CA1274335A - Rubber compositions containing a multi-component copolymer rubber - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A multi-component copolymer rubber consisting essentially of (A) 20 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate, (B) 30 to 79.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with (A), (B) and (C), excels in heat resistance, ozone resistance, sour gasoline resistance and sour gasohol resistance. These properties of said multi-component copolymer rubber can further be improved by incorpo-rating into the copolymer rubber a crosslinking agent, a metal salt, a vinylidene fluoride polymer, a vinyl chloride resin or other multi-component copolymer rubber.

Description

t3~5 This is a divisional application of the application ~erial No. 477,458 filed March 26, 1985.
The parent application relates to a novel multi-component copolymer rubber consisting essentially of a cyano-substituted alkyl (meth)acrylate, an alkyl acrylate and a diene monomer, excellent in heat resistance, ozone resistance, sour gasoline resistance and sour gasohol resistance. This application relates to a rubber composition containing said multi-component copolymer rubber and other components.

In recent years, in automobiles, gasoline-resistant rubbers arein use in atmospheres whose temperatures are becoming increasingly higher in connection with countermeasures for exhaust gas regulations and engine modifications for higher performance. Hence, there is now required a gasoline-resistant rubber excellent in heat resistance and ozone resistance. With respect to these gasoline-resistant rubbers, there is a further ~ problem that gasolines are oxidized in fuel systems oE automobiles, - ~ etc. to produce a sour gasoline [-the sour gasoline refers to a gasoline con-taining peroxides produced by gasoline oxidation at ~-~ 20 high temperatures and itis described in detail in A. Nersasian, Rubber and Plastics News, June 26 (1978)] and thls sour gasoline detexiorates gasoline-resistant rubbers.
In connection with tight supply of crudes on worldwide basis, addition of an alcohol to a gasoline has ' , :` - ' ' ~ . ................................. ..
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1 been tried. This gasoline-alcohol mixture, namely, gasohol is also oxidized to produce a sour gasohol and this sour gasohol deteriorates gasoline-resistant rubbers as well.
As gasoline-resistant rubbers, butadiene-S acrylonitrile rubber has widely been used in such applications as hoses, gaskets, O-rings, packings and oil seals. However, butadiene-acrylonitrile rubber is poor in ozone resistan~e and insufficient in heat resistance and sour gasoline resistance, and therefore, it is di~ficult to provide a rubber part having a suficient relia~ility even when used in contact with a gasoline at high temperatures as mentioned above.
In order to overcome the drawbacks of butadiene-acrylonitrile rubber, it is known to use a blend of butadiene-acrylonitrile rubber with poly(vinyl chloride), - thereby improving sour gasoline resistance and ozone - resistance ~Japanese Patent Application Kokai (Laid-Open) No. 89,388~80]. However, this blend has no improved heat resistance, is poor in other properties such as low temperature resistance and permanent compression set, which are required as gasoline-resistant rubber materials and cannot be æaid to have sufficient gasohol resistance.
Hence, it has been desired to overcome these drawbacks.
Fluororubber has been spotlighted as a gasoline-resistant rubber material because of its excellency in sour gasoline resistance, ozone resistance and heat resis~ance. Howeqert the fluororubber has an insufficient flexibility at low temperatures, and poor physical properties, and is .. . . ........... . .. .
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difficult to handle and very expensive. Accordingly it cannot be used as a general purpose gasoline resistant rubber.
Under such circumstances, the present inventors have studied on various materials which are excellent in heat resistance, ozone resistance, sour gasoline resistance and sour gasohol resistance and which can easily be used as a gasoline-resistant and gasohol-resistant material using conventional molding equipments and techniques. As a result, it has been found that the above requirements can be met by a novel multi-component copolymer consisting essentially oE a cyano-substituted alkyl (meth)acrylate, an alkyl acrylate and a crosslinkable monomer and also by a com-position of said mulit-component copolymer and other components.
According to one aspect of the invention, there is provided a multi-component copolymer rubber composition consist-ing essentially of (A) 25 to 60% by weight oE a cyano-substituted alkyl (meth)acrylate of the formula R

1 2 (I) CH2=C-CO-O-R -CN
~- wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, ` (B) 35 to 75% by weight of an alkyl acrylate, (C) 0.5 to 5% by weight of a crosslinkable monomer, and ,, ~ , ' , :- , - , . ~ :

~ 2'7~;~35 -3a- 25711-~18D

(D) 0 to 7~ by weighr. of other ethylenically unsaturated monomer copolymerizable with the components tA), (B) and (C).
According to another aspect the invention provides a multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber, consisting essentially of (A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

CH2=l-CO-O-R2-CN (I) wherein R1 is hydrogen or methyl and R CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer~
and (D) 0 to 10% by weight of other ethylenically un-saturated monomer copolymerizable with the components (A), (B) and (C), and a material selected from the group consisting of vinyl~
chloride resin, vinylidene fluoride polymer, acrylic rubber, nitrile ~ 20 rubber and partially hydrogenated nitrile rubber.
- The invention further provides a process for producing said copolymer rubber and uses of said copolymer rubber and sa~d composition.

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~ ~7~35i Specific examples of -the cyano-substltuted alkyl (meth)-acrylate are cyanomethyl ~meth)acrylate, 1-cyanoethyl (meth)-acrylate, 2-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)-- acrylate, 2-cyanopropyl (meth)acrylate, 3-cyanopropyl (meth)-acrylate, ~-cyanobutyl (meth)acrylate, 6-cyanohexyl (meth)acrylate, 2-ethyl-6-cyanohexyl (meth)acrylate, 8-cyanooctyl (meth)acrylate, etc. Of these, preferred are 2-cyanoethyl acrylate, 3-cyanopropyl acrylate and 4-cyanobutyl acrylate.
Particularly, 2-cyanoethyl acrylate is preferred.
The alkyl acrylate which is the component (B) is represented by the formula (II):
H O
H2C = l - C - O - R3 (II) .
~, , : , :
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1 wherein R3 is an alkyl group having 1 to 18 carbon atoms.
Speclfic examples of the alkyl acrylate are methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobu~yl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, etc. Of these, preferred are ethyl acrylate, propyl acrylate, n-bu~yl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate. Particularly, ethyl acrylate and n-butyl acrylate are preferred.
As the crosslinkable monomer which is ~he component (C), there can be used (C-I) a diene compound, (C-II) a (meth)acrylic acid ester containing a dihydro-dicyclopentadienyl group, (C-III) an epoxy group-containing, ethylenically unsaturated compound, ~C-IV) an active halogen-containing, ethylenically unsa-turated compound, ~C-V) an active hydrogen-containing monomer and (C-VI) a carboxyl group-containing monomer.
The diene compound (C-I~ includes nvn-conjugated dienes such as alkylidenenorbornenes, alkenylnorbornenes, dicyc10pentadiene, methyl-cyclopentadiene and dimers ~hereof as well as conjugated dienes such as butene and isoprene r Of these t non-conjugated dienes are preferred, and alkylidene-norbornenes are particularly preferred. Of the alkylidenenorbornenes, ethylidenenorbornene is most preferable.

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1 (meth)acrylic acid ester containing. a dihydrodicyclopentadienyl group (C-II) includes dihydrodicyclopentadienyl (meth)acrylate, dihydro-dicycl.opentadienyl oxyethyl(meth)acrylate and the like.
The epoxy group-containing, ethylenically unsaturated monomer (C-IIIj includes allyl glycidyl ether, vinyl glycidyl ether, 2-methyl-1-propenyl glycidyl ether, glycidyl methacrylate and glycidyl acrylate. Of these, allyl glycidyl ether, glycidyl methacrylate and glycidyl acrylate are preferred. Allyl glycidyl ether is most preferable.
The active halogen-containing, ethylenically unsaturated compound ~C-IV) includes vinylbenzyl chloride, vinylbenzyl bromide, 2 chloroethyl vinyl ether, vinyl chloroacetate, ethylene chloroacetate.methacrylate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropio-nate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, .; 2-hydroxypropylene chloroacetale methacrylate, chloro-.
methyl vinyl ketone, 2-chloroacetoxymethyl-5-norbornene, norbornylmethyl chloroacetate, 4-chloromethylstyrene, vinyl chloride, vinylidene chloride, etc. Of these, preferred are vinyl chloroacetater allyl chloroacetate,

2-chloroethyl vinyl ethar, vinylbenzyl chloride, 2-chloroethyl methacrylate and 2-chloroethyl acrylate.
The active hydrogen-containing monomer ~C-V) ; includes allyl cyanoacetate, etc.

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The carbo~yl group~containing monomer includes acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, etc.
The other ethylenically unsaturated monomer which is the component (D) is an optional component. It includes meth-acrylates such as methyl methacrylatej oc-tyl methacrylate and the like; alkoxyalkyl acrylates such as methoxyethyl acrylate, butoxy~thyl acrylate and the like; alkyl vinyl ketones such as methyl vinyl ketone ~nd the like; vinyl ethers and allyl ethers such as vinyl ethyl ether, allyl methyl e-ther and the like; vinyl aromatic compounds such as styrene, -methylstyrene, chlorostyrene, vinyltoluene and the li~e; alkenylnitriles such as acrylonitrile, methacrylonitrile and the like; alkenylamides such as acrylamide, metha~rylamide, N-methylolacrylamide and the like; and alkyl fumarates.
The proportions of the components (A), (B), (C) and (D) in the copolymer rubber are 20 to 69.5%, preferably 25 to 60~, by weight of the component (A), 30 to 79.5%, preEerably 35 to 75%, by weight of the component (B), 0.5 to 10%, preferably 0.5 to 5~, by weight of the component (C) and 0 to 10%, preferably 0 to 7~, by weight of the component (D).
When the component (A) is less than 20% by weight, the copolymer rubber is poor in gasoline resistance and sour gasoline resistance. When the component (A) exceeds 69.5~ by weight, the copolymer - , . : - ' ~ . ' '' '- ~ .- ~ ' .

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rubber is poor in physical properties such as tensile streng-th and elongation.
When the component (B) is less than 30% by weight, the multi-component copolymer rubber is poor in physical properties.
When the component (B) exceeds 79.5~ by weight, the multi-component copolymer rubber is deteriorated in gasoline resistance and sour gasoline resistance.
When the component (C) is less than 0.5~ by weight, the multi-component copolymer rubber requires a long time for cross-linking and has no sufficient tensile strength as possessed by crosslinked rubbers. When the component (C) exceeds 10% by weight, the multi-component copolymer rubber becomes hard and has a reduced elongation.
The glass transition temperature of the multi-component copolymer rubber of this invention is preferably a glass transition temperature of -10C or less.
The multi-component copolymer rubber of this invention can easily be produced by subjecting to radical polymerization a mixture consisting of (A) 15 to 70% by weight of a cyano-substituted alkyl (meth)acrylate of formula I as defined above, (B) 30 to 84.5% by weight of an alkyl acrylate, (C) 0.5 to 15% by weight of a cross-linkable monomer and (D) 0 to 15% by weight of an ethylenically unsaturated monomer copolymerizable with (A), (B) and (C). This radical polymerization can be conducted by a conventional .

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~ ~3S ~, 1 polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, wherein the monomers and other components are added at one time, continuously or intermittently.
The radical polymerization initiator used in the above polymerization may be conventional free radical catalysts such as peroxides, redox catalysts, persulfates and azo compounds. The polymerization can be conducted at a temperature ranging from 0C to 80C, preferahly 5C
to 60C.
The multi-component copolymer rubber obtained by the above polymerization can be recovered by a conven-tional coagulation method using a metal salt such as calcium chloride or the like or using a non-solvent such as ethanol, methanol or -the like.
The form of the multi-component copolymer rubber of this invention is not critical, and the multi component copolymer rubber can be produced in a solid form or in a liquid form depending upon the uses. The - molecular weight of the multi-component copolymer rubber is not critical; however, when used in a solid form, the multi-component copolymer rubber has pre~erably a Mooney viscosity (MLl+4, 100C) of 20 to 150~ more preferably 25 to 100.

Into the multi-component copolymer rubber of this invention can optionally be incorporated conven-tional compounding agents such as a crosslinking agent, a _ 9 _ : ' . ~ .. ~ ' ' ' ' ' - .,: - :

~ ~7~5 l crosslinking accelerator, a reinforcing agent, a filler, a plasticizer, a softener, an aging inhibitor, a stabilizer, a foaming agent and the like. The resulting compound can be subjected to crosslinking by a conven-tional method to easily obtain a crosslinked product.
As the above crosslinking agent, an appropriate compound may be selected depending upon the type of the fun~tional group to be used in the formation of cross-linkage of the copolymer. For example, when a cliene lO compound or a (meth)acrylic acid ester containing a dihydrodicyclopentadienyl group is introduced into the copolymer by copolymerization to form carbon-carbon double bonds in the copolymer, there can preferably be used conventional crosslinking agents which are employed for diene type rubbers ~styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber, etc.), such as vulcanizing agents ~e.g. sulfur, thiuram compound) and organic peroxides. When an epoxy group-containing monomer is introduced, the crosslinking agents 20 may be ammonium compounds, polyamines, polyamine salts, a combination of a polyamine with sulfur or dibenzothiazyl disulfide, dithiocarbamic acid salts, a com~ination of .
sulfur with a metal salt of a fatty acid, a combination of sulfur with a metal salt of a fatty acid and a maleimide J
thiourea derivatives, and a combination of a thiourea de-- rivative with red lead or dibasic lead phosphite. When an active halogen-containing, ethylenically unsaturated com-pound is used, the crosslinking agents may be polyamines, .

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1 polyamine salts, a combination of a polyamine with sulfur or dibenzothiazyl disulfide, ammonium compounds, a combi-nation of a metal salt o a fatty acid with sulfur, a com-bination of a metal salt of a fatty acid with sulfur and a maleimide, thiourea derivatives, and a combination of a thiourea derivative and red lead or dibasic lead phosphite.
When an active hydrogen-containing monomer is used, the crosslinking agents may be tetramethylthiuram disulfide or tetraethylthiuram disulfide. When a carboxyl group-containing monomer is used, the crosslinking agents may bezinc oxide or lead oxide. When the ammonium compounds are used as the crosslinking agent, they may be, for example, ammonium benzoate or ammonium adipate. When the polyamines are used, they may be, for example, triethylenetetramine, hexamethylenetetramine or triethyltrimethylenetriamine.
An example of the polyamine salts is hexamethylenediamine carbamate. Examples of the dithiocarbamic acid salts are zinc dimethyldithiocarbamate and iron dimethyldithiocarba-mate. Examples of the metal salts of fatty acids are sodium myristate, sodium palmitate, sodium stearate, sodium arachate, sodium behenate and their corresponding potassium salts. Examples of the thiourea derivatives are 2-Mercaptoimidazoline and N,N'-diethylthiourea. An example of the maleimides is N,N'-m-phenylenebismaleimide.
The amount of the crosslinking agent used in this invention is not critical and may be varied appro-priately depending upon the type and amount o~ cross-linkable monomer used and also depending upon the type o~

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1 crosslinking agent used. For example, an ammonium com-pound is used in an amount of 0.1 to 5 parts by weight; a polyamine or a polyamine salt used in an amount of 0.1 to 5 parts by weight; sulfur used in an amount of 0.1 to 2 parts by weight; a dithiocarbamic acid salt used in an amount of 0.1 to 10 parts by weight; a metal salt of a fatty acid used in an amount of 0.1 to 10 parts by weight;
and a thiourea derivative used in an amount of 0.1 to 5 parts by weight.
The crosslinked product of a vulcanizable rubber composition containing the multi-component copolymer rubber of this invention and a crosslinking agent excels in gasoline resistance, sour gasoline resistance, heat resistance and ozone resistance and has good low-temperature resitance, tensile strength and elongation~
and has a small permanent compression set. Therefore, it can be used in fuel system hoses of automobiles; other hoses, diaphragms and sealing materials (e.g. gasket, O-ring, oil seal) which come in contact with fuels, hydraulic oils, lubricating oils, etc.; rolls, transfer belts and conveyor belts requiring oil resistance and solvent resistance which are used in iron manufacure, spinning, printing, paper making, dyeing, etcJ; and so forth.
Being excellent particularly in sour gasoline resistance, the valucanizable rubber composition can preEerably be `~ used as a rubber for ~uel sys~em hoses of automobiles.
A rubber compound obtained by optionally incorporating into the multi-component copolymer rubber :` . ' :

3 ~3 - 13 - 25711~18 o~ this invention, conventional compounding chemicals such as a re-in~orcing agent, a filler, a plasticizer, a so~tener, a crosslinking agent, a stabilizer and the like and ~urther optionally incorpora-ting polymers such;as PVC, acrylic rubber, NBR, fluororubber, epi-chlorohydrin rubber and the like, is excellent in gasoline resis-tance, sour gasoline resistance, ozone resistance and heat resis-tance and ~urther good in tensile strength, elongation and low-temperature resistance. Therefore, th~ rubber compound pro~ides a very excellent material for use in inner tubes of fuel system rubber hoses of automobiles, particularly for use in inner tubes o~ rubber hoses connecting metal pipes in automobile engines.
In this invention, a mixture consisting of (A) a cyano-substituted alkyl (meth)acrylate of formula I as defined above, (B) an alkyl acrylate, ~C) a crosslinkable monomer and (D) other ethyl-enically unsaturated monomer is emulsion-polymerized at 0C to 80~C
in the presence of a radical polymerization catalyst, and to the resulting polymerization mixture is added a metal salt or a combi-~nation of an inorganic acid and a metal salt to coagulate a copoly-mer rubber, after which a releasing agent is added to the copolymer rubber coagulated, to obtain a multi-component copolymer rubber com-position which has good kneadability, excellent heat resistance, : ozone resistance and sour gasoline resistanee and good tensile strength and elongation.
The metal salt may be ealeium ehloride, magnesium - ~
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1 sulfate or the like. The inorganic acid may be sul~uric acid, or the like.
The releasing agent may be hydrocarbon compound such as paraffin wax or the like; a fatt~ acid compound such as stearic acid or the like; a fatty acid amide compound; a fatty acid ester compound; a phosphoric acid ester compound; or a metal salt of a fatty acid. Of these~
preferred are metal salts of fatty acids, phosphoric acid ester compounds and fatty acid ester compounds. Metal salts of fatty acids are more preferable in view of the good kneadability of the rubber composition obtained, and the addition of the metal salt does not result in any de-terioration of the physical properties of the vulcanizate.
The amount of the releasing agent used is pre-ferably 0.5 to 10 parts by weight per 100 parts by weightof the rubber. When the amount is less than 0.5 part by weight, the kneadability of the rubber composition obtained is not improved. When the amount exceeds 10 parts by weight, the physical properties of a vulcanizate of the rubber composition obtained are greatly deteriorated.
The releasing agent can be added mechanically by a conventional molding equipment such as a roll, a - Banbury mixer, a kneader or the like. Alternatively, it can be added in the form of an emulsion.
Addition of a plasticizer is preferred for im-provement of the low-tem~erature resistance. The plasti~
cizer may be a phthalic acid derivative compound such as diethyl phthalate, di-(2-ethylhexyl) phthalate, dibutyl .. .. . :

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3~ -_ 1 phahalate, di-n-octyl phthalate, dimethylcyclohexyl phthalate or the like; an isophthalic acid derivative compound such as diisooctyl isophthalate or the like; a tetrahydrophthalic acid derivative compound such as di-(2-ethylhexyl) tetrahydrophthalate or the like; an adipic acidderivative compound such as di-(2-e-thylhexyl) adipate, di-~buto~yethoxyethyl) adipate, butyldiglycol adipate or the like; an azelaic acid derivative compound such as di-(2-ethylhexyl) azelate or the like; a sebacic acid derivative compound such as di-(2-ethylhexyl) sebacate, di-n-butyl sebacate or the like; a fatty acid derivative compound such as diethylene glycol monolaurate or the like; a phosphoric acid derivative compound such as tri(2-ethylhexyl) phosphate, triphenyl phosphate or the like; a glycol derivative compound such as dibutyl methylene-bisthioglycolate or the like, a glycerine derivative compound; an epoxy derivative compound; or a polymeric plasticizer such as a polyester compound, a polyether - compound, a polyetherester compound or the }ike. Of these,preferred are polymeric polasticizers having a molecular weight of 300 to 3,000 such as polyester com-pounds, polyether compounds and polyetherester compounds.
The plasticizer is added in an amount of 2 to 15 parts by weight per 100 parts by weight of the rubber.
When it is used in an amount of less than 2 parts by weight, no sufficient improvement in low-temperature resistance is obtained. When the plasticizer is added in an amount of more than 15 parts by weight, reduction in tensile strength becomes Iarge.

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By further incorporating into the multi-component copoly~
mer rubber of this invention a vinylidene fluoride polymer, a vinyl chloride resin, a nitrile rubber or a partially hydrogenated product thereof, or an acrylic rubber, a rubber composition can be produced which is excellent not only in gasoline resistance, gasohol resis-tance, sour gasoline resistance and sour gasohol resistance but also in ozone resistance, heat re~istance and low-temperature resistance.
In this case, the multi-component copolymer rubber may consist essentially of ~A) 10 to 69.5~ by weight of a cyano-substituted alkyl (meth)-acrylate of formula I as defined above, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10~ by weight of other ethylenically unsaturated mo nomer copolymerizable with the components (A), (B) and (C~.
The vinylidene fluoride polymer mentioned above includes a poly(vinylidene fluoride) as well as copolymers between vinylidene : fluoride and ethylene trifluoride, propylene pentafluoride, propylene .~ hexafluoride, vinyl acetate, ethylene, propylene, butadiene, styrene, 20 an acrylate acid ester or the like wherein the content of vinylidene fluoride is usually at least ~0 mole %, preferably at least 60 mole %. The degree of polymeri~ation . ~: ' . ' - . , -.
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of the vinylidene fluoride polymer is not critical but is preferably lO0 to 100,000.
The vinyl chloride resin mentioned above in-cludes a poly(vinyl chloride) as well as copol~mers between vinyl chloxide and vinyl acetate, ethylene, propylene, butadiene, styrene or the like wherein the content of vinyl chloride is usually at least 60 mole ~
and preferably at least 80 mole ~. The degree of polym-eri~ation of the vinyl chloride resin is not critical but is preferably 500 to 2,000.
As the amount of the vinylidene fluoride polymer or the vinyl chloride resin in the rubber composition increases, the resinous property of the rubber composi-tion increases. Hence, the upper limit of the amount of said polymer or resin is governed by this property, and is preferably 60 parts by weight or less.
The proportions of the multi-component copolymer rubber and the vinylidene fluoride polymer or the vinyl chloride resin in the rubber composition of this inven-tion can be determined appropriately within the above-mentioned ranges depending upon the application purpose and the required perfomances.
The mixing method in the preparation of the composition of this invention is not critical, but the following methods may be used~
(l) A method wherein a multi-component copolymer rubber and a vinylidene fluoride polymer or a vinyl chloride resin are blended by a mixer such as a roll, `

- ` : . -1 a Banbury mixer, an intermixer or the like.
(2) A method wherein a multi-component copolymer rubber and a vinylidene fluoride polymer or a vinyl chloride resin are blended in a latex or suspension state and then subjected to coagulation and subsequent coprecipitation.
(3) A method wherein the methods ~1~ and (2) are combined.
Into the multi~component copolymer rubber composition can optionally be incorporated conventional compounding chemicals such as a reinforcing agent, a filler, a plasticizer, a softener, a crosslinking agent, a stabilizer and the like~ The resulting mixture can be subjected to crosslinking by a conventional method to easily obtain a crosslinked material.
The multi~component copolymer rubber composition of this invention is excellent not only in gasoline resist-!-~ ance, sour gasoline resistance, ozone resistance and heat resistance but also in new required performances, - 20 namely, gasohol resistance and sour gasohol resistance.
In addition, the composition is good in tensile strength, elongation and low-temperature resistance.
Therefore, the composition can be used in fuel system hoses of automobiles; other hoses, diaphragms and seals (e.g. gaskets, O-rings, oil seals) which come in contact with fuels, hydraulic oils, lubricating oils, etc.;
rolls, transfer belts and conveyor belts requiring oil resistance and solvent resistance for use in iron manu-facturing, spinning, printing, paper making, dyeing, etc.;

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1 and so forth. Utilizing the characteristic feature of the multi-component ~opolymer rubber composition being excellent in sour gasoline resistance and sour gasohol resistance, the composition can preferably be used in ~uel system hoses of automobiles.
The acrylic rubber mentioned above is a multi-component copolymer rubber consisting of (A') 99.5 to 39.5% by weight of an alkyl acrylate, (B') 0 to 60% by weight of an alkoxyalkyl ~crylate, (C') 0.5 to 10% by weight of at least one compound selected from the group consisting of diene compounds, tmeth)acrylic acid esters containing a dihydrodicyclopentadienyl group, epoxy group-containing, ethylenically unsaturated compounds and active halogen-containing, ethylenically unsaturated compounds and (D') 0 to 10~ by weight of other ethyl-enically unsaturated compound copolymerizable with (A'), (B') and (C'). The nitrile rubber mentioned above is a multi-component copolymer rubber composed of ~A'') 20 to 90~ by we-ght of a conjugated diolefin, (B'') 10 to 55~ by weight of an a,~-unsaturated nitrile, (C'') 0 to 70% by weight of an a,~-unsaturated carboxylic acid ester and ~D'') 0 to 20~ by weight of at least one monomer selected from the group consisting of carboxyl grOUp-CQntaining monomers, epoxy group-containing monomers, hydroxyl group-containing monomers and amino group-containing monomers.
The alkyl acrylate which is the component (A') of the acrylic rubber is represented by the formula (II):

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/ H O
H2C = C - C - C - O - R3 (II) 1 wherein R3 is an alkyl group having 1 to 18 carbon atoms.
Specific examples of the alkyl acrylate are as mentioned hereinbefore as to the component (B).
Specific examples of the alkoxyalkyl acrylate which is the component (B') of the acrylic rubber include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.
As the component (C') of the acrylic rubber, there can be used the diene compounds, the (meth)acrylic acid esters containiny a dihydroxypentadienyl group, the epoxy group-containing, ethylenically unsaturated com-- pounds and the active halogen-containing, ethylenically unsaturate ~ompounds, all of which have been mentioned with respect to he component (C) of the multi-component copolymer rubber o~ this invention.
~- The component (Dl), namely, other ethylenically unsaturated compound copolymerizable with the components (A'), (B') and (C') may be various compounds. Specific examples o~ the component (D') include carboxyl ; 20 group-containing compounds such as acrylic acid, methacrylic acid, crotonic acid, 2-pentanoic acid, maleic acid, fumaric acid, itaconic acid and the like;
methacrylates such as methyl methacrylate, octyl methacrylate and the like; alkyl vinyl ketones such as methyl vinyl ketone and the like; alkenyl alkyl ethers -- ~0 --~ 7 ~3 ~

l such as vinyl ethyl ether, allyl methyl ether and the like; alkenyl aromatic compounds such as styrene, ~-methylstyrene, chlorostyrene, vinyltoluene and the like;
vinylnitriles such as acrylonitrile, methacrylonitrile and the like; vinylamides such as acrylamide, methacrylamide, N-methylolacrylamide and the like; vinyl ~hloride; vinylidene chloride; and alkyl fumarates.
The acrylic rubber used in this invention consists of 99.5 to 39.5% by weight o~ the component tA'), 0 to 60% by weight of the component (B'), 0~5 to 10% by weight of the component (C') and 0 to 10% by weight of the component (D'j. When the component (A') is less than 39.5% by weight, the acrylic rubber has low heat-resistance. When the component (B') exceeds 60~ by weight, the rubber has low heat-resistance. When the component (C') is less than 0.5% by weight, the rubber is insuf~icient in crosslinkability and poor in physical properties, particularly in normal physical properties such as permanent compression set~ When the component (C') exceeds 10% by weight, the rubber has low heat-resistance. When the component (D') optionally used exceeds 10% by weight, the rubber has a poor balance between oil resistance and low-temperature resistance.
The mixing ratio o~ the acrylic rubber and the multi-component copolymer rubber o this invention is not critical. However, in order to improve the knead-ability, vulanization speed, permanent compression set and gasoline resistance of the acrylic rubber, it is . .
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.
- : ., : , ~74~35 1 desirable to use 5% by weight or more of the latter rubber. When the multi-component copolymer rubber is used in an amount of less than 5~ by weight, the effect is small. In order to improve the heat resistance of the multi-component copolymer rubber, it is preferable to use 10% by weight or more of the acrylic rubber~ When the acrylic rubber is used in an amount of less than - 10% by weight, the effect is small.
Acc~rding to this invention, the processability, vulcanization speed and permanent compression set which are the drawbacks of the conventional acrylic rubber can be improved. At the same time, it is made possible to ~reely control the balance of gasoline resistance, heat resistance and low-temperature resistance, and design a polymer meeting any desired object. Therefore, this invention is highly beneficial to related industries and the multi-component copolymer rubber composition of this invention can widely be used in rolls, hoses, packings, seal materials, diaphragms, etc.
The conjugated diolefin which is the component ~A") of the nitrile rubber mentioned above includes butadiene, isoprene, etc.
The a,~-unsaturated nitrile of the component ~B") includes acrylonitrile, methacrylonitrile, etc.
The ~ unsaturated carboxylic acid ester of the component ~C") includes methyl, ethyl, n-buty1 and 2-ethylhexyl esters of acrylic and methacrylic acids.
With respect to the component (D"), the .

.

- .

, : .. ...
. '-: . ,' .,,. , ~
, - -_ ~ 2'~;3~

l carboxyl group-containing monomer includes specifically acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. The epoxy group-containing monomer includes glycidyl (meth)acrylate, glycidyl ether, vinyl glycidyl ehter, etc. The hydroxyl group-containing monomer includes 1-hydorxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. The amino group-containing monomr includes dimethylaminoethyl (meth~acrylate, diethylaminoethyl ~meth)acrylate, dibutylaminoethyl (meth)acrylate, etc.
The content of the conjugated diolefin (A") in the nitrile rubber i5 20 to 90% by weight. When the content is less than ~0~ by weight, the rubber is insuf-ficient in low-temperature resistance and mechanical properties. When the content exceeds 90% by weight, the rubber is poor in heat resistance and sour gasoline resistance. The conjugated diolefin (A") in the nitrile rubber may be partially hydrogenated.
The content of the ~ unsaturated nitrile (B") in the nitrile rubber is lO to 55% by weight. When the content is less than lO~ by weight, the rubber is poor in oil resistance. When the content exceeds 55%
; by weight, the rubber is poor in low-temperature resistance.
The content of the ~,~-unsaturated carboxylic acid ester (C") in the nitrile xubber is 0 to 70% by weight~ When the content exceeds 70% by weight, the rubber has a low tensile strength.

.
" ' : . .: . .
. . .
:, . .' . ~ . ' ~ ., , ~,~d 74~3~
.J

1 The content of the monomer (D" ) in the nitrile rubber is 0 to 20% by weight. When the content exceeds ~- 20% by weight, the rubber has inferior low--temperature resistance or low permanent compression set.
The mixing ratio of the multi component copolymer rubber of this invention to the nitrile rubber is 20-99 to 80-1 (weight ratio), preferably 50-95 to 50-5. When the proportion of the mixted multi-component copolymer rubber of this invention is less than 20% by weight, the rubber composition is insufficient in heat resistance, sour gasoline resistance and ozone resist-ance When the ratio exceeds 99% by weight, the cross-linking reaction of the rubber composition is slow, and the freedom of selection of vulcanizing agent is reduced.
The ~orm of the nitrile rubber used can be either a solid or a liquid as long as its molecular weight is 0.01 dl/g or more in terms of intrinsic viscosity. The ~orm may be a mixture of a solid and a liquid depending upon the application of the rubber composition. When the intrinsic viscosity is lower than `0.01 dl/g, the rubber composition is high in extract-ability with oil and is not desirable as a gasoline-resistant material. The Mooney vescosity (ML1+4, 100C) of the nitrile rubber is preferably 20 to 80.
The rubber composition of this invention can be kneaded by a conventional mixing equipment such as a roll, a Banbury mixer, an ~-xtruder and other intermixers capable of mixing the components without excessively -- , . - : .

: ' . :. ~ '' ' 1 heating.
T~ the rubber composition of this invention comprising the multi-component copolymer rubber and the nitrile rubber can be added conventional compounding chemicals such as a filler (e.g. carbon black, calcium carbonate, a hydrocarbon resin, a phenolic resin~, a vulcanizing agent, a vulcaniæing adjuvant, an anti-aging agent, a softener and the like. The vulcanization of the rusulting mixture is usually conducted at 100 to 210C for about 0.5 to 120 min with heating by steam, a high temperature liquid or a microwave.
By superimposing a layer consisting of the multi-component copolymer rubber of this invention and a layer consisting of other rubber, a laminate excellent in sour gasoline resistance and sour gasohol resistance can be produced.
The other rubbers include butadiene-acrylonitrile rubber, styrene-butadiene rubber, fluoro-rubber, polychloroprene, acrylic rubber, ethylene-propylene terpolymer ~EPT), chlorinated polyethylene,chlorosulfonated polyethylene~ silicone rubber, butyl rubber and epichlorohydrin rubber.
The layer consisting of the multi-component copolymer rubber of this invention and/or the layer consisting of the other rubbers may have incorporated thereinto an oxide or hydroxide of a metal of Groups II
to IV of the Periodic Table ~or enhancing bonding strength. The oxide and the hydroxide include metal ~ - - . . - ~ , .
~, . .. .
;:
.

~/
~.27413~35 1 oxides such as magnesium oxide, aluminum oxide, zinc oxide, 7inc dioxide, calcium oxide, lead ~divalent and tetravalent~ oxides and silicon dioxide and correspond-ing metal hydroxides. Of these, particularly preferred are magnesium oxide, calcium hydroxide, aluminum hydroxide and lead (divalent) oxide. The amount of the metal oxide or hydroxide added is usually S to 30 phr.
To the layer consisting of the multi-component copolymer rubber of this invention and the layer consist-ing of the other rubbers can be added conventionaiadditives such as a reinforcing agent, a plasticizer, a processing adjuvant, a vulcanizing accelerator, a vulcanizing agent, an anti-aging agent and the like.
According to this invention, the layer consist~
ing of the multi-component copolymer rubber of this invention and/or the layer consisting of the other rubbers .: ~
may have incorporated thereinto an epoxy resin, a curing agent and a basic substance, and the two layers can be strongly vulcanization-bonded together. The vulcanizing - 20 agent may be a combination of maleic anhydride, phthalic anhydride, p-aminodiphenylamine, 2-methylimidazole and the like. The basic substance may be triethylamine, tetrabutylammonium chloride, or the lide. The above-mentioned laminate can also be produced by bonding the above vulcanized layers to one another.
Since the laminate has a thin layer of the multi-component copolymer rubber of this invention excellent in sour gasoline resistance and sour gasohol - ~ : ' , ' . : :' ,, - : , ;3S

resistance, the laminate is excellent not only in sour yasoline resistance and sour gasohol resistance but also ln various rubber properties. Therefore, the laminate can largely contribute to related industries and be used in rolls, hoses~ diaphragms, etc.
Next, the invention of this divisional application and of the parent application will be explained more specifically referring to Examples and the accompanying drawings; however, it should not be interpreted to be restricted to the Examples. In the drawings, Figures 1 to 3 show infrared absorption spectra of polymers of Examples 1, 10 and 17, respectively. In the Examples and the Comparative Examples, parts are by weight.
Examples 1 to 8 and Comparative Examples 1 to 6.
Using the monomers shown in Table 1 and the following polymerization chemicals, polymerization reaction was conducted at 10~C in an autoclave having an internal volume of 6 liters:

Monomers (Details are shown ~ in Table 1) ~ 100 parts -~ Water 200 -~ Alkylsuflate type soap 5 Potassium phosphate 0.2 - ~ EeS4-7H2 0.006 Trisodium salt of ethylenediaminetetracetic acid 0.020 Sodium formaldehydesulfoxylate 0.08 p-Methane hydroperoxide 0.06 :-.
:
. .
', , , : . :
, ~ 7 ~ ~ 3 1 When a conversion as shown in Table 1 was reached, 0.2 part, per 100 parts of monomers, of hydroquinone was added to the polymerization syskem to terminate the polymerization.
Then, the polymeri~ation mixture was heated, and unreacted monomers were removed under reduced pres-sure. To the residue was added an aqueous calcium chloride solution to coagulate polymer crumbs. The crumbs were water-washed and dried at 50C under reduced pressure, to prepare copolymer samples of Examples 1 to 8 and Comparative Examples 1 to 6.
Each copolymer sample was subjected to measure-ment of Mooney viscosity, copolymer composition and glass transition temperature. The results are shown in Table 1.
The infrared absorption specturm of the pol~mer of Example 1 is shown in Fig. 1. Since this spectrum has a characteristic absoption of C~N bond at 2,250 cm 1 and a characteristic absorption of C=O bond of ester at 1,730 cm 1 the presence of thesa two bonds in the polymer was confirmed. As shown in Table 1, this polymer has a single glass transition temperature (Tg) as measured by differential thermal analysis, which implies that the polymer is a copolymer.

[Test of characteristics of vulcanizate]
The copolymer samples shown in Table 1 were subjected to compounding in accordance with the following , ' ' `. ., . .. '', ...

.. . .. . . . . . .

3;~
1 formulations:

[Examples 1, 3, 7 and 8 and Comparative Examples 2, 3 and 4]
(Crosslinking with organic peroxide) Copolymer 100 parts Stearic acid HAFl) carbon black 50 Peroximon F402) 2 Note: 1) High abrasion furnace black 2) 1,3-bis(t-butylperoxyisopropyl~benzene [Examples 2, 4, 5 and 6 and Comparative Examples 1 and 5]
~Vulcanization with sulfur) Copolymer100 parts Zinc oxide 5 Stearic acid . HAF carbon black . 50 :~ Accelerator TT330.75 Sulfur 0.2 Note: 3~ Tetramethylthiuram disulfide :

[Comparative Example 6]
~Butadiene-acrylonitrile rubber) Copolymer100 parts Zinc oxide 5 Stearic acid SRF4) carbon black 60 .. - . : - ~
.
: . , : : :

Dop5) 5 parts Accelerator TT ) 1.5 Accelerator CZ ) 2 Sulfur 0.5 Note: 4) Semi-reinforcing furnace black 5) Dioctyl phthalate - 6) Tetramethylthiuram disulfide 7) N-cyclohexyl-2-benzothiazolsulfenamide The compounds obtained were subjected to press-curing (at 180C for 20 min for Examples 1, 3, 7 and 8 and Comparative Examples 2, 3 and 4; at 17GC for 20 min for Examples 2, 4, 5 and 6 and Comparative Examples 1 and 5; and at 160C for 20 min for Comparative Example 6) to obtain crosslinked rubbers.
Each crosslinked rubber was subjected to measurement of characteristics in accordance with JIS K
6301. The rubber was also subjected to measurement of sour gasoline resistance in accordance with the follow-ing test method.

[Test method for sour gasoline resistance]
A vulcanized rubber was immersed at 70C for 24 hr in a solution obtained by dissolving 1 g of lauryl peroxide in 99 g of Fuel C (a mixed solvent of isooctane :
toluene = 1 : 1 by volume). This 1 cycle procedure was repeated 20 times (20 cycles). Then, the rubber was dried at 100C for 15 hr under reduced pressure and subjected to measurment of tensile strength and elongation .

7 ~

at break in accordance with JIS K 6301. The changes of these properties after immersion compared with those before immersion were calculated and used as criteria of the sour gasoline resistance oE the rubber. The results are shown in Table 1.
As is obvious from Table 1, each of the multi-component copolymer rubbers of this invention provides a crosslinked material which is excellent in gasoline resistance, sour gasoline resistance, heat resistance and ozone resistance, good in low-temperature resist-ance, tensile strength and elongation and small in permanent compression set.

.

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, ~27~
1 Examples 9 to 14 and Comparative Examples 7 to 11 The copolymer samples of Examples 9 to 14 and Comparative Examples 7 to 11 were prepared by repeating the procedure of Examples 1 to 8, except that the monomers shown in Table 2 were used.
Each copolymer sample was subjected to measure-ment of Mooney viscosity, copolymer composition and glass transition temperature. The results are shown in Table 2.
The infrared absorption spectrum of the polymer of Example 10 is shown in Fig. 2. Since this spectrum has a characteristic absorption of C-N bond at 2,250 cm 1 and a characteristic absorption of C-0 bond o~ ester at 1,730 cm 1, the presence of these two bonds in the polymer was confirmed. As shown in Table 2, this polymer has a single glass transition temperature (Tg) as measured by differential thermal analysis, which implies that the polymer is a copolymer.

[Test of characteristics of vulcanizate~
The copolymer samples shown in Table 2 were subjected to compoundin~ in accordance with the following formulations.

.
(Examples 9 to 14 and Comparative Examples 7 to 9) Copolymer 100 parts Stearic acid HAFl) carbon black 50 Ammonium benzoate Note: 1) High abrasion furnace black - `: ' ', ,, , : , ` . . ' :
: , ' :' . -. '' '. ~ . , :' : : .: . . : .

~ 27~3~5 ,...,.

1 ~Comparative Example 10) Copolymer 100 parts Stearic acid HAF carbon black 50 Accelerator TRA ) 0.5 Accelerator EUR3) Calcium stearate 3 Note: 2) Dipentamethylenethiuram hexasulfide 3) 1,3-Diethylthiourea (Comparative Example 11) (Butadiene-acrylonitrile rubber) Copolymer 100 parts Zinc oxide 5 Stearic acid SRF4) carbon black 60 Accelerator TT6~ 1.5 Accelerator CZ7) 2 Sul~ur 0.5 Note: 4) Semi-reinforcing furnace black . 5) Dioctyl phthalate 6) Tetramethylthiuram disulfide 7) N-cyclohexyl-2-benzothiazolsulfenamide The compounds obtained were subjected to press-25 curing (at 175C for 20 min for Examples 9 to 14 and Comparative Examples 7 to 10 and at 160C for 20 min for Comparative Example 11) to obtain crosslinked rubbers.

: ` :

... . ,. ~ ~

~.27~

- 1 Each crosslinked rubber was subjected to measure-ment of characteristics in accordance with JIS K 6301.
The rubber was also subjected to measurement of sour gasoline resistance in accordance with the same method as in Examples l to 8. The results are shown in Table 2.
As is obvious from Table 2, each of the multi-component copolymer rubbers of this invention provides a crosslinked material which is excellent in gasoline resistance, sour gasoline resistance, heat resistance and ozone resistance, good in low-temperature resistance, tensile strength and elongation and small in permanent compression set.

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.` ` ~ . , - , ~ ; -~.27~35 1 Examples 15 to 19 and Comparative Examples 12 to 17 The copolymer samples of Examples 15 to 19 and Comparative Examples 12 to 17 were prepared by repeating the procedure of Examples 1 to 8, except that the monomers

5 shown in Table 3 were used.
Each copolymer sample was subjected to measure-ment of Mooney viscosity, copolymer composition and glass - transition temperature. The results are shown in Table 3.
The infrared absorption spectrum of the copoly-mer of Example 17 is shown in Fig. 3. Since this spectrumhas a characteristic absorption of C--N bond at 2,250 cm 1 and a characteristic absorption of C=O bond of ester at 1,730 cm 1, the presence of these two bonds in the copolymer was confirmed. As shown in Table 3, this copolymer has a single glass transition temperature (Tg) as measured by differential thermal analysis, which implies that the product is a copolymer.

~Test of characteristics of vulcanizate~
The copolymer samples shown in Table 2 were subjected to compounding in accordance with the following formulations.

[Examples 15 to 19 and Comparative Examples 12 to 16]
The same formulation as in Comparative Example 10 .

:. ~ , ~, ~

3~

1 [Comparative Example 17]
The same formulation as in Comparative Example 11 .
The compounds obtained were subjected to press~
curing (at 175C for 20 min for Examples 15 to 19 and Comparative Examples 12 to 16 and at 160C for 20 min for Comparative Example 17) to obtain crosslinked rubbers.
Each crosslinked rubber was subj~cted to measurement of characteristics in accordance with JIS K
- ~ 10 6301. The rubber was also subjected to measurement of sour gasoline resistance in accordance with the same method as in Examples 1 to 8.
As is obvious from Table 3, each of the multi-component copolymer rubbers of this invention provides a crosslin~ed material which is excellent in gasoline resistance, sour galosine resistance, heat resistance and ozone resistance, good in low temperature resistance, tensile strength and elongatlon and small in permanent compression set.

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1 Examples 20 to 25 and Comparative Example 18 The copolymers shown in Table 4 were subjected to compounding in accordance with the formulations shown in Table 5 and kneaded by a roll ko obtain unvulcanized rubber compounds. These unvulcanized rubber compounds were subjected to press-curing (at 175C for 20 min for Examples 20 to 25 and at 160C for 20 min for Comparative Example 18) to obtain vulcanized rubbers. The vulcanized rubbers were subjected to measurement of characteristics in accordance with JIS K 6301. The xubbers were also subjected to measurement of sour gasoline resistance by the same method as in Examples 1 to 8.
As is obvious from Table 4, the vulcanized - rubber compositions of this invention are excellent in sour gasoline resistance and heat resistance and good in tensile strength and elongation.

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1 Examples 26 to 34 and Comparative Examples 19 to 23 Using the monomers shown in Table 7 and the ~ollowing polymerization chemicals, polymerization reac-tion was conducted at 10C in an autoclave having an internal volume of 6 liters:

Monomers (Details are shown in 100 parts Table 7) Water 200 Alkylsulfate type soap 5 ~- 10 Potassium phosphate 0.2 FeSO4-7H2O 0.006 Trisodium salt of ethylenediaminetetracetic acid 0.020 Sodium ormaldehydesulfoxylate 0.08 15 p-Menthane hydroperoxide 0.06 When a conversion shown in Table 7 was obtained, 0.2 part of hydroquinone per 100 parts of monomers was-added to the polymerization system to terminate the polymerization.
Then, the polymerization mixture was heated, and the unreacted monomers were removed under reduced pressure. To the residue was added an aaueous calcium chloride solution to coagulate polymer crumbsO The - crumbs were water-washed and dried at 50C under reduced `~ 25 pressure, whereby the copolymers of Examples 26 to 34 and Comparative Examples 19 to 23 were prepared. These copolymers were compounded with the formulations show in Table 6 and kneaded by a Banbury mixer. The kneaded compounds were subjected to evaluation of processability :

: ` : ~ . `

.

. . _, 1 from dischargability from Banbury mixer as well as from knitting performance, and good processability was indi-cated as o, and bad processability as X.
The compounded rubbers obtained were subjected to press-curing at 175C for 20 min to obtain vulcanized rubbers. The vulcanized rubbers were subjected to measurement of characteristics in accordance with JIS K
6301. These rubbers were also subjected to measurement of sour gasoline resistance in accordance with the following method.

~Test method for sour gasoline resistance]
A vulcani~ed rubber was immersed at 70C for 24 hr in a solution obtained by dissolving 1 g of lauryl peroxide in 99 g of Fuel C (a mixed solvent of isooctane:
toluene = 1 : 1 by volume). This 1 cycle procedure was repeated 20 times ~20 cycles). Then, the rubber was dried ~- at 100C for 15 hr under reduced pressure and subjected to measurement of tensile strength and elongation in ~`~ accordance with JIS K 6301. The change (%) of the value obtained after immersion relative to the value obtained :`
- before immersion was calculated and used as criteria of the sour gasoline resistance of the rubber~ The results are shown in Table 7.
As is obvious from Table 7, the multi-component copolymer rubbers of this invention have good kneadability and the vulcanized rubbers obtained therefrom are excel-lent in sour gasoline resistance and heat resistance and good in tensile strength and elongation.

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~ ~7~35 1 Examples 35 to 42 and Comparative Examples 24 to 28 Each polymer composition sample consistin~ of a multi component copolymer rubber and a fluororubber whose formulation is shown in the upper section of Table 9 was compounded by a Banbury mixer with the formulation shown in Table 8. Each compound obtained was press-cured under the conditions shown in the lower section of Table 8.
The crosslinked rubber compositions thus obtained were subjected to measurement of characteristics in accordance with JIS K 6301.
These rubber compositions were also subjected to sour gasoline resistance and sour gasohol resistance in accordance with the following method.

[Test method for sour gasoline resistance]
- A test specimen of a crosslinked rubber com-position was immersed at 40C for 72 hr in a solution obtained by dissolving 2.5 g of lauryl peroxide in 97.5 g ~ of Fuel C (a mixed solvent consisting of equal volumes of - 20 isooctane and toluene). This 1 cycle procedure was repeated n times (n cycles~. After each cycle, the test specimen was taken out, dried at 100C for 15 hr under reduced pressure and bent at an angle of 180 to observe formation of cracks.
:
~Test method for sour gasohol resistance]
This resistance was measured by tha same method .. . .
, 3~; J

- 1 as in the case of sour gasoline resistance, except that Fuel C was replaced by a mixed solvent consisting of 80 parts by volume of Fuel C and 20 parts by volume of ethanol.
The measurement results are shown in the lower section of Table 9.
As is obvious from Table 9, the multi-component copolymer rubber compositions of this invention are excellent not only in gasoline resistance, gasohol re-sistance, sour gasoline resistance, sour gasohol resist-ance, ozone resistance and heat resistance but also in tensile strength, elongation and balance between gasoline resistance and low-temperature resistance.

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_ ~.. 274~3~ .

1 Examples 43 to 47 and Comparative Examples 29 to 31 Each sample of multi-component copolymer rubbert vinyl chloride resin (hereinafter referred to as PVC) compositions tExamples 43 to 47 and Comparative Examples 29 ts 30) and a butadiene-acrylonitrile rubber (herein-after referred to as NBR)/PVC composition (Comparative Example 31) was compounded by a Banbury mixer in accord~
ance with the formulation shown in Table 10. Each com-pound obtained was press-cured under the conditions shown in the lower section of Table 10.
The crosslinked rubber compositions obtained were subjected to measurement of characteristics in accordance with JIS K 6301.
These compositions were also subjected to measurement of sour gasoline resistance and sour gasohol resistance in the same methods as in Examples 35 to 42, except that methanol was substituted for the ethanol.
. The measurement results are shown in the lower :~ part of Table 11.
As is obvious from Table 11, the multi-component ~- copolymer rubber compositions of this invention are ` excellent not only in sour gasoline resistance, sour gasohol resistance, ozone resistance and heat resistance but also in tensile strength, elongation and balance between gasoline resistance and low-temperature resistance.

Examples 48 to 52 and Comparative Example 32 There were prepared composl~ions each consisting : - 62 -- . . ,, ~ . ............... : ., : .
- :: : . .

~,27~;~35 .. _., _,,:

1 of the same copolymer (2-cyanoethyl acrylate/ethyl acrylate/n-butyl acrylate/ethylidenenorbornene = 35/31/31/
3 by weight) and the same PVC but having a different formulation. These compositions were compounded by a Banbury mixer with the formulations shown in the upper section of Table 12.
The crosslinked rubber compositions obtained were subjected to measurement of characteristics by the same methods as in Example 43. The results are shown in the lower part of Table 12.
As is obvious from Table 12, the multi-component copolymer rubber compositions of this invention are excellent in sour gasoline resistance and sour gasohol resistance, good in tensile strength and elongation and has a practically satisfactory level of a permanent compression set.

.

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': . ~ ' ' " ' ~.~74~35 ~, 1 Examples 53 to 56 and Comparative Examples 33 to 36 Mul~i-component copolymer rubber compositions ~Examples 53 to 56) and multi-component copolymer rubbers (Comparative Examples 33 to 36) were compounded by a Banbury mixer with the form~lations shown in Table 13.
The compounds obtained wer~ evaluated for processability from dischargability from Banbury mixer as well as from knitting performance, and good processability was indicat~d so o, and bad processability as X.
These compounds were press-cured under the con-ditions shown in Table 13. The vulcanized compounds were subjected to measurement of permanent compression set, heat resistance and gasoline resistance based on JIS K
6301 using the conditions shown in Table 14.
The results are shown in Table 14.
Comparison between the results of Examples 53 and 54 with the results of Comparative Examples 33 and 34 indicates that mixing of a conventional acrylic rubber [a multi-component copolymer rubber (I)~ with a multi~ :
component copolymer rubber of this invention overcomes : the drawbacks of the conventional acrylic rubber, namely, processability, permanent compression set and gasoline resistance~
Comparison between the results of Examples 55 and 56 with the results of Comparative Examples 35 and 36 indicates that the drawbac~ of a multi-component copolymer rubber of this invention, namely, heat resistance is improved by incorporating thereinto a conventional acrylic . . -, . ~ , : ' : '` ', . -' - ' ' ' ~ ' - ' .
:- . . . : .

3~5 1 rubber [a multi-component copolymer rubber (I)].

Table 13 .

_~ B
Polymer 100 100 Zinc oxide 5 Stearic acid 1 ~AF carbon black 50 50 Accelerator TT * O. 75 .
Sulfur 0.2 Ammonium benzoate . _ _ , ..... ... _ .. ___ Conditions for press-curing 170C x 175C x 20 min20 min .~ . . ._._ _ * Tetramethylthiuram disulfide ' .

69 - :

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1 Examples 57 IO 61 and Comparative Examples 37 to 40 Each mixture having the formulation shown in Table 15 was kneaded by a Banbury mixer and an open roll and then press-cured at 170C for 20 min.
Each crosslinked rubber composition was subjected to measurement of characteristics in accord-ance with JIS K 6301.
The rubber composition was also subjected to measurement of sour gasoline resistance by the following method:

[Test method for sour gasoline resistance]
A sample was immersed at 70C for 24 hr in a solution obtained by dissolving 1 g of lauroly peroxide in 9g g of Fuel C (a mixed solvent consisting of equal volumes of isooctane and toluene). This 1 cycle procedure was repeated 20 times (20 cycles~. Then, the sample was dried at 100C for 15 hr under reduced pressure and subjected to measurement of tensile strength and elonga-tion at break in accordance with JIS K 6301. The changes (%3 from the value ob~ained before immPrsion were cal-culated and used as criteria of 50Ur gasoline resistance.
The measurement results are shown in Table 16.
- As is clear from Table 16, the composition of this invention gives a crosslinked product which is excel-lent in heat resistance, sour gasoline resistance, and ozone resistance, good in low-temperature resistance, tensile strength and elongation, and has a small permanent compres-sion set. - 71 -: ~ . . - - , , :
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- - ~ . . . .. .
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: ' ~ . :- , -' - : . - . . - .:
. . : ~ . . : . ~ .

~ 7~3~ `~

1 Examples 62 to 65 and Comparative Example 41 Test methods used in these Examples ~ere as follows:
Preparation of kneaded compounds Unvulcanized rubber compounds were kneaded by a rubber test roll mill ~6-inch and 14-inch rolls) to obtain sheet-like kneaded compounds each having a thickness of 8 mm, a width of 50 mm and a length of 80 mm and having a smooth surface.

Adhesion by vulcanization A sheet-like kneaded compound of the multi-component copolymer rubber of this invention and another sheet like kneaded compound of a different rubber both obtained above were superimposed and inserted into a compression type mold, where they were subjected to vulcanization at 170C for 15 min at a surface pressure ;~ of 2 kg/cm2 applied by an electrically heated press ` whereby a sheet-like laminate was produced.

-~ Measurement of bonding strength : 20 The laminate obtained above was cut into a - ribbon-like sample of 2.5 mm in width and the sample was ~ subjected to 90 peeling test in accordance with the : peeling test specified by item 7 of JIS K 6801, whereby the bonding strength of the laminate was measured. The results are shown in Table 17.

- . . ,: . . ~ . -. : . . . .

.
.

~ ~ ~7a~35 ~

1 Measurement of sour gasoline resistance A test specimen was immersed at 40C for 72 hr in a solution obtained by dissolving 2.5 g of lauroyl peroxide in 97.5 g of Fuel C (a mixed solvent consisting - 5 of equal volumes of isooctane and toluene), in such a way that the multi-component copolymer rubber of the laminate came in contact with the solution. This 1 cycle procedure was repeated twice (2 cycles). Then, the specimen was -taken QUt of the solution, dried at 100C for 15 hr under reduced pressure and bent at an angle of 180 to observe the formation of cracks. The results are shown in Table 17.
The unvulcanized rubber compounds used in the above preparation of kneaded compounds had the following formulations, in which unless otherwise specified, parts are by weight:

- [Formulations of multi-component copolymer rubber compounds]
Polymer a) or b) 100 parts Steatric acid HAF black 50 Peroximon F40 0.2 Ca(o~)2 10 Note: a) 2-Cyanoethylacrylate/ethyl acrylate/n-butyl acrylate/ethylidenenorbornene = 37/30/30/3 by weight b) 2-Cyanoethyl acrylate/ethyl acrylate/2-ethylhexyl acrylate/dicyclopentadiene = 25i40/32/3 by weight - . . ' ., ' . . -: ' . , - .

_ ~ ~ 7~

1 [Formulations of o~her rubbex compounds]

NBR: Polymer 1 100 parts Stearic acid ZnO

Ca(OH)2 10 Epoxy resin 2 5 Maleic anhydride 0.3 2-Methylimidazole 1.0 Sulfur 0.3 TET . 1.5 TS
: *3 FKM: Polymer 100 parts CMP #2 4 1.85 CMB #3*4 2.6 MgO
Ca(OH)2 6 MT black 20 : Note: *1 N 220S, manufactured by Japan Synthetic Rubber~C-o., Ltd.
~: *2 Epicoat ~828, manufactured by Shell *3 E45, manufactured by Du pont : *4 Vulcanization accelerator, manufactured by Du Pont, #20 is a polycyclic quaternary phosphate and #30 is an aromatic salt.
CZ: N-cyclohexylbenzothia~yl sulfenamide TET: Tetraethylthiuram disulfide -~ - 77 -.' ., ~ .. ~ , :~ ,: . .
~ :
,. ., ' '' ' ' ' ' ' :

: - - : . - : . ., .. . .

~. ~74;~35 , TS: Tetramethylthiuram 25 CR: Neoprene WRT 5 100 parts Stearic acid 0.5 SRF black 60 Hydrous silicic - acid 20 Aromatic oil 15 ZnO 5 Accelerator 22 0.5 Note: *5 A polychloroprene rubber, manufactured by Du Pont.
1 As seen from Examples 62 to 65, laminates between the multi-component copolymer rubber of this invention and a commercially available rubber have a strong bonding strength between the two rubbers as a result of vulcaniza-tion. tThe two rubbers may be allowed to adhere to each other by the use of an adhesive.) Comparison of Example 62 with Comparative Example 41 indicates that a laminate of a multi-component copolymer rubber of this invention and an NBR has a strikingly improved sour gasoline resistance over the NBR.

:

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1 Examples 66 to 72 and Comparative Example 42 Each sample of multi-component copolymer rubbers (Examples 66 to 72) and a butadiene-acrylonitrile rubber (NBR) (Comparative Example 42) shown in the upper section of Table 19 was subjected to compounding by a Banbury mixer in accordance with the formulation shown in Table 18. Each compound obtained was press-cured undex the conditions shown i.n the bottom section of Table 18.
The crosslinked rubber compounds obtained were subjected to measurement of characteristics in accordance with JIS K 6301. The results are shown in Table 19.
The crosslinked rubber compounds were also sub-jected to measurement of sour gasoline resistance by the following mehtod. The resutls are shown in Table 19.

[Text method for sour gasoline resistance]
A test specimen was immersed at 40C for 72 hr in a solution obtained by dissolving 2.5 g of lauroyl peroxide in 97.5 g of Fuel C (a mixed solvent consisting of e~ual volumas of isooctane and toluene). This 1 cycle procedure was repeated n times (n cycles). After each cycle, the specimen was taken out, dried at 100C for 15 hr undex reduced pressure and bent at an angle of 180 to observe the formation of cracks.
As appreciated from Table 19, the rubber com-pounds of this invention are excellent in sour gasolineresistance, heat resistance and ozone resistance and good in permanent compression set and balance between - ' ' '` ............. ~ ,: ~ , , . .

- . .

7~35 gasoline resistance and low-temperature resistance.
Therefore, they provide a very superior material for inner tubes of fuel rubber hoses.

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Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber, consisting essentially of (A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with the components (A), (B) and (C), and a material selected from the group consisting of vinyl chloride resin, vinylidene fluoride polymer, acrylic rubber, nitrile rubber and partially hydrogenated nitrile rubber.

2. A multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber, consisting essentially of:
(A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with the components (A), (B) and (C), and a vinyl chloride resin.

3. A multi-component copolymer rubber composition according to Claim 2, wherein the multi-component copolymer rubber consists essentially of (A) 20 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 79.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C).

4. A multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber, consisting essentially of:

(A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C), and vinylidene fluoride polymer.

5. A multi-component copolymer rubber composition according to Claim 4, wherein the multi-component copolymer rubber consists essentially of (A) 20 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 79.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C).

6. A multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber consisting essentially of (A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C), and an acrylic rubber.

7. A multi-component copolymer rubber composition according to Claim 6, wherein the multi-component copolymer rubber consists essentially of (A) 20 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 79.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C).

8. A multi-component copolymer rubber composition according to Claim 7, wherein the acrylic rubber is a copolymer consisting essentially of 99.5 to 39.5% by weight of an alkyl acrylate, 0 to 60% by weight of an alkoxyalkyl acrylate, 0.5 to 10% by weight of a crosslinkable monomer and 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with the alkyl acrylate, the alkoxyalkyl acrylate and the crosslinkable monomer.

9. A multi-component copolymer rubber composition consisting essentially of a multi-component copolymer rubber, consisting essentially of:
(A) 10 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 89.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C), and a nitrile rubber.

10. A multi-component copolymer rubber composition according to Claim 9, wherein the multi-component copolymer rubber consists essentially of (A) 20 to 69.5% by weight of a cyano-substituted alkyl (meth)acrylate of the formula I

(I) wherein R1 is hydrogen or methyl and R2CN is a cyanoalkyl group of 2 to 12 carbon atoms, (B) 30 to 79.5% by weight of an alkyl acrylate, (C) 0.5 to 10% by weight of a crosslinkable monomer, and (D) 0 to 10% by weight of other ethylenically unsaturated monomer copolymerizable with components (A), (B) and (C).

11. A multi-component copolymer rubber composition according to Claim 10, wherein the nitrile rubber is a copolymer or a hydro genated product thereof, the copolymer consisting essentially of 20 to 90% by weight of a conjugated diene, 10 to 55% by weight of an .alpha.,.beta.-unsaturated nitrile, 0 to 70% by weight of an .alpha.,.beta.-unsaturated carboxylic acid ester and 0 to 20% by weight of a monomer containing a carboxyl, epoxy, hydroxyl or amino group.