JPS591548A - Rubber composition - Google Patents

Abstract

PURPOSE:To provide a rubber compsn. having excellent resistance to saline solutions and weather, adhesion to other material than rubber, etc., by blending 2,4,6-trithiol-s-triazine compd. (derivative), sulfur and a thermosetting phenolic resin with a rubber component. CONSTITUTION:1-15pts.wt. at least one member selected from 2,4,6-trithiol-s- triazine compd. and 2-substd.-4,6-dithiol-s-triazine derivative of the formula (wherein R is OR', SM, SR', NR'R'', NHC6H4NHC6H5; R', R'' are each H, alkyl, alkenyl, phenyl, phenylalkyl, naphthyl; M, M1, M2 are each H, Na, etc.) 0.5- 10pts.wt. sulfur and 5-40pts.wt. thermosetting phenolic resin are blended with 100pts.wt. rubber component such as natural rubber or polyisoprene rubber to obtain the desired rubber compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber composition, and more specifically, it has excellent adhesion to materials other than rubber such as steel cord, salt water resistance,
The present invention relates to a rubber composition with excellent properties such as weather resistance and bending resistance.

Conventionally, adhesion to dissimilar materials such as rubber, especially metals, has been difficult for composites that require reinforcement in the same way as adhesion to rubber and other organic fiber materials such as nylon, rayon, polyester fibers, resins, etc. It is an important factor and is used in a wide range of industrial applications. For this reason, various methods are known for bonding rubber and dissimilar materials, especially metals. For example, there is a method of using a halogenated T-lastomer such as chlorinated rubber or chloride oxide rubber, but the adhesive force is low against highly polar acryloni-1-helyl butadiene rubber, chloroprene rubber, etc. Also, polyisocyanates having two or more sardine-1~ groups in the molecule, such as 4.4'', 4''-1~rifhenylmethane triisocyanate-1~, 4.4''-diphenylmethane diisocyanate,' Polyarylbolyisocyanate, 1helis (4-) dinylisocyanate) thiophosph x-
Either a solution prepared by dissolving 1~ etc. in an organic solvent is applied alone, unvulcanized rubber is applied thereon and pressure vulcanized, or chloride rubber or chloroprene rubber is applied to the polyisocyaner 1~ and the A mixed solution of a specific ratio using a common solvent is applied to the metal surface, dried, and then a tie rubber containing no sulfur is added on top of the solution.
There are methods to cover the vulcanization by applying a rubber layer containing zinc white, vulcanization accelerator, etc., but the adhesive process is complicated,
Because it uses an organic solvent, there are restrictions on where it can be used, and polyisocyanate is affected by moisture in the air, resulting in variations in adhesive strength. Butyl rubber has some disadvantages such as poor adhesion.

There is also a method of pressure bonding using thermosetting adhesives such as urea or formaldehyde resin and an effect agent, but these have volumetric shrinkage and are not only inferior in water resistance, but also lack flexibility and are subject to repeated bending. It is not recommended for use in complexes that require a number.

The present invention was made to solve these drawbacks, and an object of the present invention is to provide a rubber composition that has excellent adhesion to dissimilar materials, especially metal materials, and has excellent properties after vulcanization.

This object of the present invention is based on 100 parts by weight of rubber,
1 to 15 parts by weight of 2.4.6-1 Helich A-Rue S-1
It is produced by a rubber composition containing a riazine compound or a derivative thereof, 0.5 to 10 parts by weight of a thermosetting phenolic resin and 5 to 40 parts by weight of a thermosetting phenolic resin. This rubber composition has excellent properties such as salt water resistance, weather resistance, and bending resistance after vulcanization, and also provides high adhesion to composite materials that can be bonded with different types of materials and bonded after vulcanization. Therefore, it is used to manufacture functional parts for automobiles, aircraft, ships, etc., and industrial rubber products such as rubber wheels, rubber rolls, rubber linings, belts, and hoses.

There is no particular restriction on the rubber content used in the present invention, and examples include natural rubber, diene-based synthesis of polyisoprene rubber, polybutadiene rubber, acrylonitrile butadiene rubber, styrene-butadiene copolymer rubber, chloroprene rubber, etc. Rubber, butyl rubber, ethylene-propylene-diene terpolymer rubber, ethylene vinyl acetate rubber,
Examples include olefinic synthetic rubber such as acrylic rubber, halogenated modified products thereof such as brominated butyl rubber, chlorinated butyl rubber, other fluororubbers, ether/thioether rubbers, polysulfide rubbers, urethane rubbers, silicone rubbers, etc. One or more of these may be blended in any proportion. The rubber components are mixed by mixers, closed mixers such as kneaders, continuous mixers such as Rus1 to Lugu, and mixing machines that are normally used in the rubber industry and Plus Book Industry. . In the present invention, materials other than rubber,
In particular, after the metal and the rubber composition are bonded and vulcanized, they are strongly bonded,
And when forming an integrated composite material, the rubber composition can be molded into any shape before vulcanization, and can be molded by continuous extrusion methods such as duper, rubber sheets by no. Essentially any molding method can be carried out, such as integral vulcanization by . The rubber composition according to the present invention exhibits its effects even when used alone or when two or more thereof are combined.

The rubber composition according to the present invention (well, composition A) has a high degree of adhesiveness after vulcanization, but of course it can be used not only as a solid rubber composition but also as a rubber composition dissolved in a general organic solvent when used. -b can be used in the form of a so-called cement paste.In this case, methods for treating the adherend include coating,
Any method used industrially such as spraying or dipping can be used. With this type of solvent () benzene,
Aromatic solvents such as cylene, carbon tetrachloride, styrene chloride, halogen-containing solvents such as 1-helichloroethylene, ester-based solvents such as dichloroethyl acetate, 11-hexadi, n
- Paraffinic hydrocarbon solvents such as octane, chain or cyclic ether solvents such as ethyl ether and tetrahydrofuran, and other solvents such as ketones alone or in combination can be used, but are not limited to these.

Vulcanization as used in the present invention means creating a crosslinking bond in the linear polymer of the rubber component in unvulcanized rubber to generate a three-dimensional network structure. Therefore, in addition to the most basic sulfur vulcanization, sulfur-containing vulcanization, organic peroxide vulcanization, metal salt vulcanization, quinoid vulcanization, organic polyvalent amine vulcanization, organic azo vulcanization, radiation vulcanization, Examples include electron beam vulcanization, crosslinking with polyisocyanate-1, and the like.

The general formula of the 2,4,6-trithiol-S-triazine compound or the 2-substituted-4°6-dithiΔ-ruS-1~riazine derivative used in the present invention is shown as follows.

R (However, R is OR+, SM, SR=, NR= R''
NHCa H4N1-Ic51-15, NHCs Hz
(t −C4Lls ) 0R1NHCs H
2(C+3) (t-04H7)
Of-1,5-C4C2(t-C41~l9)Of-
1, S-R--CO-R'', N11Cs l-14N (Cs 1-15) 2,
OC4H5 (01-1) COC4H5: R-OJ here
s and Ru are the same or different from each other and are hydrogen atom, al'nyl M (1 to 18 carbon atoms), ) fulkenyl group (1 to 18 carbon atoms), phenyl group, phenylalkyl group, naphthyl group, cycloalkyl group, or molyboryl group: where M, fvl+, and M2 are mutually the same or different, and are 1-1, positive, K, l r, 1/2 Ca,
1/2 Fka, 1/2Ba, 1/2Sr, 1/2Z
y, 1/2Ni, or 1/2Cu. ) 2.4.6-1-RithiΔ-ru-S-triazine compound or 2-substituted-4,4-dithiol-S,-1-lyazine derivative is preferably blended in an amount of 1 to 1 to 100 parts by weight of rubber. It is 15 parts of omega, more preferably 1 to 10 parts. If the blending amount is more than 15 parts by weight, the vulcanization rate will not be fast enough, and problems with so-called burning will occur during rolling, extrusion, etc., and processing will be difficult (this is disadvantageous; if it is less than 1 part by weight, There is no combination effect.

In the present invention, sulfur has the function of an adhesion aid, and for rubber components having a diene structure, it also functions as a vulcanizing agent. Its compounding amount is rubber content 10
The amount is 0.5 to 10 parts by weight based on the 0-fold assembly. If the amount of sulfur is less than 0.5 parts by weight, there will be no adhesive strength, and if it is more than 10 parts by weight, a bloom phenomenon will occur (undesirable as insufficient tack will occur when unvulcanized pieces are bonded together).

By blending the thermosetting phenolic resin, the rubber composition can become a rubber elastic body having good adhesive performance after vulcanization. The mixing ratio is between 5 and 40 parts by weight per 100 parts by weight of rubber. In the present invention, thermosetting phenolic resins include phenolic compounds such as 71nol, cresol, xylenol, resorcinol, pi[cogalol] and formaldehyde, ace]-aldehyde,
A general term for resins A5 obtained by reactions with aldehydes such as furfural, and their modified resins. Examples include phenol-acetaldehyde resin, phenol-formaldehyde resin, phenol-furfural resin, and resorcinol resin, which is a combination of phenol and aldehyde. Formaldehyde resin, etc. Further, among these phenolic compounds, those modified with alkyl groups include cresol-modified phenolic resins, oil-modified phenol resins, cashew-modified phenol 9-resins, and other terpene-modified phenol resins. Further, as phenol modified products, phenoxyacetic acid formaldehyde resins synthesized from aldehydes such as phenoxyacetic acid and its derivatives, such as methyl ester compounds, 1-methyl ester compounds, and phenyl 1-sumomides, are also included.

Also naturally included are phenolsulfonic acid type resins synthesized from phenolsulfonic acid and formaldehyde, and other phenol alkyd hybrid resins.

In addition to these essential ingredients, the rubber composition of the present invention contains various ingredients before vulcanization, such as vulcanization/crosslinking agents, vulcanization accelerators, activators, scorch inhibitors, anti-aging agents, and antioxidants. agent,
Ozone deterioration inhibitors, ultraviolet absorbers, plasticizers represented by mineral oil and vegetable oil, softeners, viscosity W4=J additives, rubber reinforcing agents such as carbon black, silica, clay, calcium carbonate, fillers, Vulcanization activators, foaming agents, foaming aids, antifoaming agents, stabilizers such as organic acid metal salts, lubricants, flame retardants, antistatic agents, coloring agents, coupling agents, antifoaming agents, flavoring agents, etc. can be kneaded in advance.

The rubber composition used in the rubber composition of the present invention,
Rubbers that are not normally subjected to sulfur vulcanization, such as 1" loprene rubber (CR), are metal vulcanized by a combination of zinc oxide and magnesila oxide 11, and ethylene propylene copolymer rubber, acrylonitrile butadiene rubber (N1"(I')<
), the present invention can also be used appropriately for those containing a small amount of sulfur.

Propylene; 44 cytorubber, tyrene vinyl acetate rubber,
The fact that the present invention can be applied to peroxide vulcanized products, such as silicone rubber, has great industrial significance, and a more preferable adhesive effect can be achieved depending on the use of the composite.

In the present invention as described above, in the early stage of vulcanization, compound i It is assumed that a chemical reaction takes place and a metal salt of triazine is formed. As a result, 2.4.6
-TrithiΔ-ru-5-1-lyazine compound and derivative Ij
Vulcanization progresses rapidly because the body is involved in crosslinking the rubber.
.

2.4.6 Trithi A-Rue S-1~Ryazine compound J
, and its derivatives have 1 to mercap groups in the same molecule, so they are particularly suitable for use in rubbers that have unsaturated bonds in the main chain and side chain, or in rubbers that use a radical initiator as a crosslinking agent. It will be done.

That is, mercap 1-it reacts with an unsaturated bond or the like to form a radical, and the lyazine compound or its derivative may be bonded to the pendant 1-type in the rubber molecule.

Generally, when the degree of vulcanization is at a very low level, the strength of the rubber material itself is weak, and the interface peeling phenomenon is likely to occur because K/V shear strain is applied near the interface of the adherend other than rubber. Copper metal is known as a substance that prevents vulcanization, so-called vulcanization-inhibiting action. Since the compound deactivates copper as a complex, the present invention can also be effectively applied to copper or alloys containing copper. Therefore, it goes without saying that the present invention can also be applied to alloys containing copper, such as copper-2-zinc alloy, copper-tin alloy 41, and alloys in arbitrary proportions. Others, aluminum,
It is also used for steel, light metal alloys such as chromium, nickel, manganese, and titanium, and stainless steel alloys.

The conventional ebonite bonding method, in which rubber contains sulfur in the range of 15 to 45% by weight, and a large amount of slaked lime, red iron oxide, and aluminum powder, has an extremely long vulcanization time compared to soft rubber, and also contains copper and copper. It does not adhere to the alloy, and excess sulfur adheres to the bonded area, causing a bloom phenomenon.

Therefore, the rubber composition of the present invention is essentially different from the ebonite method, and provides a composite l composed of a highly elastic vulcanized rubber classified as a soft rubber as one component.

In addition, as a conventionally known separate adhesion method, phenol-formaldehyde resin is used as a condensation catalyst.
Novolac-type reaction mode using acidic catalysts such as ilIM, hydrochloric acid, oxalic acid, phosphoric acid, etc., and resol-type reaction mode using basic catalysts such as 1-lium hydroxide, ammonia, and carbonate salts. However, the rubber composition of the present invention is essentially different from these methods.However, although the phenol-formaldehyde resin can provide a highly rigid product after curing, it has poor flexibility. As a result, stress concentration occurs at the adhesive interface, resulting in a lack of impact resistance and vibration resistance.

In addition to the above-mentioned metals, the adherends adjacent to the vulcanized rubber in the present invention include acrylonitrile butadiene-styrene resin, styrene-butadiene-styrene resin, high-impact polystyrene, polyvinyl chloride resin, and methyl methane resin. Homopolymers or copolymers made of conjugated diene compounds or vinyl compounds such as acrylate-1 resins, polyvinyl acetate resins and other polyvinyl alcohols, polyesters, bouylons, aramid m and other resins, melamine, epoxy,
Examples include, but are not limited to, plastic materials such as phenol resin, natural cords and composites thereof, woven fabrics, wood, other synthetic and natural leathers, and inorganic materials such as ceramics and glass.

The present invention will be explained in detail below based on Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, Table 1, 3J, and 4
The formulation in the table is as follows.

To Example 1・6 and L Meeting 1・4 Table 1 shows the small compounded Cf rubber and the compounding agents. Molded.

A 1 mm thick copper plate coated with brass plating (plating thickness 20 microns) with a ratio of 70-30 Zn was placed between the top and bottom of the rubber composition (unvulcanized rubber) and pressed at 148°C for 30 minutes. After sulfurizing, one rectangular specimen with a width of 25 mm and a length of 150 mm was obtained. O1 ~ Tensile speed Lσ50 in the graph
11111I /m1nr! A 1Jlift test was conducted. In addition, the rubber N point (%) represents the area of rubber monthly damage that occupies the area of peeling.

Further, the rubber composition (unvulcanized rubber sheet 1 to 1) was added to 148
℃ x 30 minutes press vulcanization and 150 depressions x 150min
Obtain a vulcanized rubber sheet of x2mm, J13 K6301
The JIS hardness was measured according to the following. The results are shown in Table 1.

15-375- J, sea urchin NBR exemplified in Table 1 is subjected to rubber separation to remove sulfur, 2,4.6-1 helithiol-3-triazine compound a3 and its derivatives, and thermosetting phenolic resin. Examples 1 to 6, in which the essential ingredients were mixed, were excellent in adhesion and rubber bonding points, and the JIS hardness was within an appropriate range. 2,4.6
-Trithiol-S-1 - Comparative Example 1.2, which does not contain the riazine compound, has extremely low adhesion horns, and the rubber f=J
The points are also inferior. Comparative Example 3, which did not contain sulfur, had good JIS hardness but poor adhesive strength and rubber mark. Comparative example 4, which does not contain thermosetting nof-nor resin, is J
Although the IS hardness is good, the adhesive strength is at a low level.

Examples 7 to 11 and Comparative Examples 5 to 9 The rubber components and compounding agents were kneaded on a roll machine according to the formulations shown in Table 2, and based on the same method as in Example 1 - C-applied horns, with rubber Table 2 shows the bonds whose JIS hardness and JIS hardness were measured.

17-377- As shown in Table 2, natural rubber is separated into three components: sulfur, 2,4.6-1 helithiol-8-1-lyazine compound, and thermosetting phenolic resin. All of the modified Examples 7 to 10 have favorable adhesive strength, rubberized dots, and JIS hardness. In Example 11, a part of the natural rubber was replaced with chloroprene rubber, but good results were obtained. Comparative Example 5 without TTC△, Comparative Example 6 without sulfur, Comparative Example 7 without thermosetting 9-Nol resin, and Comparative Example 8 with large amount of sulfur are JIS.
Hardness is relatively good, but adhesive strength and rubber attachment points are at a low level. In Comparative Example 8, since a large amount of sulfur was blended, a bloom phenomenon was observed on the surface of the vulcanized rubber. Comparative Example 9, in which the thermosetting phenol resin strip M was blended, is unfavorable because it loses rubber elasticity.

Examples 12 to 16 and Comparative Examples 10 to 14 With the formulations shown in Table 3, the rubber components and compounding agents were kneaded on a roll machine, and the adhesive strength, rubber dots and JIS were determined based on the same method as in Example 1. The results of hardness measurements are shown in Table 3.

19-379- Shown in Table 3", - Rubberize sea urchin SBR 2,
4.6-1 Examples 12 to 15 in which the three components of helithio-ru S-1 heliazine compound and thermosetting 14-Nol resin were blended and hung curved had favorable adhesive strength, rubbery
1 point J: indicates JIS hardness.

In Example 16, a part of SBR was replaced with natural rubber, and good results were obtained. However, in Comparative Example 14, which has the same rubber content as Example 16, the rubber attachment point is low because a small amount of thermosetting phenol resin is blended.

Comparative Example 10 without TCA, Comparative Example 11 without sulfur
, Comparative Example 12 without phenolic resin and Comparative Example 13 with sulfur between the strips.Although the JIS hardness is relatively good, the adhesive strength and rubbery point are at a low level. Also, IE comparative example 13
In this case, the vulcanization speed of the unvulcanized rubber becomes too fast, and burns occur during processes such as rolling and extrusion, which tends to cause trouble.

As described above, Comparative Example 14 contains only a small amount of thermosetting phenol resin, and therefore has poor adhesive strength and rubber attachment points.

Examples 17 to 20 J and Comparative Examples 15 to 17 Rubber and compounding agents were kneaded on a roll machine according to the formulations shown in Table 4, and the adhesive strength, -r iz f, was determined in the same manner as in Example 1. =
The results of measuring I hardness and JIS hardness were 811/1.
'I' shown in the table +1 As shown in Table 4, 1 dylene-propylene-diene 5-component polymer rubber (EPDM) is used as a rubber component, 2,4.6
Example 17 in which three components of -1-lithio-S-triazine compound and thermosetting phenol resin were blended and varied.
20 shows preferable adhesive strength, rubber point and JIS hardness. At this time, a small amount of sulfur is added to aTTC to improve basic physical properties such as compression set.
Comparative Example 15 without A, Comparative Example 16 without phenol resin, Comparative Example 17 without sulfur and TTCA.
S hardness is relatively good, but adhesive strength and rubber attachment points are at a low level.

As explained above, the rubber content contains 2.4.6-h lithio-
The rubber composition of the present invention, which contains a S-triazine compound or a derivative thereof, sulfur, and a thermosetting phenolic resin in a specific range, can be heated and vulcanized by bringing the rubber composition itself into contact with a material other than rubber before vulcanization. At the same time, a composite material containing the strongly bonded vulcanized rubber elastic body as one component is formed. In addition, since no organic solvent is required, it is suitable for producing a highly elastic composite agent which is excellent in terms of safety and health, is easy to handle, has a simplified adhesive treatment process, and has high productivity.

Furthermore, according to the present invention, in addition to being used as a solid rubber composition, it can also be used as cement 1, and furthermore, different rubbers can be laminated by laminating different rubbers together and then heating them. An integrated product is formed, and if used as a binder between vulcanized rubbers, it can also be used to manufacture bullets with complex shapes.

Patent applicant: Yokohama Rubber Co., Ltd. Representative Patent Attorney Tatsuo Ito Representative Patent Attorney Tetsuya Ito

Claims (1)

[Claims] 1. For 100 parts by weight of rubber, add 1 to 1.2 to 15 parts by weight. i 6-Trithiol-Sl~at least 1f of lyazine compound or 2-substituted-4,6-dithiA-S-triazine derivative! Rubber composition 1, characterized in that it contains 0.5 to 10 parts of sulfur and 5 to 40 parts of thermosetting phenolic resin.