KR900006525B1 - Reinforced rubber composition and production thereof - Google Patents

Abstract

A fibre-reinforced rubber compsn. comprises vulcanisable rubber including fine short fibres of a thermoplastic polymer (I) including -CO-NH-groups. The rubber and (I) are grafted to each other through a resol alkyl phenol formaldehyde resin precondensate (II) or a novolak phenol formaldehyde resin precondensate (III) at an interface of the fibre. The ratio of fibres to rubber is 1-70 wt.% if (II) is used or 1-100 wt.% if (III) is used. The vulcanised compsn. has high tensile and tear strength and modulus and good fatigue characteristics. It is used for tyre belts, carcasses, beads, treads or sidewalls, belts, hoses or footwear.

Description

Reinforced rubber composition and its manufacturing method

The present invention relates to a novel reinforced rubber composition excellent in workability and excellent in strength and modulus of a vulcanizate and a method for producing the same.

Conventionally, reinforcing rubber compositions used for respective members of tires are manufactured by blending short fibers such as nylon, polyester, vinylon, and the like with vulcanizable rubber. However, the reinforced rubber composition obtained in this way has a large fiber diameter and does not have a bond between the fiber and the rubber, which is why the strength and modulus of the vulcanizate, in particular, the modulus and strength at high elongation, are not sufficient. There is a demand for development of reinforced rubber compositions that provide vulcanizates with superior modulus and strength.

Therefore, an elastomer reinforcement method and a reinforced elastomer composition have been proposed in which a polymer having a fiber forming ability and a rubber are kneaded and then the mixture is extruded. (Japanese Patent Laid-Open No. 53-8682). However, even with this method, coarse fibers and films are produced, and there is no bond between rubber and polymer (fiber) at the fiber interface, so that the tensile strength of the vulcanizate and the peel strength indicating the adhesive strength between the modulus and other substrates at high elongation are small. It is not possible to obtain a reinforced rubber composition that can be used as a tire member.

Japanese Unexamined Patent Publication No. 55-41652 describes a method of kneading vulcanizable rubber and powder 1,2-polybutadiene to extrude a kneaded material and then roll into a roll to produce a reinforced rubber composition. The reinforcing rubber composition obtained by this method has high elasticity, high elongation, high strength and high peeling strength, but the strength of the fiber formed from 1,2-polybutadiene is small, so that the fiber during rubber processing, especially in carbon black kneading Has a drawback that the fiber length is shortened and the stress at the time of elongation of the vulcanizate is small.

Thus, in order to remedy the shortcomings of the conventionally known reinforcing rubber composition, the present inventors melt-extrude a composition containing a block copolymer of liquid diene rubber and nylon into a vulcanizable rubber to fiberize nylon and at the same time vulcanize rubber and liquid A method for preparing a reinforced rubber composition for grafting diene rubber is proposed (Special Element No. 56-117044). However, this manufacturing method has problems in practical use because the reproducibility of block polymerization is not so good and the cost is high.

MEANS TO SOLVE THE PROBLEM The present inventors completed this invention as a result of earnest research for the purpose of providing the reinforced rubber composition which does not have the above fault, and its manufacturing method.

기를 가진 열가소성폴리머의 미세한 단섬유 1 내지 100중량부가 매봉(埋封)되어 있고 또한 이 섬유의 계면에 있어서 상기 폴리머와 가황가능한 고무가 노볼락형 페놀포름알데히드계수지의 초기축합물을 통하여 그라프트하고 있는 강화고무조성물 및 가황가능한 고무와 분자량 200,000미만의 폴리머 분자중에

기를 가진 열가소성 폴리머와 이들 고무와 열가소성 폴리머와의 합계량 100중량부당 0.2 내지 5중량부의 노볼락형 페놀 포름알데히드계수지의 초기축합물(이하 단순히 노볼락이라고 말하기도 한다)과 가열시에 포름알데히드를 발생시킬 수 있는 화합물을 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 혼련하여 얻어진 혼련물을 혼련물중의 고무와 열가소성 폴리머와의 비율이 고무 100중량부당 열가소성 폴리머가 1 내지 100중량부인때는 그대로, 혼련물중의 고무와 열가소성 폴리머와의 비율이 고무 100중량부당 열가소성 폴리머가 1중량부보다 많아질때는 추가의 가황가능한 고무를, 전부의 고무 100중량부당 열가소성 폴리머가 1 내지 100중량부로 되도록 혼련물에 첨가하여 다시 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 혼련한후 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 압출하여 압출물을 열가소성 폴리머의 융점보다 낮은 온도에서 연신하는 것을 특징으로 하는 강화고무조성물의 제조법에 관한 것이다.In other words, the present invention is 100 parts by weight of vulcanizable rubber in the polymer molecule

1 to 100 parts by weight of the fine short fibers of the thermoplastic polymer having groups are buried, and at the interface of the fibers, the polymer and the vulcanizable rubber are grafted through the initial condensation product of the novolak type phenol formaldehyde resin. Reinforcing rubber compositions and vulcanizable rubber and polymer molecules with molecular weight less than 200,000

The initial condensate of a novolak-type phenol formaldehyde-based resin (hereinafter referred to simply as novolak) with a thermoplastic polymer having a group and 0.2 to 5 parts by weight per 100 parts by weight of these rubbers and thermoplastic polymers is generated. The kneaded product obtained by kneading the compound capable of being kneaded above the melting point of the thermoplastic polymer and at a temperature of 270 ° C. or lower is as it is when the ratio of the rubber and the thermoplastic polymer in the kneaded material is 1 to 100 parts by weight of the thermoplastic polymer per 100 parts by weight of the rubber. When the ratio of the rubber in the kneaded material to the thermoplastic polymer is more than 1 part by weight of the thermoplastic polymer per 100 parts by weight of rubber, the additional vulcanizable rubber is kneaded so that the thermoplastic polymer is 1 to 100 parts by weight per 100 parts by weight of the rubber. Added to water and again above the melting point of the thermoplastic polymer and at a temperature of After kneading, the present invention relates to a method for producing a reinforced rubber composition characterized by extruding the extrudate at a temperature lower than the melting point of the thermoplastic polymer by extruding it above the melting point of the thermoplastic polymer and below 270 ° C.

The reinforced rubber composition of the present invention is excellent in productivity and processability, and can be given a vulcanized product having excellent modulus, tensile strength, and adhesiveness at low and high elongation.

기를 가진 열가소성 폴리머, 노볼락형 페놀 포름알데히드계수지의 초기 축합물(노볼락) 및 가열시에 포름알데히드를 발생시킬 수 있는 화합물로부터 우수한 물성을 가진 가황물을 부여하는 강화고무조성물을 간단한 조작으로 재현성 좋게 제조할 수가 있다.In addition, according to the method of the present invention, vulcanizable rubber, a molecular weight of less than 200,000

Reproducibility of the reinforcement rubber composition which gives the vulcanizate with excellent physical properties from the thermoplastic polymer having the group, the initial condensate of the novolak-type phenol formaldehyde resin (novolak) and the compound capable of generating formaldehyde upon heating It can be manufactured well.

기를 가진 열가소성 폴리머와 노볼락과 가열시에 포름알데히드를 발생시킬 수 있는 화합물과의 혼합물을 혼련하고 이어서 혼련물을 압출할때에 겔화하는 일이 거의 없는 천연고무가 바람직하다.As the vulcanizable rubber in the present invention, all rubbers which give rubber elasticity by vulcanization can be used. For example, natural rubber, cis-1,4-polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer rubber, isoprene- Isoprene copolymer, ethylene-propylene-non-conjugated diene terpolymer, and mixtures thereof. Among these rubbers, vulcanizable rubbers and molecules

Preference is given to kneading a mixture of a thermoplastic polymer having a group with a novolak and a compound capable of generating formaldehyde upon heating, and then natural rubber which hardly gels when the mixture is extruded.

기를 가진 열가소성 폴리머의 미세한 단섬유 1 내지 100중량부, 바람직하기는, 1 내지 70중량부, 특히 바람직하기는 30 내지 70중량부가 매봉되어 있으며 또한 이 섬유의 계면에 있어서 상기 폴리머와 가황가능한 고무가 노볼락을 통하여 그라프트(결합)하고 있는 것이다.The reinforced rubber composition of the present invention is contained in 100 parts by weight of the vulcanizable rubber in the polymer molecule.

1 to 100 parts by weight, preferably 1 to 70 parts by weight, and particularly preferably 30 to 70 parts by weight, of fine short fibers of the thermoplastic polymer having groups, and at the interface of the fibers, It is grafting through a novolac.

기를 가진 열가소성 폴리머, 바람직하기는 나일론으로 형성되어 있으며 평균경이 0 05 내지 0.8μ이며 원형단면의 최단섬유길이가 바람직하기는 1μ이상이며 섬유측방향으로 분자가 배열된 미세한 단섬유의 형태로 가황가능한 고무중에 매봉되어 있다.The fine short fibers of the thermoplastic polymers described above have nylons such as nylon 6, nylon 610, nylon 12, nylon 611, nylon 612 having a melting point of 190 to 235 ° C, preferably 190 to 225 ° C, particularly 200 to 220 ° C. In polymer molecules such as polyurea and polyurethane such as poly-heptamethylene urea and polyundecamethylene urea

Thermoplastic polymer having groups, preferably made of nylon, having an average diameter of 0 05 to 0.8μ, the shortest fiber length of a circular cross section, preferably 1μ or more, and vulcanizable in the form of fine short fibers in which molecules are arranged in the fiber side direction. It is embedded in rubber.

기를 가진 열가소성 폴리머와 가황가능한고무가 노볼락을 통하여 그라프트하고 있다.Furthermore, in the polymer molecule at the interface of the fiber described above

Thermoplastic polymers and vulcanizable rubbers are grafted through novolacs.

The above-mentioned novolac is a solubility obtained by condensation reaction of a phenol such as phenol or bisphenol with formaldehyde (may be paraformaldehyde) by using a catalyst of its own known, for example, sulfuric acid, hydrochloric acid, phosphoric acid, or hydroxy acid as a catalyst. It is resin of jung, and its modification (modified substance). As the novolak, for example, a novolak-type phenol formaldehyde initial condensate, a novolak-type lactum-bisphenol F-formaldehyde initial condensate, a novolak-type styrenated phenol-phenol-formaldehyde initial condensate and the like can be preferably used.

기를 가진 열가소성 폴리머의 미세한 단섬유의 강도가 크고 더우기 이 섬유의 계면에 있어서 상기 열가소성 폴리머와 가황가능한 고무가 노볼락을 통하여 그라프트 결합하고 있기 때문에 저신장시 및 고신장시의 모듈러스및 인장강도가 우수하고 더우기 천연고무가황물과 같은 고무 가황물이나 스티일등의 부재에 대한 접착성이 뛰어난 가황물을 부여하는 강화 고무 조성물을 얻을 수가 있는 것이다.In the reinforced rubber composition of the present invention, polymer molecules embedded in vulcanizable rubber

The strength of the fine short fibers of the thermoplastic polymer having a group is high, and further, at the interface of the fibers, the thermoplastic polymer and the vulcanizable rubber are grafted through the novolac, so the modulus and tensile strength at low and high elongation are excellent. In addition, it is possible to obtain a reinforced rubber composition for imparting a vulcanizate having excellent adhesion to a rubber vulcanizate such as a natural rubber vulcanizate or a member such as a styre.

기를 가진 열가소성 폴리머, 노볼락 및 포름알데히드 공여체인 가열시에 포름알데히드를 발생시킬 수 있는 화합물의 반응양식에 대해서는 단정적으로는 말할 수 없으나 노볼락에 포름알데히드 공여체로부터 발생한 포름알데히드가 먼저 작용하여 노볼락에 적어도 2개의 메틸롤기가 생성되어 이 복수의 메틸롤기중의 하나의 수산기와 가황가능한 고무의 폴리머분자중의 메틸렌기의 수소원자와의 탈수반응, 및 열가소성 폴리머 분자중의

기의 수소원자와 가황가능한 고무와 결합하고 있는 노볼락의 나머지의 메틸롤기의 수산기와의 탈수반응에 의해서 생성하는 것이라고 생각된다.In addition, the graft bonds are used in vulcanizable rubber and polymer molecules.

The reaction mode of the thermoplastic polymer having the group, the novolak and the compound that can formaldehyde upon heating as a formaldehyde donor can not be stated with certainty, but the formaldehyde generated from the formaldehyde donor in the novolak first acts as a novolak. At least two methylol groups are formed in the hydroxyl group of one of the plurality of methylol groups and the dehydration reaction between the hydrogen atom of the methylene group in the polymer molecule of the vulcanizable rubber and in the thermoplastic polymer molecule.

It is thought that it produces | generates by dehydration reaction with the hydroxyl group of the remainder of the methylol group of novolak couple | bonded with the hydrogen atom of group and vulcanizable rubber | gum.

기를 가진 열가소성 폴리머의 미세한 단섬유의 비율은 가황가능한 고무 100중량부당 이 섬유가 1 내지 100중량부, 바람직하기는 1 내지 70중량부, 특히 바람직하기는 30 내지 70중량부이다. 가황가능한 고무에 매봉되어있는 섬유의 비율이 상기 하한보다 적으면 가황물의 강도 및 모듈러스가 개선되지 않으며, 가황가능한 고무에 매봉되어 있는 섬유의 비율이 상기 상한보다 많으면 가황물의 접착성이 저하한다.Among the polymer molecules embedded in the vulcanizable rubber in the reinforced rubber composition of the present invention

The proportion of the fine short fibers of the thermoplastic polymer having groups is 1 to 100 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 30 to 70 parts by weight, per 100 parts by weight of the vulcanizable rubber. If the proportion of the fibers embedded in the vulcanizable rubber is less than the lower limit, the strength and modulus of the vulcanizate will not be improved. If the proportion of the fibers embedded in the vulcanizable rubber is more than the upper limit, the adhesion of the vulcanizate will be reduced.

In addition, in the reinforcing rubber composition of the present invention, the weight of the vulcanizable rubber graft bonded to the thermoplastic polymer through the novolak at the interface of the fiber to the weight of the fine short fibers of the thermoplastic polymer embedded in the vulcanizable rubber. The thermoplastic polymer and the vulcanizable rubber which form the fiber such that the graft ratio expressed in the ratio (fine short fibers of the vulcanizable rubber / thermoplastic polymer) are 3 to 25% by weight, in particular 5 to 20% by weight, are grafted through the novolac. It is desirable to do.

기를 가진 열가소성 폴리머와 이들 고무와 열가소성 폴리머와의 합계량 100중량부당 0.2 내지 5중량부의 노볼락형 페놀포름알데히드계 수지의 초기 축합물과 포름알데히드 공여체를 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 혼련하여 얻어진 혼련물을 혼련물중의 고무와 열가소성 폴리머와의 비율이 고무 100중량부당 열가소성 폴리머가 1내지 100중량부인 때는 그대로, 혼련물중의 고무와 열가소성 폴리머와의 비율이 고무 100중량부당 열가소성 폴리머가 1중량부보다 많아질때는 추가의 가황가능한 고무를, 전부의 고무 100중량부당 열가소성 폴리머가 1내지 100중량부로 되도록 혼련물에 첨가해서 다시 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 혼련한 후 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 압출하고 압출물을 열가소성 폴리머의 융점보다 낮은 온도에서 연신하므로써 제조할 수가 있다.The reinforced rubber composition of the present invention having the above characteristics is, for example, vulcanizable rubber and molecular weight of less than 200,000

The initial condensate and the formaldehyde donor of 0.2-5 parts by weight of novolac-type phenol formaldehyde-based resin per 100 parts by weight of the total amount of the thermoplastic polymer having a rubber and the thermoplastic polymer and the temperature above the melting point of the thermoplastic polymer When the kneaded product obtained by kneading in the ratio of the rubber and the thermoplastic polymer in the kneaded product is 1 to 100 parts by weight of the thermoplastic polymer, the ratio of the rubber and the thermoplastic polymer in the kneaded product is 100 parts by weight of rubber as it is. When the thermoplastic polymer is more than 1 part by weight, an additional vulcanizable rubber is added to the kneaded material so that the thermoplastic polymer is 1 to 100 parts by weight per 100 parts by weight of the rubber, and again the melting point of the thermoplastic polymer and the temperature below 270 ° C. After kneading at and above the melting point of the thermoplastic polymer and at a temperature below 270 ° C. Output and can be prepared by stretching the extrudate at a temperature below the melting point of the thermoplastic polymer.

기를 가진 열가소성 폴리머와 이들 고무와 열가소성 폴리머와의 합계량 100중량부당 0.2 내지 5중량부, 바람직하기는 고무 100중량부당 0.5 내지 5중량부, 특히 바람직하기는 0.5 내지 3중량부의 상기한 노볼락과 바람직하기는 고무 100중량부당 0.02 내지 1중량부의 포름알데히드 공여체를 상기한 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도에서 혼련한다.In the process of the present invention, first, the vulcanizable rubber and molecular weight (number average molecular weight) of less than 200,000, preferably from 10,000 to 100,000 of the above polymer molecules

0.2 to 5 parts by weight, preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight of the novolac described above, per 100 parts by weight of the thermoplastic polymer having a group and the total amount of these rubbers and the thermoplastic polymer. The following is kneading of 0.02 to 1 part by weight of formaldehyde donor per 100 parts by weight of rubber above the melting point of the above-mentioned thermoplastic polymer and at a temperature below 270 ° C.

, 파라포름알데히드, α--폴리옥시메틸렌. 다가메틸롤멜라민유도체, 옥사졸리딘유도체, 다가메틸롤화아세틸렌 요소등을 들수 있다.As the above-mentioned formaldehyde donor, a compound which generates formaldehyde by heating is used. For example, formaldehyde donor as hexamethylenetetramine, acetaldehyde ammonia

, Paraformaldehyde, α-polyoxymethylene. And polyvalent methylol melamine derivatives, oxazolidine derivatives, and polyvalent methylolated acetylene urea.

기를 가진 열가소성 폴리머와의 비율은 특히 제한은 없으나 통상 가황가능한 고무 100중량부당 열가소성 폴리머가 1 내지 2000중량부, 바람직하기는 1 내지100중량부, 특히 바람직하기는 1 내지 70중량부이다.Among the vulcanizable rubber and polymer molecules described above

The ratio with the thermoplastic polymer having groups is not particularly limited, but is usually 1 to 2000 parts by weight, preferably 1 to 100 parts by weight, particularly preferably 1 to 70 parts by weight, per 100 parts by weight of the vulcanizable rubber.

기를 가진 열가소성 폴리머와 노볼락과 포름알데히드공여체와의 혼련은 상기 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도, 바람직하기는 열가소성 폴리머의 융점보다 5℃이상 높게 또한 260℃이하의 온도에서, 가황가능한 고무와 열가소성 폴리머와 노볼락과 포름알데히드 공여체와의 혼합물이 일종의 용융상태에서 행하여진다. 상기 각 성분의 혼련은 브라벤더플라스트그래프, 밴버리혼합기, 로울, 압출기등을 사용하여 바람직하기는 1내지 15분간 행해진다.Among vulcanizable rubber and polymer molecules

The kneading of a thermoplastic polymer having a group with a novolak and a formaldehyde donor is vulcanized at a temperature above the melting point of the thermoplastic polymer and below 270 ° C, preferably at least 5 ° C above the melting point of the thermoplastic polymer and below 260 ° C. Possible mixtures of rubber and thermoplastic polymers with novolac and formaldehyde donors are carried out in a kind of molten state. The kneading of the above components is preferably performed for 1 to 15 minutes using a brabender platter graph, a Banbury mixer, a roll, an extruder or the like.

기를 가진 열가소성 폴리머를 투입하여 혼련하고 열가소성 폴리머를 용융시켜 고무중에 열가소성 폴리머를 분산시켜 이어서 노볼락을 투입하여 더욱 혼련후 최후로 포름알데히드 공여체를 투입하여 1내지 15분간 혼련하여 각 성분을 혼련하는 방법이 호적하게 채용된다.In addition, there is no particular limitation in Bangbi, which adds and kneads each component to a kneading apparatus such as a brabender plastograph, but first, by adding vulcanizable rubber and an anti-aging agent to the kneading apparatus, the Soviet Union is added, and then the polymer molecules

A method of kneading each component by kneading by adding and mixing a thermoplastic polymer having a group and melting the thermoplastic polymer to disperse the thermoplastic polymer in the rubber, and then adding a novolak, and finally kneading the formaldehyde donor for 1 to 15 minutes. This is adopted suitably.

기를 가진 열가소성 폴리머와 노볼락과 포름알데히드 공여체를 상기한 바와같이 혼련하므로써 가황가능한 고무와 상기 열가소성 폴리머를 노볼락을 통하여 그라프트 결합시키는 동시에 가황가능한 고무중에 상기 열가소성 폴리머를 미세(분산된 열가소성 폴리머의 입경은 통상 1내지 2μ이다)하고 균일하게 분산시킬 수가 있다.In the method of the present invention, rubber and polymer molecules vulcanizable using the above-mentioned novolac and formaldehyde donors

By kneading the vulcanizable rubber and the thermoplastic polymer through the novolac by kneading the thermoplastic polymer having a group with the novolak and the formaldehyde donor as described above, the thermoplastic polymer is finely divided in the vulcanizable rubber. The particle diameter is usually 1 to 2 mu m) and can be uniformly dispersed.

When the amount of the novolac is less than the lower limit, the graft reaction between the vulcanizable rubber and the thermoplastic polymer through the novolac is unlikely to occur, which causes coarse fibers or films of the thermoplastic polymer to be produced and the thermoplastic at the fiber interface. Since the bond between the polymer and rubber is weak, the strength, adhesiveness, and fatigue characteristics of the vulcanized product obtained by vulcanizing the reinforced rubber composition decrease. If the amount of novolac is higher than the above upper limit, gelation of the thermoplastic polymer by novolak occurs and fiber formation of the thermoplastic polymer decreases, so that the strength and modulus of the vulcanizate obtained by vulcanizing the reinforced rubber composition decreases.

기를 가진 열가소성폴리머를 사용하는 것이 필요하며 이에따라 모듈러스, 인장강도, 접착성 및 피로특성(특히 내열성)이 뛰어난 가황물을 부여하는 강화고무조성물을 얻을수가 있는 것이며, 섬유형성이 가능한 폴리머라 하더라도 폴리머분자중에

기를 갖지 않은 열가소성 폴리머로는 고무중에 분산한 열가소성 폴리머의 입경이 크게되어 굵은 섬유나 필름이 생성하여, 섬유계면에서의 열가소성폴리머와 고무와의 그라프트결합이 생기지 않으므로 본 발명의 방법에 사용할 수가 없는 것이다.In the method of the present invention, as a polymer forming the fiber,

It is necessary to use a thermoplastic polymer having a group, and thus a reinforcing rubber composition giving a vulcanizate having excellent modulus, tensile strength, adhesiveness and fatigue properties (especially heat resistance) can be obtained. During

As the thermoplastic polymer having no group, the particle diameter of the thermoplastic polymer dispersed in the rubber is increased to produce coarse fibers or films, and graft bonding between the thermoplastic polymer and the rubber at the fiber interface does not occur and thus cannot be used in the method of the present invention. will be.

In the process of the present invention, an anti-aging agent such as N- (3-methacryloyloxy-2-hydroxypropyl) is added to a vulcanizable rubber for the purpose of preventing gelation of the vulcanizable rubber during kneading and extrusion of the respective components. N'-phenyl-P-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N'-diphenyl-P-phenylenediamine, N-isopropyl-N'-phenyl -P-phenylenediamine, N-cyclohexyl-N'-phenyl-P-phenylenediamine, 2,6-di tertiary butyl-4-methylphenol, 2,6-ditertbutyl-α-dimethylamino Incorporating low-volatile antioxidants such as -P-cresol and 2,2'-dihydroxy-3,3'-bis (α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane desirable.

기를 가진 열가소성 폴리머와의 비율이 고무 100중량부당 상기 열가소성 폴리머가 1내지 100중량부, 바람직하기는 1 내지 70중량부, 특히 바람직하기는 30내지 70중량부인 때는 그대로 압출하며 혼련물중의 고무와 상기 열가소성 폴리머와의 비율이 고무 100중량부당 상기 열가소성 폴리머가 1중량부보다 많아질때는 상기한 가황가능한 고무중에서 선택되는 추가의 가황가능한 고무를, 전부의 고무 100중량부당 열가소성 폴리머가 1내지 100중량부, 바람직하기는 1내지 70중량부, 특히 바람직하기는 30내지 70중량부로 되도록 혼련물에 첨가하여 다시 상기 열가소성 폴리머의 융점이상으로 또한 270℃이하의 온도, 바람직하기는 상기 열가소성 폴리머의 융점보다 5℃이상 높게 또한 260℃이하의 온도에서 혼련한후 압출한다.In the method of the present invention, the kneaded product obtained by kneading the respective components as described above is placed in the rubber and polymer molecules

When the ratio of the thermoplastic polymer having a group is 1 to 100 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 30 to 70 parts by weight, per 100 parts by weight of the rubber, it is extruded as it is and the rubber in the mixture When the ratio with the thermoplastic polymer is more than 1 part by weight of the thermoplastic polymer per 100 parts by weight of rubber, the additional vulcanizable rubber selected from the above vulcanizable rubber is 1 to 100 parts by weight of the thermoplastic polymer per 100 parts by weight of the total rubber Parts, preferably 1 to 70 parts by weight, particularly preferably 30 to 70 parts by weight, and added to the kneaded material again, above the melting point of the thermoplastic polymer and at a temperature below 270 ° C., preferably above the melting point of the thermoplastic polymer. It is extruded after kneading | mixing at the temperature of 5 degreeC or more and below 260 degreeC.

If the ratio of the thermoplastic polymer in the kneaded material at the time of extruding the kneaded material is less than the lower limit, it is not possible to obtain a reinforced rubber composition which gives an excellent vulcanizate of strength and modulus, and in the kneaded material at the time of extruding the kneaded material. When the ratio of nylon is more than the above upper limit, it is difficult to obtain a reinforcing rubber composition giving a vulcanizate excellent in adhesion.

The kneaded material can be extruded in the form of a string (or sheet) through a circular or spherical die such as a circular die or a spherical die. In the case of using a round die, the inner diameter of the discharge hole is preferably 0.1 to 5 mm, and the ratio (L / D) of the length of the discharge hole to the inner diameter of the discharge hole is preferably 1 to 20. In the case of using the die, the slit gap is 0.1 to 5 mm. It is preferable that the width is 0.2 to 200 mm and the length of the dieland is 10 to 20 mm.

It is preferable to use a circular die among the above-mentioned various dies. As the circular die, one having one discharge port or one having a plurality of discharge holes (multi-forward type) can be used.

In the extrusion of the kneaded material, a known extruder, such as a screw extruder, is used, and the temperature of the screw at the temperature of the screw top is higher than the melting point of the thermoplastic polymer, and the temperature of the die is lower than the melting point of the thermoplastic polymer. In particular, it is preferable to extrude the kneaded product at a temperature of at least 5 ° C. above the melting point of the thermoplastic polymer and at a temperature of 260 ° C. or less.

In the method of the present invention, the thermoplastic polymer in the vulcanizable rubber of the extrudate obtained by extruding the kneaded product as described above is in a fibrous form, and moreover, at the interface of the fibrous thermoplastic polymer, the thermoplastic polymer and the vulcanizable rubber are grafted through the novolac. Is bound.

The reinforcing rubber composition of the present invention is preferably cooled by an inert organic solvent for rubber and thermoplastic polymers such as methanol, air-cooled and water-cooled, while continuously exerting the above-mentioned extrudate, or from the die. 1 to 100 m / min to a winding machine such as a bobbin or a winding roll by cooling to a temperature lower than the melting point of the thermoplastic polymer by a method such as lengthening the distance to the winding machine (also called a winding machine), and by a method known per se. After winding at a winding speed of 20 to 40 m / min, it can be obtained by rolling using a pair of rolling rolls or stretching by uniaxial stretching using a stretching roll. The temperature of the winder in taking out the extrudate is preferably 0 to 100 ° C. When the extrudate is wound up without cooling, a part of the fibrous thermoplastic polymer may be flat (film in the extreme case), and a good result may not be obtained.

As for the temperature of the rolling by said rolling roll, 0-100 degreeC is preferable. Moreover, it is preferable to perform extending | stretching by extending | stretching roll so that draw ratio may be 1.1-10.

In the method of the present invention, the thermoplastic polymer in the vulcanizable rubber of the reinforcing rubber composition obtained by stretching the extrudate as described above is converted into a fibrous structure in which the fibers are molecularly oriented so as to be fine short fibers having high strength. .

기를 가진 열가소성 폴리머가 함유되고 이 열가소성폴리머가 미세한 단섬유이며 더우기 이 섬유의 계면에 있어서 열가소성폴리머와 가황가능한 고무가 노볼락을 통하여 그라프트 결합하고 있는 것이며, 단독 또는 가황가능한 고무와 혼합하여 사용해서 저신장시 및 고신장시의 모듈러스, 인장강도,각종 부재와의 접착성 및 피로 특성이 뛰어난 가황물을 부여할 수가 있다.The reinforced rubber composition obtained by the method of the present invention is contained in 1 to 100 parts by weight of polymer molecules per 100 parts by weight of vulcanizable rubber.

It contains a thermoplastic polymer having a group and the thermoplastic polymer is a fine short fiber, and at the interface of the fiber, the thermoplastic polymer and the vulcanizable rubber are graft-bonded through the novolac, and used alone or in combination with the vulcanizable rubber. It is possible to give a vulcanizate excellent in modulus, tensile strength, adhesion to various members, and fatigue properties at low and high elongation.

The reinforcing rubber composition of the present invention utilizes its excellent properties in the use of tire inner members such as belts, carcasses and beads, tire outer members such as treads and sidewalls, industrial products such as belts and hoses, and shoes materials. I can minister.

Next, an Example, a comparative example, and a reference example are shown.

The physical property test of the vulcanizate which was performed in order to evaluate the (reinforced) rubber composition obtained in the Example, the comparative example, and the reference example was measured according to JISK 6301.

The manufacture example of the novolak used in the Example is shown next. In the following description, parts represent parts by weight.

A. Novolak-type phenol-formaldehyde initial condensate (hereafter simply referred to as novolak A)

Initial condensation product of novolac type phenolformaldehyde, which is a powder crystal of softening point 106 ℃, water content 0.12% by weight, and 0.13% by weight of prephenol, obtained by condensation of phenol and paraformaldehyde using catalysis as a catalyst. Product name 55OPL).

B. Novolak-type lactam-bisphenol F-formaldehyde initial condensate (sometimes simply referred to as novolak B)

141 parts of epsilon caprolactam and 55.6 parts of paraformaldehyde having a purity of 81% were reacted at 120 ° C for 5 hours to obtain an addition reaction liquid containing an addition reaction product of epsilon caprolactam and formaldehyde. The total amount of the addition reaction solution was slowly added dropwise to a mixture of bisphenol F315 part, 32 parts of water and 1.6 parts of hydrochloric acid at a concentration of 35%, condensation reaction of ε-caprolactam-formaldehyde adduct and bisphenol F was carried out under reduced pressure from the reaction mixture. (180 degreeC, 10 mmHg) and 469 parts of novolak-type lactam bisphenol F-formaldehyde initial condensate were obtained.

C. Novolac-type styrenated phenol-phenol-formaldehyde initial condensate (sometimes simply referred to as novolac C)

1041 parts of styrene was slowly added dropwise to a mixture of 1412 parts of phenol and 40.3 parts of hydrochloric acid at a concentration of 35%, and mixed for 2 hours at 130 ° C. to styrenate the phenol, and distilled under reduced pressure (180 ° C., 40 mmHg) from the reaction mixture to produce a styrenated phenol. To the total amount of this styrenated phenol, 1426 parts of formalin and 87 parts of 40% sodium hydroxide were added and mixed at 80 ° C for 5 hours to formaldehyde was added (betaylated) to the styrenated phenol. Part and 123 parts of water were added and condensation reaction of the styrenated phenol and phenol methylated at 100 ° C. for 2 hours.

It distilled under reduced pressure (100-180 degreeC, 40 mmHg) from the reaction mixture, and obtained 2959 parts of styrene-phenol-phenol-formaldehyde initial condensates of 73 degreeC (circulation method) of the softening point.

Example 1

100 parts of natural rubber (NR) of 1 * 10 <^6> pose and N- (3-methacryloyloxy- 2-hydroxypropyl) -N in the Brabender platograph set to 220 degreeC and 50 rpm. 1.0 parts of '-phenyl-P-phenylenediamine [Norak-G-1, manufactured by Ouchi Shin-Kogagaku Kogyo Co., Ltd.] was added for 30 seconds, followed by Soviet Union 6-nylon (trade name: 1030B, Ubegosan Co., Ltd.). ), Melting point 221 ° C., molecular weight 300000), 50 parts of the mixture was kneaded for 4.5 minutes, then 2.25 parts of novolak A was kneaded for 3 minutes, followed by 0.225 parts of hexamethylenetetramine for 3.5 minutes (the temperature in the brabender was 230 Rise to ° C) to obtain a kneaded product.

The resulting kneaded product was extruded in a string at a die set temperature of 235 ° C using a 20 mm ψ extruder (manufactured by Hoake) having an inner diameter of 2 mm and a ratio between the length and the inner diameter (L / D) of two circular dies. Funnel installed at a vertical position from the funnel (coolant at 0 ° C is supplied by the pump and tube in the funnel, and the supplied coolant flows through the funnel and flows into the coolant storage vessel installed at the vertical position of the funnel, Was passed into the funnel by means of a pump and a tube, and was then wound through a guide roller to the bobbin at a speed of 35 m / min with a draping ratio of 9. The wound was vacuum dried at room temperature for one night to remove adhered water, and then 500 wounds were bundled and formed into a sheet (about 2 mm thick and about 150 mm wide). The sheet was cut into a roll gap of 0.2 mm and a temperature of 60 ° C. Roll rolling was carried out about 10 times with a pair of rolled rolls to obtain a reinforced rubber composition (master batch).

Fractionation, Graft Rate Measurement

2 g of the reinforced rubber composition obtained in Example 1 was added to 200 ml of benzene at room temperature to dissolve the rubber part in the reinforced rubber composition, and the resulting slurry was centrifuged at room temperature to be divided into a solution part and a precipitate part. For the precipitated portion, the above operation was repeated seven times, and then the precipitated portion was dried to obtain nylon fibers. The nylon fibers of phenol and one of the o-dichlorobenzene: from NMR cha art dissolved in a mixture of 3 (by weight) analyzed by nuclear magnetic resonance spectrum (NMR) of ¹ H (internal standard tetramethylsilane) attributable to the natural rubber The molar ratio of 6-nylon to natural rubber is determined by cutting area method for each peak of the methyl group, the methylene group, the methylene group adjacent to the CO group derived from 6-nylon, the methylene group adjacent to the NH group, and the other three methylene groups. The shape of the nylon fiber was measured using a scanning microscope at a magnification of 10,000 times for about 200 fibers. The fiber was an extremely thin short fiber of circular cross section. The results are summarized in the first table.

Evaluation test

The reinforced rubber composition obtained in Example 1 was vulcanized at 150 ° C. for 40 minutes by the formulation shown in the second table to measure physical properties. The results are shown in the second table.

Example 2

The same procedure as in Example 1 was carried out except that 30 parts of 6-nylon, 1.93 parts of novolak A, and 0.193 parts of hexamethylene tetramine were used. The results were collectively shown in the first and second tables.

Example 3

It carried out similarly to Example 1 except having used 40 parts of 6- nylon, 2.10 parts of novolak A, and 0.21 part of hexamethylene tetramine. The results were collectively shown in the first and second tables.

Example 4

70 parts of 6-nylon, 2.25 parts of novolak A, and 0.255 parts of hexamethylene tetramine were used in the same manner as in Example 1. The results were collectively shown in the first and second tables.

Example 5

0.75 parts of novolak A and 0.075 parts of hexamethylenetetramine were used in the same manner as in Example. The results were collectively shown in the first and second tables.

Example 6

The same procedure as in Example 1 was carried out except that 1.88 parts of novolak A and 0.188 parts of hexamethylenetetramine were used. The results were collectively shown in the first and second tables.

Comparative Example 1

It carried out similarly to Example 1 except not having added novolak A and hexamethylene tetramin. The results were collectively shown in the first and second tables.

Example 7

The procedure of Example 1 was repeated except that novolak B was used instead of novolak A. The results were collectively shown in the first and second tables.

Example 8

It carried out similarly to Example 1 except having used novolak C instead of novolak A. The results were collectively shown in the first and second tables.

Example 9

It carried out similarly to Example 1 except having used 0.225 part of (alpha)-polyoxymethylene (n> 100, Kadayama Kagaku Kogyo Co., Ltd. product) instead of hexamethylenetetramine. The results were collectively shown in the first and second tables.

Example 10

100 parts of NR and 1 part of Nocturnal G-1 were added to Brabender Plasto Graph at 220 ℃ and 50rpm, and then kneaded for 4 minutes by adding 50 parts of 6-nylon (1030B) to the Soviet Union for 30 seconds. 0.75 parts of novolac A was added, and after kneading for 1 minute, 0.075 parts of hexamethylenetetramine was added, and kneaded for 2 minutes (the temperature in the brabender increased to 230 ° C), and 0.75 parts of novolak A was added again for 1 minute. After kneading, add 0.075 parts of hexamethylenetetramine, knead for 2 minutes (the temperature in the brabender is 230 ° C), add 0.75 parts of novolak A, knead for 1 minute, and add 0.075 parts of hexamethylenetetramine for 2 minutes. Kneading was carried out (the temperature in the brabender during this period was 230 ° C). The obtained kneaded material was extruded in the same manner as in Example 1 to be wound and rolled to obtain a reinforced rubber composition. The results were collectively shown in the first and second tables.

Example 11

100 parts of NR and 1 part of Nokrak G-1 were put into the Banbury mixer (made by Minami Senju) set at 150 degreeC, and 150 rpm, 1 minute after Soviet Union, and 50 parts of 6-nylon (1030B) were added, and it knead | mixed for 4 minutes. During this time, the temperature in the mixer rose to 230 ° C. and 6-nylon melted. Next, 2.25 parts of Novolac A was kneaded for 7 minutes, and 0.225 part of hexamethylenetetramine was added and kneaded for 2.5 minutes. (The temperature in Banbury during this time was 230 ° C). The obtained kneaded material was extruded, wound and rolled in the same manner as in Example 1 to obtain a reinforced rubber composition. The results were collectively shown in the first and second tables. In addition, the extrudate was not cut at all during 6 hours of continuous extrusion and winding.

The fiber lengths of the nylon fibers embedded in the reinforcing rubber compositions obtained in each example were all about 200 µm or less (based on calculated values).

TABLE 1

(Note) It is divided into three times, and wound up for 6 hours continuously using Example 110,000 Banbury mixer.

TABLE 2

Note 1): Carbon Black (Product Name: Diamond Black I. Mitsubishi Kasei Kogyo Co., Ltd.)

Note 2): N-phenyl-N'-isopropyl-p-phenylenediamine

Note 3): 2,2,4-trimethyl-1,2-dihydroquinoline polymer (trade name: Nocturnal 224, Ouchi Shinkoo Chemical Co., Ltd.)

4) dibenzothiazyl disulfide

Note 5): N, N'-diphenylguanidine

Note 6): Adhesiveness to natural rubber vulcanizates

Note 7): Total of nylon fiber and nylon film

The stress-distortion line of the vulcanizate obtained from each of the reinforced rubber compositions of Examples 1 to 11 was a smooth &quot; inverse S-shape &quot;. On the other hand, in the stress-distortion line of the vulcanizate obtained from the reinforcing rubber composition of Remarks Example 1, a wave-shaped disturbance was generated at around 50% of the distortion.

The physical properties of the vulcanized products obtained from the respective reinforced rubber compositions of Example 1, Example 7, Example 8 and Comparative Example 1 were measured.

PICO abrasion test according to ASTM D 2228, fatigue test using a statically loaded tensile fatigue test apparatus at 100 ° C in air and 50% modulus after tension 1 × 10 ⁴ times at a static load of 3Okg / cm ² Tensile recovery (fatigue life) until tensile fracture at a tensile load of 50 kg / cm ² was obtained. The results are shown in Table 3.

TABLE 3

A): Vulcanization time of the composition 40 minutes

B): Vulcanization time of the composition 30 minutes

The results shown in the third table indicate that the reinforced rubber composition of the present invention gives a vulcanizate having extremely excellent properties under high temperature and high stress.

Claims (2)

In 100 parts by weight of vulcanizable rubber

1 to 100 parts by weight of fine short fibers of a thermoplastic polymer having a group are embedded, and at the interface of the fibers, the polymer and the vulcanizable rubber are formed of a novolac phenol formaldehyde resin. Reinforced rubber composition grafted through the initial condensate. In vulcanizable rubber and polymer molecules with molecular weight less than 200000

A thermoplastic polymer having a group and a compound capable of generating formaldehyde upon heating with an initial condensate of 0.2 to 5 parts by weight of a novolak-type phenol formaldehyde-based resin per 100 parts by weight of the total amount of these rubbers and thermoplastic polymers. As mentioned above, when the kneaded product obtained by kneading at a temperature of 270 ° C. or lower is 1 to 100 parts by weight of the thermoplastic polymer per 100 parts by weight of the rubber and the thermoplastic polymer in the kneaded material, the rubber and the thermoplastic polymer in the kneaded product are intact. When the ratio of the amine is greater than 1 part by weight of the thermoplastic polymer per 100 parts by weight of rubber, additional vulcanizable rubber is added to the kneaded mixture so that the thermoplastic polymer is 1 to 100 parts by weight per 100 parts by weight of the rubber, and the melting point of the thermoplastic polymer Above and further, after kneading at a temperature of 270 ° C. or lower, the melting point of the thermoplastic polymer is higher. Furnace further extruding the extrudate at a temperature below the melting point of the thermoplastic polymer by extruding at a temperature of 270 ℃ or less.