CN1938375A - Masterbatch composition, rubber composition containing the same, and vulcanizate - Google Patents

Abstract

A masterbatch composition with which the dispersibility of short fibers in a rubber composition can be heightened. The masterbatch composition comprises 5 to 78 parts by weight of a copolymer rubber (A) having units of an alpha,beta-ethylenically unsaturated nitrile monomer, 5 to 78 parts by weight of a polyfunctional compound (B) and/or a plasticizer (B') having a molecular weight of 400 or higher, and 17 to 90 parts by weight of short fibers (C) having a length of 0.1 to 12 mm (provided that the sum of (A), (B) and/or (B'), and (C) is 100 parts by weight.

Description

Masterbatch composition, the rubber combination that contains it and sulfide

Technical field

The present invention relates to contain the masterbatch composition of staple fibre, and then, also relate to rubber combination that contains this masterbatch composition and the sulfide that this rubber combination sulfuration is formed.

Background technology

In recent years, for automobile, because the high discharge capacityization of engine, preposition engine/engineization, exhaust emissions scheme etc., engine spatial thermal environment condition is too harsh, as the rubber that can fully tolerate this type of working conditions, the high performance that alkene nitrile-divinyl rubber etc. is contained the copolymer rubber of itrile group has carried out various researchs.On the other hand, at present known by in rubber combination, cooperating staple fibre, the mechanical characteristics of the tensile strength of gained rubber molding thing and tensile stress etc. is improved.Yet it is very difficult that this staple fibre is scattered in the rubber combination equably, when only adding staple fibre separately in rubber combination, exists to be wound in piece between the staple fibre, is difficult to obtain the problem of desirable effect.

As the method that addresses this problem; following technology is disclosed in patent documentation 1: by making staple fibre dispersive rubber (base rubber) granulating base rubber and the contact area between the staple fibre when mixing are increased; and then the use level by control staple fibre and base rubber and base rubber with respect to mixing roll filling ratio, staple fibre is scattered in the base rubber.Yet,, also be difficult to staple fibre is disperseed with good state even control mixing condition like this.

In addition, disclose in the patent documentation 2: in rubber combination, make staple fibre dispersive technology by using tenderizer when mixing polymkeric substance and the staple fibre.This technology is impregnated into the winding that prevents in the staple fibre between the staple fibre by making tenderizer, thereby improves the dispersiveness of the staple fibre in the rubber combination.Yet, for tenderizer fully being impregnated in the staple fibre the essential above staple fibre of 10 volume % that cooperates, for example, when using the higher rubber of acrylonitrile-butadiene copolymer rubber isopolarity, the intermiscibility variation of tenderizer and rubber, like this, be difficult to cooperate a large amount of tenderizers.In addition, in this patent documentation 2, example as the phthalic acid two of tenderizer (2-ethyl oneself) ester and hexanodioic acid two (2-ethyl oneself) ester.Yet, when using these tenderizers in a large number, can produce and ooze out, be difficult to cooperate the purpose of enough tenderizers to realize soaking into staple fibre.In addition, because heat-resistant aging is insufficient, therefore exist in unworkable problem under the harsh thermal environment condition.

On the other hand, disclose the master batch that in aqueous elastomerics, is combined with staple fibre and weighting agent by using in the patent documentation 3, thereby improved the technology of the dispersiveness of the staple fibre in the rubber combination.By this technology, in advance that staple fibre and weighting agent is mixing, make staple fibre untie winding after, cooperate with aqueous elastomerics and the master batch that forms, the dispersiveness of the staple fibre in the rubber combination is improved.Yet, for a large amount of staple fibres is disperseed, must increase the use level of weighting agent, be difficult and these staple fibres and weighting agent are disperseed equably.

Patent documentation 1: Japanese kokai publication hei 6-207027 communique

Patent documentation 2: Japanese kokai publication hei 8-239484 communique

Patent documentation 3: Japanese kokai publication sho 63-137940 communique

Summary of the invention

Main purpose of the present invention is to provide the masterbatch composition of the dispersiveness that can improve the staple fibre in the rubber combination.

In view of the foregoing, the inventor etc. further investigate, found that: by using the multi-functional compounds to replace tenderizer, even can when being to use the higher rubber of acrylonitrile-butadiene copolymer rubber isopolarity, also can cooperate enough amounts, and softening agent (comprising tenderizer) by the specified molecular weight that uses, can cooperate q.s to prevent to twine between the staple fibre being used to, thereby finish the present invention.In addition, the inventor etc. also find: stipulate the matrix components of the liquid rubber composition of range of viscosities as master batch by use, and use this liquid rubber composition and staple fibre to scale, at the consumption of weighting agent when specified amount is following, can not improve the dispersiveness of the staple fibre in the rubber combination even further do not improve its use level yet, thereby finish the present invention.

Therefore by the present invention, can provide 1～7 following summary of the invention.

1. masterbatch composition, it contains: 5～78 weight parts contain α, β-unitary the copolymer rubber of ethylenic unsaturated nitrile monomer (A), 5～78 weight part multi-functional compounds (B) and/or molecular weight be more than 400 softening agent (B '), and 17～90 weight part length be the staple fibre (C) of 0.1～12mm, wherein (A), (B) and/or (B ') and total amount (C) are 100 weight parts.

2. as above-mentioned 1 described masterbatch composition, wherein, contain α, the α of β-unitary copolymer rubber of ethylenic unsaturated nitrile monomer (A), β-ethylenic unsaturated nitrile monomer unit content is below the 40 weight %.

3. rubber combination, it contains above-mentioned 1 or 2 described masterbatch compositions.

4. sulfide, it forms above-mentioned 3 described rubber combinations sulfurations.

5. masterbatch composition, its viscosity of 70 ℃ measuring with brookfield's viscometer with respect to 100 weight parts is the liquid rubber compositions (X) of 500 handkerchiefs below second, containing 25～550 weight part length is the staple fibre (Y) of 0.1～12mm, it is characterized by, the weighting agent content in the described masterbatch composition is below the 8 weight %.

6. rubber combination, it contains above-mentioned 5 described masterbatch compositions.

7. sulfide, it forms above-mentioned 6 described rubber combinations sulfurations.

The masterbatch composition of invention effect the application of the invention can be brought into play the effect in the rubber combination that staple fibre easily is dispersed in use it and obtains.The sulfide that the sulfuration of this rubber combination is formed is in excellence aspect the mechanical characteristicies such as tensile strength and tensile stress.And, use the masterbatch composition of the multi-functional compounds contain the afore mentioned rules amount and softening agent and the sulfide that obtains excellence aspect compression set and heat-resistant aging also.

Embodiment

Below, to masterbatch composition of the present invention and contain its rubber combination and sulfide that the sulfuration of this rubber combination is formed is elaborated.

A. masterbatch composition

Masterbatch composition of the present invention has the dual mode of the 1st mode and the 2nd mode.For this dual mode, describe respectively.

(the 1st mode)

Masterbatch composition of the present invention, it is characterized by and contain: 5～78 weight parts contain α, β-unitary the copolymer rubber of ethylenic unsaturated nitrile monomer (A), 17～90 weight part multi-functional compounds (B) and/or molecular weight are that softening agent (B ') 5～78 weight parts and the length more than 400 is the staple fibre (C) of 0.1～12mm, wherein, (A), (B) and/or (B ') and total amount (C) are 100 weight parts.

The present invention is used contains α, and the β-unitary copolymer rubber of ethylenic unsaturated nitrile monomer (A) (the following copolymer rubber (A) that contains itrile group that abbreviates as) is to make α, β-ethylenic unsaturated nitrile monomer and other monomer copolymerizations and the rubber that obtains.

At this, for the above-mentioned copolymer rubber (A) that contains itrile group, the α when using softening agent (B ') by 5～78 weight part scopes, β-ethylenic unsaturated nitrile monomer unit content is preferably below the 40 weight %, more preferably below the 39 weight %, more preferably below the 38 weight %.α, β-when ethylenic unsaturated nitrile monomer unit content is too much then is difficult to obtain to have the intermiscibility of the copolymer rubber (A) that contains itrile group and softening agent (B '), and has the tendency of oozing out easily.In addition, also there is the low tendency of lower temperature resistance.On the other hand, α, β-ethylenic unsaturated nitrile monomer unit content is preferably more than the 10 weight %, more preferably more than the 12 weight %, more preferably more than the 14 weight %.α, β-when ethylenic unsaturated nitrile monomer unit content is very few, then have the tendency that oil-proofness reduces.That is, α, β-ethylenic unsaturated nitrile monomer unit content is preferably 10～40 weight %, more preferably 12～39 weight %, more preferably 14～38 weight %.

In addition, the consumption of softening agent (B ') is the above-mentioned α that contains the copolymer rubber (A) of itrile group when above-mentioned scope not, β-ethylenic unsaturated nitrile monomer unit content is preferably 10～60 weight %, more preferably 12～55 weight %, more preferably 14～50 weight %.α, β-when ethylenic unsaturated nitrile monomer unit content is too much then possibly can't obtain oil-proofness, otherwise then has the tendency of winter hardiness difference too much the time.

α, β-ethylenic unsaturated nitrile monomer can exemplify out vinyl cyanide, methacrylonitrile, α-Lv Daibingxijing etc., wherein, preferred vinyl cyanide.

With above-mentioned α, other monomers of β-ethylenic unsaturated nitrile monomer copolymerization can exemplify out conjugated diene monomer, non-conjugated diene class monomer etc.

The conjugated diene monomer can exemplify out 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene etc., wherein, preferred 1,3-butadiene, isoprene.

The preferred carbonatoms of non-conjugated diene class monomer is 5～12 monomer, can exemplify out 1,4-pentadiene, 1,4-hexadiene, vinyl norbornene, Dicyclopentadiene (DCPD) etc.

And then, as other monomers, can with alpha-olefin, aromatic vinyl base class monomer, fluorine-containing vinyl monomer, α, β-ethylenic unsaturated monocarboxylic and ester thereof, α, the copolymerization such as protective agent of unsaturated polycarboxylic acid of β-ethylenic and acid anhydrides thereof or its ester, copolymerization.

The preferred carbonatoms of alpha-olefin is 2～12, can exemplify out ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.

Aromatic vinyl base class monomer can exemplify out vinylbenzene, alpha-methyl styrene, vinyl pyridine etc.Fluorine-containing vinyl monomer can exemplify out fluoro ethyl vinyl ether, fluoro propyl vinyl ether, o-trifluoromethyl vinylbenzene, pentafluorobenzoic acid vinyl acetate, difluoroethylene, tetrafluoroethylene etc.

α, β-ethylenic unsaturated monocarboxylic can exemplify out vinylformic acid, methacrylic acid etc.α, β-ethylenic unsaturated monocarboxylic ester can exemplify out methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, butyl methacrylate etc.α, the unsaturated polycarboxylic acid of β-ethylenic can exemplify out methylene-succinic acid, fumaric acid, toxilic acid etc.α, the unsaturated polybasic acid anhydride of β-ethylenic can exemplify out itaconic anhydride, maleic anhydride etc.α, the unsaturated multi-carboxylate of β-ethylenic can exemplify out ethyl maleate, dimethyl maleate, dimethyl fumarate, DEF, di n butyl fumarate, fumaric acid two (the 2-ethyl is own) ester, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, methylene-succinic acid two (the 2-ethyl is own) ester etc.

The protective agent of copolymerization can exemplify out N-(4-anilino phenyl) acrylamide, N-(4-anilino phenyl) Methacrylamide, N-(4-anilino phenyl) cinnamide, N-(4-anilino phenyl) crotonamide, N-phenyl-4-(3-vinyl benzyl oxygen base) aniline, N-phenyl-4-(4-vinyl benzyl oxygen base) aniline etc.

Preferred usually acrylonitrile-butadiene copolymer rubber and the hydride thereof of using of copolymer rubber (A) that contains itrile group.

For the above-mentioned copolymer rubber (A) that contains itrile group, when the rubber combination that will use masterbatch composition is used for the purposes of special requirement for height thermotolerance and weathering resistance etc., the preferred less material of iodine value that uses, for example iodine value is the material below 120.

The above-mentioned copolymer rubber (A) that contains itrile group is preferably 5～300 at 100 ℃ mooney viscosity ML (1+4), and more preferably 10～250, more preferably 15～200.When mooney viscosity was too small, then the mechanical characteristics of gained sulfide had the tendency of variation, otherwise, the excessive tendency that poor in processability is then arranged.

The multi-functional compounds (B) that the manner is used is as long as have 2 above ethylenic unsaturated double-bonds, preferably have 2～3, and there is no particular limitation, but be aqueous below 150 ℃ preferably.This is because it is aqueous that multi-functional compounds (B) needs only in this temperature range, then can fully soak in staple fibre, can effectively prevent to twine between the staple fibre.

The used multi-functional compounds (B) of the manner can exemplify out allylic cpd with 2 above ethylenic unsaturated double-bonds, vinyl compound, (methyl) acrylate, (methyl) acrylamide etc.

Allylic cpd can exemplify out tricyanic acid three (methyl) allyl ester, isocyanuric acid three (methyl) allyl ester, diallyl isophthalate, diallyl p phthalate etc.

Vinyl compound can exemplify out divinyl phenylbenzene, Vinylstyrene, trivinyl hexanaphthene etc.

(methyl) acrylate can exemplify out isocyanuric acid three (methyl) acrylate, isocyanuric acid triethoxy three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris oxyethyl group three (methyl) acrylate, trimethylolpropane tris propoxy-three (methyl) acrylate, glycerine propoxy-three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, propoxylated bisphenol two (methyl) acrylate, alkoxylate Hydrogenated Bisphenol A two (methyl) acrylate, propoxylation Hydrogenated Bisphenol A two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, neopentyl glycol dialkoxy two (methyl) acrylate, dicyclopentadienyl two (methyl) acrylate etc.

(methyl) acrylamide can exemplify out methylene-bisacrylamide etc.

In these multi-functional compounds, preferred triallyl cyanurate, isocyanuric acid triallyl, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diallyl isophthalate, diallyl p phthalate.

These multi-functional compounds (B) can use a kind separately, also can will be used in combination more than 2 kinds.

In the manner, even cooperate its sufficient amount of soaking into that makes in staple fibre, the also harmless and above-mentioned intermiscibility that contains the copolymer rubber (A) of itrile group can make it disperse equably by using above-mentioned multi-functional compounds (B).

It is more than 400 that the used softening agent of the manner (B ') needs molecular weight, is preferably more than 410, more preferably more than 420.Molecular weight is too small, and then the heat-resistant aging of rubber molding product has the tendency of variation.

Softening agent (B ') as long as molecular weight is that just there is no particular limitation more than 400, can exemplify out phthalic acid derivative, hexanodioic acid derivative, azelaic acid derivant, sebacic acid derivative, dodecane-2-acid derivative, trimellitic acid derivative, succinic acid derivative, citric acid derivant, phosphoric acid derivatives, glutaric acid derivatives, glycol derivative, epoxy derivative, polyester softening agent, Reoplex etc.

It is 6～11 phthalic acid dialkyl (phthalic acid two heptyl esters, phthalic acid ester in two ninth of the ten Heavenly Stems, phthalic acid two (undecane) ester etc.), phthalic acid benzyl ester, phthalic acid kind polyester etc. that the phthalic acid derivative can exemplify out phthalic acid dinonyl, phthalic acid two isodecyl esters, phthalic acid two (tridecane) ester, carbonatoms.

The hexanodioic acid derivative can exemplify out diisodecyl adipate, di-n-hexyl adipate, diethoxyethy adipate, hexanodioic acid kind polyester etc.

Azelaic acid derivant can exemplify out nonane diacid two (two sufferings) ester etc.

Sebacic acid derivative can exemplify out the substituent of dioctyl sebacate, sebacic acid two (butoxy oxyethyl group second) ester etc.

Dodecane-2-acid derivative can exemplify out dodecanedioic acid two (the 2-ethyl is own) ester etc.

The trimellitic acid derivative can exemplify out tri trimellitate (the 2-ethyl is own) ester, tri trimellitate n-octyl, triisodecyl trimellitate, triisooctyl trimellitate, trimellitic acid high alcohol ester, linear trimellitate, tri trimellitate alkane ester etc.

Succinic acid derivative can exemplify out dioctyl succinate etc.

Citric acid derivant acetyl triethyl citrate, acetyl tributyl citrate three (the 2-ethyl is own) ester etc.

Phosphoric acid derivatives can exemplify out tricresyl phosphate (the 2-ethyl is own) ester, tricresyl phosphate (dimethylbenzene) ester etc.

Glutaric acid derivatives can exemplify out pentanedioic acid dialkyl group diethyl ester, dibutoxyethoxyethyl glutarate, didecyl glutarate, diisodecyl glutarate, polyester type glutarate etc.

The glycol derivative can exemplify out triglycol two (2-ethylhexanoate), triethylene glycol dipelargonate, polyoxyethylene glycol etc.

Epoxy derivative can exemplify out epoxidised soybean oil, epoxidised linseed oil, epoxidized fatty acid monoesters, epoxidation hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester, epoxidation hexahydrobenzene dioctyl phthalate two isodecyl esters, epoxidation talloleic acid monooctyl ester, epoxidation glycol two acid esters etc.

Reoplex can exemplify out polyester softening agent, polyethers softening agent, poly--alpha-methyl styrene etc.

These softening agent (B ') can use a kind separately, also can will be used in combination more than 2 kinds.

In the manner, have the softening agent (B ') of specified molecular weight by such use, even cooperate its sufficient amount of soaking into that makes in staple fibre, also harmless and the above-mentioned intermiscibility that contains the copolymer rubber (A) of itrile group can make it disperse equably.

The used staple fibre (C) of the manner needs the length of 0.1～12mm, is preferably 0.3～10mm, more preferably 0.5～8mm.When the length of staple fibre (C) is long, then is wound in easily between the staple fibre and determines, have in rubber combination, to be difficult to the dispersive tendency; Otherwise too short then possibly can't obtain mechanical characteristicies such as required tensile strength and tensile stress, and also has the tendency of compression set difference.

Staple fibre (C) can exemplify out organic fibre and inorganic fibre.Organic fibre can exemplify out natural fibers such as cotton, lumber fibre cellulose fiber; The synthon of polymeric amide, polyester, polyvinyl alcohol, artificial silk, polyparaphenylene benzo two  azoles, polyethylene, polypropylene, polyene propionic ester, polyimide, polyphenylene sulfides, polyether etherketone, poly(lactic acid), polycaprolactone, polybutylene succinate, fluorine based polymer etc. etc.Inorganic fibre can exemplify out glass fibre, carbon fiber etc.In the manner, wherein preferably use synthon, more preferably use polymeric amide owing to give the rubber molding thing with the effect height of the mechanical characteristics of tensile strength and tensile stress etc.Polymeric amide can exemplify out polymeric amide based on aliphatic chain, based on polymeric amide of fragrant chain etc., wherein, preferably based on the polymeric amide of fragrant chain.In polymeric amide based on fragrant chain, preferably be commonly called the polymeric amide of aromatic polyamide, especially preferably contain polymeric amide to the phenylene terephthalamide.

In addition, staple fibre can be the material with fibriilar pulpous state, can also be to have carried out various processing and the material that obtains with epoxy adhesive, isocyanuric acid ester class tackiness agent, resorcinol-formaldehyde resin/latex etc.These staple fibres can use a kind separately, also can will be used in combination more than 2 kinds.

The masterbatch composition of the manner is the copolymer rubber (A) that contains above-mentioned nitrile group-containing, multi-functional compounds (B) and/or molecular weight are that the staple fibre (C) that softening agent (B ') more than 400 and length are 0.1～12mm forms, these components in proportions are: 5～78 weight parts contain the copolymer rubber (A) of itrile group, 5～78 weight part multi-functional compounds (B) and/or molecular weight are the softening agent (B ') more than 400,17～90 weight part length are the staple fibre (C) (wherein (A) of 0.1～12mm, (B) and/or (B ') and total amount (C) be 100 weight parts, down together), preferred 10～71 weight parts contain the copolymer rubber (A) of itrile group, 10～71 weight part multi-functional compounds (B) and/or softening agent (B '), 19～80 weight parts and length are the staple fibre (C) of 0.1～12mm, and more preferably 15～65 weight parts contain the copolymer rubber (A) of itrile group, 15～65 weight part multi-functional compounds (B) and/or softening agent (B '), 20～70 weight parts and length are the staple fibre (C) of 0.1～12mm.

If multi-functional compounds's (B) content is very few, then, therefore the tendency of the dispersed variation of the staple fibre in the rubber combination is arranged owing to can't in staple fibre, fully soak into.Otherwise, if too much, then in the gained rubber combination, produce probably and ooze out.In addition,, it is fully soaked in staple fibre, therefore the tendency of the dispersed variation of the staple fibre in rubber combination is arranged if the content of softening agent (B ') is very few.Otherwise,, be difficult to handle if too much, then softening agent is exuded to the surface easily.The tendency that also has the heat-resistant aging reduction of rubber molding product.

In addition, if the content of staple fibre (C) is very few, then be difficult to give the rubber molding thing sometimes with mechanical characteristicies such as required tensile strength and tensile stresses.The tendency that particularly has tensile stress or hardness to become not enough.On the other hand, if too much, then the dispersed variation of staple fibre (C) particularly has the tendency that is difficult to obtain tensile strength and unit elongation.

In the masterbatch composition of the manner, in the scope of the purpose that can't harm the manner, softening agent, tenderizer and the lipid etc. that can contain except that softening agent of the present invention are becoming aqueous material below 150 ℃.These aqueous materials are so long as generally be used to the material of rubber and get final product, and there is no particular limitation.The use level of these materials is generally below the 50 weight % in the total amount of multi-functional compounds (B) and/or softening agent (B ') and above-mentioned aqueous material, is preferably below the 30 weight %, more preferably below the 10 weight %.

In the masterbatch composition of the manner, can also contain Synergist S-421 95 used in the general rubber, for example weighting agent, antiaging agent, vulcanizing agent, vulcanization accelerator, pigment, tackifiers, antiscorch(ing) etc.The use level of these Synergist S-421 95s is as long as in the scope of the effect of not damaging the manner substantially, and there is no particular limitation.

There is no particular limitation for the manufacture method of the masterbatch composition of the manner, for example can make: at first by following method, mixing copolymer rubber (A), multi-functional compounds (B) and/or the softening agent that contains itrile group (B ') and staple fibre (C), then, can be as required by mixing manufacturing the behind the Synergist S-421 95s such as absorb fillers.In addition, can also afterwards, the laggard one-step melting of copolymer rubber (A) that contains itrile group by interpolation be made at mixing staple fibre (C) and multi-functional compounds (B) and/or softening agent (B ').Like this, in the manner, need not copolymer rubber (A) granulating that to contain itrile group, just can obtain the masterbatch composition of staple fibre favorable dispersity with easy method.

In addition, in the composition of the copolymer rubber that contains itrile group (A) of latex state, add staple fibre (C) and in cakey material, mix multi-functional compounds (B) and/or softening agent (B '), perhaps in the composition of the copolymer rubber that contains itrile group (A) of latex state, add multi-functional compounds (B) and/or softening agent (B ') and in cakey material, mix staple fibre (C), can obtain masterbatch composition thus.

Can also in the composition of the copolymer rubber that contains itrile group (A) of latex state, add multi-functional compounds (B) and/or softening agent (B ') and staple fibre (C), solidify, can obtain masterbatch composition thus.

In this case, can directly add the Synergist S-421 95 that contains above-mentioned multi-functional compounds (B) and/or softening agent (B ') and staple fibre (C), add after also can in advance these Synergist S-421 95s being made emulsion.Can also add tensio-active agent, stablizer, colloid protective agent, thermosensitizing agent, frostproofer, defoamer, tackifier, water, emulsifying agent, pH regulator agent etc.

By using the masterbatch composition of above-mentioned the manner, staple fibre easily is distributed in the rubber combination.As mentioned above, be distributed in the rubber combination, then can improve mechanical characteristicies such as the tensile strength of the rubber molding thing that uses it and obtain and tensile stress by making staple fibre.In addition, can make the material of compression set and heat-resistant aging excellence.

(the 2nd mode)

Masterbatch composition of the present invention, its viscosity of 70 ℃ measuring with Brookfield type viscometer with respect to 100 weight parts is that liquid rubber composition (X), 25～550 weight parts of 500 handkerchiefs below second contain the staple fibre that length is 0.1～12mm (Y), it is characterized by, the weighting agent content in the described masterbatch composition is below the 8 weight %.

Liquid rubber composition described herein (X) need contain aqueous rubber, and then contains softening agent, tenderizer, lipid and multi-functional compounds etc. as required and becoming aqueous material below 150 ℃.

In the manner, 70 ℃ the viscosity that above-mentioned liquid rubber composition (X) is measured with Brookfield type viscometer is 500 handkerchiefs below second, is preferably 300 handkerchiefs below second, and more preferably 100 handkerchiefs are below second.If be higher than this scope, then staple fibre is difficult to mix in above-mentioned liquid rubber composition (X), so the dispersiveness of staple fibre in rubber combination has the tendency of variation.

On the other hand, the viscosity of above-mentioned liquid rubber composition (X) is generally 0.0001 handkerchief more than second.If be lower than this scope, then used its rubber combination to produce probably and oozed out.

That is, the above-mentioned viscosity of liquid rubber composition (X) was preferably for 0.0001～500 handkerchief second, 0.0001～300 handkerchief second more preferably, more preferably 0.0001～100 handkerchief second.

The aqueous rubber that above-mentioned liquid rubber composition (X) is contained is so long as generally get final product as the known material of aqueous rubber, there is no particular limitation, but consider from the better effects if that improves the staple fibre dispersiveness, 70 ℃ the viscosity of measuring with Brookfield type viscometer is preferably 900 handkerchiefs below second, more preferably 800 handkerchiefs are below second, and more preferably 700 handkerchiefs are below second.If be higher than this scope, then staple fibre is difficult to mix in above-mentioned liquid rubber composition (X), so the dispersiveness of staple fibre in rubber combination has the tendency of variation.

On the other hand, the viscosity of above-mentioned liquid rubber composition (X) is generally 0.0001 handkerchief more than second, is preferably 0.0002 handkerchief more than second, and more preferably 0.0003 handkerchief is more than second.If be lower than this scope, then do not have shear-stress, so masterbatch composition has and is difficult in rubber combination the dispersive tendency.

That is, the above-mentioned viscosity of aqueous rubber was preferably for 0.0001～900 handkerchief second, 0.0002～800 handkerchief second more preferably, more preferably 0.0003～700 handkerchief second.

By the measured value of measuring in gel permeation chromatography (polystyrene standard scaled value), the weight-average molecular weight of above-mentioned aqueous rubber (Mw) is preferably 100～50,000, and more preferably 200～40,000, more preferably 300～30,000.Mw can show as above viscosity usually at the aqueous rubber of described scope.

Used aqueous rubber can exemplify out known aqueous polydiene, aqueous silicone based rubber, aqueous acrylic rubber, liquid polyurethane class rubber and aqueous polysulfide rubber etc. in the manner.In these aqueous rubber, preferably use aqueous polydiene, further aqueous polydiene and the hydride thereof that contains itrile group of preferred therein use.The polydiene by containing itrile group and the interaction of hydride and staple fibre thereof, can show more significant reinforced effects, and the rubber combination of the cooperation masterbatch composition of the manner use the polydiene that contains itrile group and hydride thereof as rubber constituent the time, can be formed in the material of excellent dispersion of the masterbatch composition of the manner in this rubber combination.In addition, these aqueous rubber can use a kind separately, also can will be used in combination more than 2 kinds.

The manner is preferably used aqueously contains the polydiene of itrile group so long as have the aqueous polydiene of itrile group and get final product, and there is no particular limitation, for example, with α, β-ethylenic unsaturated nitrile monomer and other monomer copolymerizations and the rubber that obtains.α in this polydiene, the content of β-ethylenic unsaturated nitrile monomer is preferably 10～45 weight %, more preferably 15～40 weight %.In addition, iodine value is preferred below 120.α, β-ethylenic unsaturated nitrile monomer can exemplify out vinyl cyanide, methacrylonitrile, α-Lv Bingxijing etc., preferred vinyl cyanide.

With α, other monomers of β-ethylenic unsaturated nitrile monomer copolymerization can exemplify out conjugated diene monomer, non-conjugated diene class monomer etc.The conjugated diene monomer can exemplify out 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene etc., preferred 1,3-butadiene, isoprene.The preferred carbonatoms of non-conjugated diene class monomer is 5～12 monomer, can exemplify out 1,4-pentadiene, 1,4-hexadiene, vinyl norbornene, Dicyclopentadiene (DCPD) etc.And then, can also with alpha-olefin, aromatic vinyl base class monomer, fluorine-containing vinyl monomer, α, β-ethylenic unsaturated monocarboxylic and ester thereof, α, the protective agent of unsaturated polycarboxylic acid of β-ethylenic and acid anhydrides thereof or its ester, copolymerization etc. carries out copolymerization.

The preferred carbonatoms of alpha-olefin is 2～12, can exemplify out ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.Aromatic vinyl base class monomer can exemplify out vinylbenzene, alpha-methyl styrene, vinyl pyridine etc.Fluorine-containing vinyl monomer can exemplify out fluoro ethyl vinyl ether, fluoro propyl vinyl ether, o-trifluoromethyl vinylbenzene, pentafluorobenzoic acid vinyl acetate, difluoroethylene, tetrafluoroethylene etc.α, β-ethylenic unsaturated monocarboxylic can exemplify out vinylformic acid, methacrylic acid etc.α, β-ethylenic unsaturated monocarboxylic ester can exemplify out methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, butyl methacrylate etc.α, the unsaturated polycarboxylic acid of β-ethylenic can exemplify out methylene-succinic acid, fumaric acid, toxilic acid etc.α, the unsaturated polybasic acid anhydride of β-ethylenic can exemplify out itaconic anhydride, maleic anhydride etc.α, the unsaturated multi-carboxylate of β-ethylenic can exemplify out ethyl maleate, dimethyl maleate, dimethyl fumarate, DEF, di n butyl fumarate, fumaric acid two (the 2-ethyl is own) ester, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, methylene-succinic acid two (the 2-ethyl is own) ester etc.The protective agent of copolymerization can exemplify out N-(4-anilino phenyl) acrylamide, N-(4-anilino phenyl) Methacrylamide, N-(4-anilino phenyl) hydrocinnamamide, N-(4-anilino phenyl) crotonamide, N-phenyl-4-(3-vinyl benzyl oxygen base) aniline, N-phenyl-4-(4-vinyl benzyl oxygen base) aniline etc.

Preferred usually acrylonitrile-butadiene copolymer rubber and the hydride thereof of using of aqueous rubber.

The content of the above-mentioned aqueous rubber in the liquid rubber composition (X) is preferably more than the 3 weight %, more preferably more than the 6 weight %, more preferably more than 9 weight.The content of aqueous rubber is very few, and then the dispersiveness of the staple fibre in the rubber combination reduces probably, and perhaps rubber combination produces probably and oozes out.

As mentioned above, in the scope of the purpose that can't harm the manner, can also contain softening agent, tenderizer, lipid and multi-functional compounds etc. in the above-mentioned liquid rubber composition (X) is becoming aqueous material below 150 ℃.Softening agent (comprising tenderizer) and multi-functional compounds preferably use at the material described in the 1st mode.With respect to the usage ratio of aqueous rubber, also can be according to usage ratio with respect to the copolymer rubber that contains itrile group (A) in the 1st mode.By using these aqueous materials, even when the viscosity of the aqueous rubber in the liquid rubber composition (X) is high, the viscosity that also can make said composition is 500 handkerchiefs below second, therefore, can improve the dispersiveness of staple fibre in rubber combination.Just there is no particular limitation so long as generally be used for the material of rubber for these aqueous materials.

There is no particular limitation for the manufacture method of above-mentioned liquid rubber composition (X), can cooperate each composition by the manufacture method according to general rubber combination, carries out mixing the manufacturing.When cooperating above-mentioned aqueous material, can be pre-mixed aqueous rubber and aqueous material, and mix staple fibre therein, can also when aftermentioned is made masterbatch composition, join in the mixing roll together with mixing roll.

With regard to the length and kind of the used staple fibre of the manner (Y), owing to identical, therefore in this description will be omitted with situation about illustrating in above-mentioned the 1st mode as staple fibre (C).

With respect to the above-mentioned liquid rubber composition of 100 weight parts (X), the content of staple fibre (Y) is 25～550 weight parts, is preferably 27～500 weight parts, more preferably 29～450 weight parts.If the content of staple fibre (Y) is very few, then be difficult to give rubber molding thing (rubber combination being vulcanized the sulfide that forms) sometimes with mechanical characteristicies such as required tensile strength and tensile stresses; Otherwise, if too much, then dispersed variation, the special tendency that is difficult to obtain tensile strength and unit elongation that exists.

In the manner, by using the liquid rubber composition (X) of regulation viscosity, even the consumption of weighting agent below specified amount, even further do not cooperate weighting agent, also can make staple fibre be dispersed in the rubber combination.Therefore, the content of the weighting agent in the masterbatch composition of the manner can be made as below the 8 weight %.From further making the dispersiveness of weighting agent become good consideration, the content of weighting agent preferably is made as below the 7 weight %, more preferably is made as below the 5 weight %.In the manner, reduce the content of weighting agent by aforesaid method, need not to consider the dispersiveness of weighting agent thus, can make that staple fibre is easier to be disperseed in rubber combination.Weighting agent can exemplify out the carbon black that generally is used for rubber, silicon-dioxide, clay, talcum, lime carbonate etc.

It should be noted that by aqueous rubber and convert that the content of the liquid rubber composition in the masterbatch composition of the manner (X) is preferably 15～80 weight %, more preferably 20～75 weight %.

In the masterbatch composition of the manner, can also contain the Synergist S-421 95 that is useful on ordinary rubber, for example the weighting agent except that above-mentioned (comprising toughener), antiaging agent, vulcanizing agent, vulcanization accelerator, vulcanization aid, vulcanization retarder, pigment, tackifiers, antiscorch(ing) etc.The use level of these Synergist S-421 95s is as long as in the scope of the effect of not damaging the manner substantially, and there is no particular limitation.

There is no particular limitation for the manufacture method of the masterbatch composition of the manner, for example can followingly make: at first, and mixing liquid rubber composition (X) and staple fibre (Y), then, can be as required by mixing manufacturing the behind the Synergist S-421 95s such as absorb fillers.Like this, in the manner, need not in advance staple fibre to be untied winding, just can obtain the masterbatch composition of staple fibre favorable dispersity with easy method.In addition, can obtain masterbatch composition even in the liquid rubber composition (X) of latex state, add staple fibre (Y) and solidify also.In this case, above-mentioned Synergist S-421 95 can directly add, and also can make emulsion in advance and add afterwards.Can also add tensio-active agent, stablizer, colloid protective agent, thermosensitizing agent, frostproofer, defoamer, tackifier, water, emulsifying agent, pH regulator agent etc.

By using the masterbatch composition of above-mentioned the manner, staple fibre easily is distributed in the rubber combination.Be distributed in the rubber combination by the aforesaid staple fibre that makes, can improve mechanical characteristicies such as the tensile strength of the rubber molding thing that uses it and obtain and tensile stress.

B. rubber combination

Being characterized as of rubber combination of the present invention, it is to contain the 1st mode that describes in detail or the masterbatch composition of the 2nd mode forms in above-mentioned " A. masterbatch composition " one.In the present invention, by containing above-mentioned masterbatch composition, can make the rubber combination of the excellent dispersion of staple fibre.

The masterbatch composition that the present invention is used, consider from masterbatch composition more easily being distributed to the rubber combination, the aqueous rubber of the preferred copolymer rubber that contains itrile group (A) of suitably selecting to be used for this masterbatch composition or liquid rubber composition (X) and with the good material of intermiscibility as the rubber of the matrix components of the rubber combination that cooperates it.

The content of the masterbatch composition in the rubber combination of the present invention is as long as in the scope that can be distributed in the rubber combination, there is no particular limitation, with respect to the total amount of 100 weight parts as the above-mentioned rubber constituent of the matrix components of rubber combination, be preferably 0.12～175 weight part, 0.6～100 weight part more preferably, further preferred 1.2～50 weight parts.If the content of masterbatch composition is very few, then can not obtain mechanical characteristicies such as sufficient tensile strength and tensile stress sometimes; Otherwise, if too much, poor in processability sometimes then, contained multi-functional compounds's etc. aqueous composition might ooze out in masterbatch composition.

For rubber combination of the present invention,, staple fibre is disperseed easily by containing above-mentioned masterbatch composition.The content of the staple fibre in the rubber combination of the present invention, with respect to the total amount of 100 weight parts as the above-mentioned rubber constituent of the matrix components of rubber combination, be preferably 0.1～35 weight part, more preferably 0.5～20 weight part, more preferably 1～10 weight part.As long as in this scope, just can make the rubber combination of staple fibre excellent dispersion by common blending means.

The rubber that contains as matrix components in the rubber combination of the present invention, so long as generally well-known rubber gets final product, there is no particular limitation, but consider from can access significant reinforced effects by staple fibre is disperseed, preferred polydiene and the hydride thereof that contains itrile group, for example acrylonitrile-butadiene copolymer rubber and the hydride thereof of using.When particularly essential heat-resistant aging, weathering resistance etc., preferably use hydride.

Can contain the Synergist S-421 95 that is useful on ordinary rubber in the rubber combination of the present invention.Synergist S-421 95 can exemplify out with at the identical example of material described in above-mentioned " A. masterbatch composition ".Wherein, particularly preferably contain α, β-ethylenic metallic salts of unsaturated carboxylate, organic peroxide sulfuration agent as vulcanizing agent.

The manufacture method of rubber combination of the present invention is identical with the manufacture method of general rubber combination, for example, in the rubber combination that constitutes at the rubber that contains the matrix components that has carried out mixing formation rubber combination more than a kind in advance, cooperate above-mentioned masterbatch composition, further carry out mixing and make.In the present invention, by as above cooperating above-mentioned masterbatch composition, carrying out mixing short-cut method, can obtain the rubber combination of the excellent dispersion of staple fibre.

C. sulfide

Being characterized as of sulfide of the present invention cooperates vulcanizing agent that its sulfuration is obtained in its rubber combination that describes in detail in above-mentioned " B. rubber combination " one.Sulfide of the present invention is owing to be that rubber combination sulfuration with the excellent dispersion of staple fibre forms, so mechanical characteristics excellences such as tensile strength and tensile stress.In addition, sulfide of the present invention excellence aspect compression set and heat-resistant aging.The compression set excellence refers to, if this distortion is little, even then distortion also can keep definite shape for a long time.In addition, the heat-resistant aging excellence is meant, is not easy Yin Re and wears out.

The use level of the vulcanizing agent in the rubber combination of the present invention, the total rubber composition with respect in the 100 parts by weight of rubber compositions is preferably about 1～10 weight part.

Vulcanization process can exemplify out the method that rubber combination is shaped the back or heats when being shaped.

Curing temperature is preferably 100～200 ℃ according to the kind of rubber combination and different, and more preferably 130～195 ℃, further preferred 140～190 ℃.If curing temperature is low excessively, then sulfuration is essential long-time, perhaps vulcanizes the density step-down sometimes.Otherwise if too high, it is bad then might to be shaped.

Though curing time is according to vulcanization process, curing temperature or shape etc. and greatly different, consider from the sulfuration density that obtains suiting and the idea of production efficiency, be preferably 1 minute usually～12 hours.

Heating means can exemplify out pressurized, heated, steam-heated cal(l)andria, baking oven for heating, hot blast heating etc. as the vulcanization process of rubber and normally used known method.According to the shape of sulfide, size etc., even vulcanize on the surface sometimes, does not vulcanize inside yet.In this case, as mentioned above, after vulcanizing, can maintain the post cure of the condition of high temperature.

There is no particular limitation for the purposes of sulfide of the present invention; for example industrial goods or its parts with sealing, string rubber, rubber rollers, rubber hose, tire, liner, boot, brake rod, clutch plate etc. are representative, can also be used in used wrapping machine such as oil well, gas well, outer shield, the protection of pipe device etc.Sealer can exemplify out rotation with, shake usefulness, the motion of back and forth employing etc. is with sealer and fixedly uses sealer.Motion can exemplify out oil seal, piston packing, mechanical seal etc. with sealer, fixes with sealing and can exemplify out O shape ring, メ Application Le レ ジ エ Application ト sealing, various pads etc.String rubber can exemplify out flat rubber belting, V band, many ditches belt, round belt, angle band, cingulum etc.Rubber rollers can exemplify out as printing press, duplicate the parts of OA machine such as machine roller, spin with draw roll, weaving with fiber process such as draw rolls with system iron such as roller, bridle rolls, damping roller, steering roller with roller etc.Rubber hose can exemplify out single tube rubber hose, multilayer rubber flexible pipe, woven enhancing flexible pipe, batching formula enhancing flexible pipe etc.Consider that from mechanical characteristicies such as tensile strength and tensile stress are excellent sulfide of the present invention is suitable for the nacelle of various tires, band, flexible pipe, liner, sealer, boot, automobile etc.Rubber molding product that can under severe condition, use as the nacelle of automobile etc. particularly.

The present invention is not limited to above-mentioned embodiment.Above-mentioned embodiment only is an example, comprises any in the technical scope of the present invention and has and the essentially identical formation of the described technical idea of claims of the present invention, and bring into play the mode of same action effect.

Embodiment

Enumerate embodiment below and comparative example specifies the present invention.It should be noted that % relevant in part or the cooperation unless otherwise specified, be weight basis.In addition, each evaluating characteristics test is carried out with following method.

(1) the piece number (individual) of staple fibre

The surface of the flap of difference visual observations masterbatch composition described later and the sulfuration flap of rubber combination is to the staple fibre piece number more than the flap counting 1mm, to the staple fibre piece number more than the sulfuration flap counting 0.5mm.

(2) tension test

The shape thing carries out punching press along the direction parallel with the grain direction (roller is extruded direction) of rubber to the sulfuration flap with No. 3 type dumbbells, make test film, use this test film,, measure tensile strength (MPa), unit elongation (%) and 25% tensile stress (MPa) according to the JISK6251 standard.

(3) hardness test (Duro A)

According to JIS K6253 standard, use Durometer A type hardness tester trier to measure the hardness of sulfuration flap.

(4) permanent compression test

Use internal diameter to be 29mm, the thickness mould as 12.5mm, through 25 minutes, 10MPa vulcanized vulcanizable rubber composition with pressure under 170 ℃, obtained test film.Use this test film,, under 25% compressed state, remain on 150 ℃ after 168 hours, measure compression set (%) according to JIS K6262 standard.

(5) air oven ageing test

Use No. 3 type dumb-bell test pieces identical with above-mentioned tension test, the air oven ageing test (normal Oven Method) according to JIS K6257 prescribed by standard makes its aging 504 hours at 150 ℃.Test film after using this aging according to JIS K6253 standard, uses Durometer A type hardness tester trier to measure the hardness of sulfide, calculates the changes in hardness (mark) of aging front and back.

(6) viscosity (handkerchief second)

Use brookfield's viscometer (Brookfield [BROOK FIELD] corporate system, trade(brand)name: MODEL DV-1+), measure liquid rubber composition (X) 70 ℃ viscosity.

(embodiment 1)

Press the prescription of table 1 record, use closed mixing machine (BRAVENDER corporate system, trade(brand)name: LABSTATION, W50 type mixing tank, cam type rotor, 70cc), under 50 ℃, 50rpm, 10 minutes, the condition of filling ratio 70%, each composition is made masterbatch composition.

The gained masterbatch composition is packed in the mould of 15cm * 8cm * 0.2cm, 100 ℃ keep pressurization 5 clocks down after, under 40 ℃, carry out 10 hours press moldings, obtain flap.Measure the piece number of the staple fibre more than the 1mm that contains in the gained flap.And confirm to have or not to ooze out.

Then, the rubber combination I of ready made following cooperation is put in the closed mixing machine (BRAVENDER corporate system, trade(brand)name: LABSTATION, W50 type mixing tank, cam type rotor, 70cc), after mixing 1 minute, drop into above-mentioned masterbatch composition, mixing 3 minutes, make rubber combination II.Mixingly under 50 ℃, 30rpm condition, carry out.Filling ratio is that the use level of 70%. masterbatch compositions is as follows: with respect to the rubber constituent among 100 parts of above-mentioned rubber combination I, the staple fibre amount is 4 parts.

(composition among the rubber combination I 〉

Solid rubber: 100 parts

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 11, acrylonitrile unit content 36%, Japanese ZEON (strain) system, Zetpol 2010L)

Zinc dimethacrylate: 15 parts

Weighting agent: 25 parts

(carbon black, East Sea CARBON (strain) system, SEASTSN-770)

Softening agent: 10 parts

(tri trimellitate (the 2-ethyl is own) ester)

Vulcanizing agent: 10 parts

(1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 3-, Japanese grease (strain) system, PEROXYMON F-40)

Vulcanization accelerator: 10 parts

(No. 1, zinc oxide, zinc white)

Antiaging agent 1:1.5 part

(4,4 '-(α, α '-3,5-dimethylphenyl) pentanoic, the emerging chemical industry of imperial palace (strain) system, NOCLACCD)

Antiaging agent 2:1.5 part

(zinc salt of 2-mercaptobenzimidazole, the emerging chemical industry of imperial palace (strain) system, NOCLACMBZ)

The rubber combination II that so obtains is carried out the sheet roller with 50 ℃ roller go out, make thickness reach 0.23cm, in the mould of the 15cm * 8cm that packs into then * 0.2cm, the limit adds flanging and carry out 20 minutes press moldings under 170 ℃, obtains vulcanizing flap.Use this sulfuration flap, carry out tension test, hardness test and air oven ageing test.And then, should vulcanize after flap grinds the surface with shredder, measure the piece number of the above staple fibre of the 0.5mm that contains in the sulfuration flap.The results are shown in (following embodiment 2,3, comparative example 1～6 are identical) in the table 1.

(embodiment 2)

Except the kind of the copolymer rubber that will contain itrile group changes, prepare masterbatch composition according to similarly to Example 1 method, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(embodiment 3)

Except the kind of softening agent is changed, prepare master batch according to similarly to Example 1 method, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(comparative example 1 and 2)

Except the kind with softening agent becomes molecular weight is the softening agent below 400, prepares master batch according to similarly to Example 1 method, uses it to make the sulfuration flap, carries out each evaluating characteristics test.

(comparative example 3)

30 parts of copolymer rubbers that contain itrile group are altered to 70 parts, do not use softening agent, in addition, prepare masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to similarly to Example 1 method.

(comparative example 4)

30 parts of copolymer rubbers that contain itrile group are altered to 3 parts, 40 parts of softening agent are altered to 77 parts, further 30 parts of staple fibres are altered to 20 parts, in addition, prepare masterbatch composition according to similarly to Example 1 method, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(comparative example 5)

Except mismatching staple fibre, make the sulfuration flap according to method similarly to Example 1, carry out each evaluating characteristics test.

(comparative example 6)

Except cooperating staple fibre to replace the masterbatch composition, make the sulfuration flap according to method similarly to Example 1, carry out each evaluating characteristics test.

Table 1

	Embodiment 1 embodiment 2 embodiment 3 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6
		＜masterbatch composition〉copolymer rubber 1 (part) that contains itrile group contains copolymer rubber 2 (part) plasticizer 1 (part) plasticizer 2 (part) plasticizer 3 (part) plasticizer 4 (part) short fiber (part) of itrile group	30 - 30 30 30 70 3 - - - 30 - - - - - - - 40 40 - - - - 77 - - - - 40 - - - - - - - - - 40 - - - - - - - - - 40 - - - - 30 30 30 30 30 30 20 - -
Add up to (part)	100 100 100 100 100 100 100 - -
		The piece number (individual) of the staple fibre that (evaluating characteristics) 1mm is above has or not and oozes out	26 22 25 28 23 420 16--have a small amount of nothing to have to have on a small quantity have on a small quantity a small amount of nothing a large amount of--
＜rubber combination II〉rubber combination I (part) masterbatch composition (comprising staple fibre) (part) staple fibre (part)	173 173 173 173 173 173 173 173 173 13.33 13.33 13.33 13.33 13.33 13.33 20 - - - - - - - - - - 4
		Piece number (individual) tensile test tensile strength (MPa) percentage elongation (%) tensile stress (MPa) hardness test (Duro A) the hardness air oven ageing test firmness change (mark) of the short fiber that (evaluating characteristics) 0.5mm is above	9 7 7 10 9 113 3 0 260 19.2 19.4 19.1 18.8 17.9 15.8 16.4 26.9 14.8 360 350 350 340 330 150 250 470 70 12.2 12.3 11.9 11.2 11.1 12.9 9.4 1.2 13.2 76 75 75 75 75 76 70 68 76 +7 +7 +8 +11 +11 +8 +14 +9 +8

Composition in the＜table 〉

The copolymer rubber 1 that contains itrile group

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 28, acrylonitrile unit content 36%, 100 ℃ mooney viscosity ML ₍₁₊₄₎Be 78, Japanese ZEON corporate system, Zetpol2020)

The copolymer rubber 2 that contains itrile group

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 27, acrylonitrile unit content 19%, 100 ℃ mooney viscosity ML ₍₁₊₄₎Be 70, Japanese ZEON corporate system, Zetpol4320)

Softening agent 1

(tri trimellitate (the 2-ethyl is own) ester, molecular weight 547, Asahi Denka Kogyo K. K's system, ADEKA SIZER C-8)

Softening agent 2

(di adipate compounds, molecular weight 434, Asahi Denka Kogyo K. K's system, ADEKA SIZER RS107)

Softening agent 3

(phthalic acid two (the 2-ethyl is own) ester, molecular weight 391, Kao Corp's system, VINYCIZER 80)

Softening agent 4

(hexanodioic acid two (the 2-ethyl is own) ester, molecular weight 371, J-PLUS Co., Ltd. system, DOA)

Staple fibre

(length is contraposition-Fang acid amides pulp fibers, Teijin Twaron BV corporate system, the Twaron 1091 of 1.0～1.8mm)

Following as shown in Table 1 result.When using molecular weight less than 400 softening agent, heat-resistant aging poor (comparative example 1 and 2).When not using softening agent, the dispersiveness of staple fibre is extremely low, can not obtain the mechanical characteristics (comparative example 3) of sulfuration flaps such as tensile strength and unit elongation.Otherwise, containing the copolymer rubber of itrile group when very few, can ooze out, the mechanical characteristics of sulfuration flap also reduces (comparative example 4).On the other hand, do not use masterbatch composition and when being added with staple fibre, the dispersed extreme difference of staple fibre can not obtain to vulcanize the mechanical characteristics (comparative example 6) of flap.

Relative therewith, using acrylonitrile unit content is the following copolymer rubbers that contain itrile group of 40 weight %, and with specified proportion when to cooperate molecular weight be softening agent more than 400, staple fibre all disperses in masterbatch composition and sulfuration flap well, compare with the situation of mismatching staple fibre (comparative example 5), show higher mechanical characteristics.Also prove its heat-resistant aging excellence (embodiment 1～3).

(embodiment 4)

Press the prescription of table 2 record, according to the method identical with embodiment 1, make masterbatch composition, the operation according to similarly to Example 1 obtains flap.Measure the piece number of the staple fibre more than the 1mm that contains in the gained flap.

Then, use the rubber combination I of embodiment 1 record,, obtain rubber combination III according to operation similarly to Example 1.

Use the rubber combination III that so obtains,, obtain vulcanizing flap according to operation similarly to Example 1.Use this sulfuration flap, carry out tension test, hardness test, permanent compression test and air oven ageing test by aforesaid method.And then, with shredder this sulfuration flap is carried out after the surface grinding, measure the piece number of the above staple fibre of the 0.5mm that contains in the sulfuration flap.The results are shown in (identical in following embodiment 5～8, comparative example 7～12) in the table 2.

(embodiment 5)

40 parts of multi-functional compounds are altered to 50 parts, 30 parts of staple fibres are altered to 20 parts, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 4.

(embodiment 6)

30 parts of copolymer rubbers that contain itrile group are altered to 50 parts, 40 parts of multi-functional compounds are altered to 30 parts, 30 parts of staple fibres are altered to 20 parts, in addition, make masterbatch composition according to method similarly to Example 4, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(embodiment 7)

30 parts of copolymer rubbers that contain itrile group are altered to 15 parts, 40 parts of multi-functional compounds are altered to 65 parts, 30 parts of staple fibres are altered to 20 parts, in addition, make masterbatch composition according to method similarly to Example 4, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(embodiment 8)

40 parts of multi-functional compounds are altered to 20 parts, and use 20 parts in softening agent, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 4.

(comparative example 7)

Except using 40 parts of softening agent to replace making masterbatch composition according to method similarly to Example 4 the multi-functional compounds, use it to make the sulfuration flap, carry out each evaluating characteristics test.In this comparative example, observe and ooze out.

(comparative example 8)

30 parts of copolymer rubbers that contain itrile group are altered to 67 parts, 40 parts of multi-functional compounds are altered to 3 parts, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 4.

(comparative example 9)

30 parts of copolymer rubbers that contain itrile group are altered to 70 parts, do not use the multi-functional compounds, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 4.

(comparative example 10)

30 parts of copolymer rubbers that contain itrile group are altered to 3 parts, 40 parts of multi-functional compounds are altered to 77 parts, 30 parts of staple fibres are altered to 20 parts, in addition, make masterbatch composition according to method similarly to Example 4, use it to make the sulfuration flap, carry out each evaluating characteristics test.In this comparative example, observe and ooze out.

(comparative example 11)

Except not using the staple fibre, make the sulfuration flap according to method similarly to Example 4, carry out each evaluating characteristics test.

(comparative example 12)

Except using staple fibre to replace making the sulfuration flap according to method similarly to Example 4 the masterbatch composition, carry out each evaluating characteristics test.

Table 2

	Embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 comparative examples 7 comparative examples 8 comparative examples 9 comparative examples 10 comparative examples 11 comparative examples 12
		＜masterbatch composition〉contain copolymer rubber (part) multi-functional compounds (part) softening agent (part) staple fibre (part) of itrile group	30 30 50 15 30 30 67 70 3 - - 40 50 30 65 20 - 3 - 77 - - - - - - 20 40 - - - - - 30 20 20 20 30 30 30 30 20 - -
Add up to (part)	100 100 100 100 100 100 100 100 100 - -
		The piece number (individual) of the staple fibre that (evaluating characteristics) 1mm is above	26 18 17 16 25 28 310 420 14 - -
＜rubber combination III) rubber combination I (part) masterbatch composition (comprising staple fibre) (part) staple fibre (part)	173 173 173 173 173 173 173 173 173 173 173 13.33 20 20 20 13.33 13.33 13.33 13.33 20 - - - - - - - - - - - - 4
		Piece number (individual) tensile test tensile strength (MPa) percentage elongation (%) tensile stress (MPa) hardness test (Duro A) hardness permanent compression test compression set (%) the air oven ageing test firmness change (mark) of the short fiber that (evaluating characteristics) 0.5mm is above	8 4 3 2 6 10 93 113 3 0 260 19.6 18.2 19.2 17.6 19.8 18.8 16.3 15.8 16.4 26.9 14.8 350 270 310 260 370 340 160 150 240 470 70 12.6 11.5 12.7 11.1 12.1 11.2 12.7 12.9 10.9 1.2 13.2 77 75 77 74 76 75 77 76 74 68 76 55 57 52 58 60 68 67 67 60 55 67 +7 +8 +6 +8 +8 +11 +7 +8 +12 +9 +8

Composition in the＜table 〉

The copolymer rubber 1 that contains itrile group

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 28, acrylonitrile unit content 36%, 100 ℃ mooney viscosity ML ₍₁₊₄₎Be 78, Japanese ZEON corporate system, Zetpol2020)

The multi-functional compounds

(isocyanuric acid triallyl, Nippon Kasei Chemical Company's system, TAIC)

Softening agent

(phthalic acid two (the 2-ethyl is own) ester, molecular weight 391, Kao Corp's system, VINYCIZER 80)

Staple fibre

(contraposition-Fang acid amides pulp fibers, Teijin Twaron bv corporate system, the Twaron 1091 of long 1.0～1.8mm)

Following as shown in Table 2 result.When using molecular weight to replace the multi-functional compounds, can ooze out less than 400 softening agent, and compression set and heat-resistant aging poor (comparative example 7).Even if use the multi-functional compounds, its use level is crossed the dispersed variation of staple fibre (comparative example 8) at least.When not using multi-functional compounds and softening agent, the then dispersed further reduction (comparative example 9) of staple fibre.As mentioned above, if the dispersiveness of staple fibre reduces, then can not obtain the mechanical characteristics of sulfuration flaps such as tensile strength and unit elongation.Otherwise, when multi-functional compounds's use level is too much, can ooze out, the mechanical characteristics of sulfuration flap is variation (comparative example 10) also.On the other hand, do not use masterbatch composition and when being added with staple fibre, the dispersed extreme difference of staple fibre can not obtain to vulcanize the mechanical characteristics (comparative example 12) of flap.

Relative therewith, when using the multi-functional compounds in specified range, staple fibre all disperses in masterbatch composition and sulfuration flap well, compares with the situation of mismatching staple fibre (comparative example 11), shows higher mechanical characteristics.Prove that also its compression set is little, heat-resistant aging is excellent (embodiment 4～8).

(embodiment 9)

Press the prescription of table 3 record, according to the method identical with embodiment 1, make masterbatch composition, the operation according to similarly to Example 1 obtains flap.Measure the piece number of the staple fibre more than the 1mm that contains in the gained flap.

Then, use the rubber combination I of embodiment 1 record,, obtain rubber combination IV according to operation similarly to Example 1.

Use the rubber combination IV that so obtains,, obtain vulcanizing flap according to operation similarly to Example 1.

Use this sulfuration flap, measure tensile strength, unit elongation, tensile stress and hardness by aforesaid method.And then, with shredder this sulfuration flap is carried out after the surface grinding, measure the piece number of the above staple fibre of the 0.5mm that contains in the sulfuration flap.The results are shown in (identical in following embodiment 10～15, comparative example 13～16) in the table 3.

(embodiment 10,11)

To be altered to 30 parts by the use level of 60 parts of aqueous rubber 1, use 30 parts of multi-functional compounds or 30 parts of softening agent, in addition, make masterbatch composition according to method similarly to Example 9, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(embodiment 12,13)

Cooperate weighting agent, make the use level of this weighting agent and aqueous rubber 1 use level add up to 60 parts, in addition, make masterbatch composition according to method similarly to Example 9, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(embodiment 14)

The use level of aqueous rubber 1 is altered to 20 parts by 60 parts, makes 40 parts of staple fibres be altered to 80 parts, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 9.

(embodiment 15)

Use 10 parts of following aqueous rubber 2, use 50 parts of multi-functional compounds, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 9.

(comparative example 13)

The use level of aqueous rubber 1 is altered to 50 parts by 60 parts, cooperates 10 parts of weighting agents, in addition, make masterbatch composition, use it to make the sulfuration flap, carry out each evaluating characteristics test according to method similarly to Example 9.

(comparative example 14)

Except using aqueous rubber 2 to replace making masterbatch composition according to method similarly to Example 9 the aqueous rubber 1, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(comparative example 15)

Except using solid rubber to replace making masterbatch composition according to method similarly to Example 9 the aqueous rubber 1, use it to make the sulfuration flap, carry out each evaluating characteristics test.

(comparative example 16)

Except cooperating staple fibre to replace making the sulfuration flap according to method similarly to Example 9 the masterbatch composition, carry out each evaluating characteristics test.

Table 3

	Embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 comparative examples 13 comparative examples 14 comparative examples 15 comparative examples 16
		＜masterbatch composition〉aqueous rubber 1, (part) aqueous rubber 2, (part) solid rubber, (part) multi-functional compounds, (part) softening agent, (part)	60 30 30 53 57 20 - 50 - - - - - - - - - 10 - 60 - - - - - - - - - - - 60 - - 30 - - - - 50 - - - - - - 30 - - - - - - - -
Staple fibre (part) weighting agent (part)	40 40 40 40 40 80 40 40 40 40 - - - - 7 3 - - 10 - - -
		Add up to (part)	100 100 100 100 100 100 100 100 100 100 -
(viscosity) rubber constituent (handkerchief second) liquid rubber composition (handkerchief second)	10 10 10 10 10 10 600 10 600 can not measure-10 4.7 4 10 10 10 100 10 600 can not measure-
		The piece number (individual) of the staple fibre that (evaluating characteristics) 1mm is above	2 2 3 15 7 32 12 50 70 460 -
＜rubber combination IV〉rubber combination I (part) masterbatch composition (comprising staple fibre) (part) staple fibre (part)	173 173 173 173 173 173 173 173 173 173 173 10 10 10 10 10 5 10 10 10 10 - - - - - - - - - - - 4
		The piece number of the staple fibre that (evaluating characteristics) 0.5mm is above, (individual) tensile strength, (MPa) unit elongation, (%) tensile stress, (MPa) hardness test, (Duro A)	0 2 3 11 6 20 8 42 40 130 260 20.1 19.2 19.4 19.2 20.2 18.8 19.5 17.8 17.5 15.2 14.8 380 340 370 320 360 310 300 260 240 130 70 12.3 12.5 11.2 12.2 12.4 12.4 13.2 12.6 12.4 12.9 13.2 75 77 74 76 75 75 78 76 76 76 76

Composition in the＜table 〉

Aqueous rubber 1

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 30, acrylonitrile unit content 36%, 70 ℃ the viscosity of measuring with brookfield's viscometer are 10 handkerchief second)

Aqueous rubber 2

(acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36%, 70 ℃ the viscosity of measuring with brookfield's viscometer are 600 handkerchief second)

Solid rubber

(acrylonitrile-butadiene copolymer rubber hydride, iodine value 28, acrylonitrile unit content 36%, Japanese ZEON corporate system, Zetpol 2020,100 ℃ the mooney viscosity that records according to JIS K6300 standard are 78)

Staple fibre

(contraposition-Fang acid amides pulp fibers, Teijin Twaron bv corporate system, the Twaron 1091 of long 1.0～1.8mm)

The multi-functional compounds

(isocyanuric acid triallyl, Nippon Kasei Chemical Company's system, TAIC)

Softening agent

(tri trimellitate (the 2-ethyl is own) ester, molecular weight 547, Asahi Denka Kogyo K. K's system, ADEKASIZFRC-8)

Weighting agent

(carbon black, East Sea CARBON (strain) system, SEAST SO N-550)

Following as shown in Table 3 result.When use contained the masterbatch composition of 10% weighting agent, the dispersed variation of the staple fibre in the masterbatch composition can be observed polylith staple fibre (comparative example 13) in gained sulfuration flap.When the viscosity of use liquid rubber composition (X) is higher than the material of specialized range, the dispersed further variation (comparative example 14 and 15) of staple fibre in masterbatch composition and sulfuration flap.Do not use masterbatch composition and when being added with staple fibre, the dispersed extreme difference of staple fibre also can't obtain to vulcanize the mechanical characteristics (comparative example 16) of flap.Like this, when the dispersiveness of staple fibre was hanged down, the tensile strength and the unit elongation of sulfuration flap were all insufficient.

Relative therewith, the liquid rubber composition (X) that has specialized range viscosity in use, and when reducing the use level of weighting agent, staple fibre all disperses in masterbatch composition and sulfuration flap well, show high mechanical characteristics, demonstrate high-tensile and unit elongation.And its tensile stress and hardness all are in the excellent scope (embodiment 9～15).

Claims (7)

1. masterbatch composition, it contains: 5～78 weight parts contain α, β-unitary the copolymer rubber of ethylenic unsaturated nitrile monomer (A), 5～78 weight part multi-functional compounds (B) and/or molecular weight be more than 400 softening agent (B '), and 17～90 weight part length be the staple fibre (C) of 0.1～12mm, wherein, (A), (B) and/or (B ') and total amount (C) are 100 weight parts.

2. masterbatch composition as claimed in claim 1 wherein, contains α, the α of β-unitary copolymer rubber of ethylenic unsaturated nitrile monomer (A), and β-ethylenic unsaturated nitrile monomer unit content is below 40 weight parts.

3. rubber combination, it contains claim 1 or 2 described masterbatch compositions.

4. sulfide, it forms the described rubber combination sulfuration of claim 3.

5. masterbatch composition, its viscosity at 70 ℃ of measuring with brookfield's viscometer with respect to 100 weight parts is the liquid rubber compositions (X) of 500 handkerchiefs below second, containing 25～550 weight part length is the staple fibre (Y) of 0.1～12mm, it is characterized by, the weighting agent content in the described masterbatch composition is below the 8 weight %.

6. rubber combination, it contains the described masterbatch composition of claim 5.

7. sulfide, it forms the described rubber combination sulfuration of claim 6.