 1 to 5 minutes at about 0°C. The vulcanization is carried out at 140 to 180° C. by a conventional method such as indirect air vulcanization, direct steam vulcanization, press vulcanization, or leaded vulcanization. The vulcanization time may be appropriately selected depending on conditions such as the vulcanization temperature.

The fiber rubber composite of the present invention can be used for belts, hoses, tires, etc. In the case of a belt, it may have a structure as shown in FIG. A structure may also be provided in which a cover rubber layer having a compounded composition is provided. Further, in the case of a hose, the fiber layer in the fiber rubber composite of the present invention can be used as a reinforcing layer.

<Example> The present invention will be specifically described below based on Examples.

(Example 1) The rubber composition shown in Table 1 was molded into a sheet, and the organic peroxide vulcanization system (A-1 to A-6, B-1, B-2)
Vulcanization was carried out at 0°C for 45 minutes, and in the case of the sulfur vulcanization system (C-1, C-2), vulcanization was carried out at 150 tons for 30 minutes.

The obtained vulcanized rubber sheet was subjected to a tensile test in accordance with JIS K2SO3, and the 300% modulus was measured.

The results are shown in FIG. 2, with the modulus being 100% and 300% of the system without 1.3-PBO.

As is clear from Table 1 and Figure 2, in the sulfur vulcanization system, 1,3-phenylenebis(2-oxazoline) (1,
3-PBO) significantly reduced the modulus. However, in organic peroxide vulcanization system, 1.3
-If the amount of PBO added was within 10 parts by weight, the modulus decreased only slightly.

Such a decrease in the modulus of sulfur-vulcanized rubber is mainly caused by the reaction of 1,3-PBO with the amine-based vulcanization accelerator contained in the sulfur-vulcanized rubber composition, which retards vulcanization. It is presumed that this was done in order to

Since the organic peroxide vulcanization rubber composition does not contain an amine vulcanization accelerator, a decrease in modulus due to vulcanization delay does not substantially occur.

(Example 2) Nylon 66 840d/lX840d/1 density 110
A plain woven fabric of x40 wood/5 cm was immersed in the dip liquid (D-1) shown in Table 2, squeezed with a roll so that the resin solid content was 6%, and then dried at 120°C for 3 minutes. death,
Further, heat treatment was performed at 220° C. for 2 minutes.

As a conventional example, the above-mentioned plain woven fabric was
' According to the method disclosed in Publication No. 7, it was immersed in the dip liquid (D-2) shown in Table 2, squeezed with a roll so that the resin solid content was 6%, and then dried at 120 ° C. for 3 minutes. Then, it was further heat-treated at 220°C for 2 minutes.

The dip liquid obtained in this way! Table 1
Rubber composition shown in (however, only organic peroxide vulcanization type)
The sample was laminated to the substrate and press-vulcanized at 160° C. for 45 minutes to prepare a sample for adhesion evaluation having a two-braid structure as shown in FIG.

Adhesion was evaluated by an initial adhesion test in which the sample was left in room salt for 1 day after vulcanization, and then the fabric-rubber layer was peeled off to determine the rubber adhesion rate on the peeled surface, and after the sample was left at 150°C for 30 minutes. ,1
A heat battle adhesion test was carried out in which the textile-rubber layer was peeled off at 50°C or lower to determine the rubber adhesion rate on the peeled surface.The sample was heat-aged at 150°C for 7 days, then cooled to room temperature, and the textile-rubber layer was separated at room temperature. It was peeled off and a heat aging adhesion test was conducted to determine the rubber adhesion rate on the peeled surface.

The results are shown in Table 3 and Figure 3 (However, Figure 3 shows only the combinations of dip liquid D-1 and rubber compositions A-1 to A-6)
It was shown to.

As is clear from Table 3 and Figure 3, 1.3-PBO
When using a rubber composition containing 31i parts or more of ia
The heat-fighting and heat-aging adhesion between fiber and rubber were significantly improved.

On the other hand, in a conventional example using fibers treated by the method disclosed in Japanese Patent Publication No. 63-40227, 1
．． When 3-PBO was included, heat battle adhesion was improved compared to a system without 1,3-PBO, but heat aging adhesion was reduced.

<Effects of the Invention> The present invention provides a fiber and organic peroxide vulcanized ethylene/propylene system that has excellent initial and hot-fight adhesion, little deterioration of adhesion due to heat aging, and a rubber layer with sufficient rubber physical properties. A fiber rubber composite comprising a copolymer rubber composition is provided.

Therefore, the applications of the ethylene-propylene copolymer rubber composition, which has excellent heat resistance, weather resistance, and ozone resistance, are expanded.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of the fiber rubber composite of the present invention. Figure 2 shows the 1.3-PBO content of the rubber composition and the 300
It is a graph showing the relationship with % modulus change rate. FIG. 3 is a graph showing the relationship between the 1.3-PBO content of the rubber composition and the adhesion shown by the rubber adhesion rate. Explanation of symbols 1...Fiber treated with dipping liquid, 2...Organic peroxide vulcanized ethylene/propylene copolymer rubber composition FIG, 1 FIG, 2 1 3-PBO building t! H (It part)

Claims (2)

[Claims] (1) Contains fibers treated with a dip liquid containing an initial condensate of resorcinol and formaldehyde (RF) and chlorosulfonated polyethylene latex (L), and 75% by weight or more of ethylene-propylene copolymer rubber. An organic peroxide vulcanized ethylene/propylene copolymer rubber composition containing 3 to 10 parts by weight of 1,3-phenylenebis(2-oxazoline) per 100 parts by weight of raw rubber is vulcanized and integrated. A fiber-rubber composite characterized by the ability to (2) The fiber rubber composite according to claim 1, wherein the organic peroxide vulcanized ethylene/propylene copolymer rubber composition contains halogenated rubber in a range of 0 to 10 parts by weight based on 100 parts by weight of raw rubber. thing.