JP2001026688A - Crosslinkable rubber composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent strength, wear resistance and compression permanent set resistance by using a rubber composition which can be bonded to a polyamide and shows adhesive strength of not less than a specific value. SOLUTION: A rubber composition preferably comprises an ethylene-α-olefin- nonconjugated polyene random copolymer (A), a methacrylate-based or allyl- based compound (B) having not less than two functional groups and an organic peroxide (C), the amounts of the compound B and the organic peroxide C being 0.1 to 30 pts.wt. and 0.1 to 20 pts.wt. respctively per 100 pts.wt. of the copolymer rubber A. The copolymer rubber A is preferably the ethylene-α-olefin- nonconjugated polyene random copolymer rubber the polyene of which is composed of a norbornene compound containing a vinyl-terminated group represented by formula I or II (wherein n is an integer of 0 to 10; R1 and R3 are each H or a 1-10C alkyl; and R2 is H or a 1-5C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crosslinkable rubber composition,
Polyamide rubber laminate using the rubber composition, and its use, more specifically, can be bonded to untreated polyamide, more specifically, compression set resistance, strength properties, heat resistance, weather resistance The present invention relates to a crosslinkable rubber composition, a polyamide rubber laminate, and uses thereof which are excellent in characteristics such as wear characteristics.

[0002]

BACKGROUND OF THE INVENTION Ethylene / α-olefin / non-conjugated polyene random copolymer rubbers such as EPDM generally have excellent weather resistance, heat resistance and ozone resistance, and are suitable for industrial parts for automobiles and industrial rubber. It is used for products, electrical insulating materials, civil engineering and building materials, rubberized fabrics, etc.

[0003] The conventional ethylene / α-olefin / non-conjugated polyene random copolymer rubber has a disadvantage that its adhesiveness to synthetic fibers is inferior to polar rubbers such as nitrile rubber, chloroprene rubber and chlorosulfonated polyethylene. is there. As a method to solve this drawback,
JP-A-2-23632 discloses an improvement in the adhesiveness between an ethylene / α-olefin / non-conjugated polyene random copolymer rubber and a synthetic fiber by using an adhesive solution of a chlorosulfonated copolymer. However, in today's environment issues such as non-halogenation, the bonding technique utilizing the polarity by such halogenation is hardly optimal. In addition, as a conventional bonding method,
A method is known in which synthetic fibers are subjected to resorcinol formaldehyde latex treatment (RFL treatment), and then embedded in rubber and crosslinked to adhere. More specifically, a method using an isocyanate or isocyanuric acid derivative in the RFL treatment is known. However, even if these methods are applied to a case where an ethylene / α-olefin / non-conjugated polyene random copolymer rubber is used as the rubber, it is difficult to obtain sufficient adhesion.

Accordingly, ethylene / α-olefin /
There is a demand for the bonding of the non-conjugated polyene random copolymer rubber composition to the synthetic fibers and the emergence of bonding technology that is excellent in strength properties, abrasion resistance and compression set resistance.

Accordingly, the present inventors have conducted intensive studies on an ethylene / α-olefin / non-conjugated polyene random copolymer rubber composition and found that the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), By crosslinking a rubber composition comprising a methacrylate-based or allyl-based crosslinking assistant (B) having two or more functional groups and an organic peroxide (C), it is possible to adhere to a polyamide, and furthermore, to obtain strength properties, They have found that a molded article having excellent wear resistance and compression set resistance can be produced, and have completed the present invention.

[0006]

SUMMARY OF THE INVENTION The crosslinkable rubber composition according to the present invention is characterized in that the adhesive strength between the crosslinked rubber sheet and the polyamide fiber is 10 N / cm or more. Further, it is characterized by having excellent strength properties, abrasion resistance and compression set resistance.

In the vulcanizable rubber composition according to the present invention, specifically, the non-conjugated polyene comprises at least one kind of norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II]. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A);
A methacrylate or allylic crosslinking aid having two or more functional groups (B), and an organic peroxide (C)
Consists of

[0008]

Embedded image Wherein, n is 0 to 10 integer, ^{R 1} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, ^{R 2}
Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

[0009]

Embedded image [Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms].

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has a (i) molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin). (Ii) the iodine value is in the range of 0.5 to 50, and (iii) the intrinsic viscosity [η] of the decalin solution measured at 135 ° C. is 0.5 to 50/60. It is in the range of 10 dl / g.

The present invention also comprises a laminate of a fiber base material containing polyamides and a layer of the crosslinkable rubber composition provided on the fiber base material, wherein the rubber composition layer is crosslinked. A polyamide rubber laminate, particularly an automotive hose, a water supply hose, a gas hose; a power transmission belt, a transportation belt;
Also relates to rubber for escalator handrails.

The polyamide rubber laminate such as the hose (automotive hose, water supply hose, gas hose), belt (power transmission belt, transport belt), escalator handrail rubber, etc. according to the present invention is vulcanizable according to the present invention. It is produced by laminating a suitable rubber composition on a fiber base made of polyamides, cross-linking and integrating.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the vulcanizable rubber composition according to the present invention and its use will be specifically described.

The crosslinkable rubber composition according to the present invention is characterized in that the crosslinked rubber sheet has an adhesive strength of 10 N / cm or more with the polyamide fiber. Also,
It is characterized by excellent strength properties, abrasion resistance and compression set resistance.

The vulcanizable rubber composition according to the present invention exhibiting the above-mentioned physical properties has an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and has two or more functional groups. It is composed of a methacrylate or allylic crosslinking assistant (B) and an organic peroxide (C).

[Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)] The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention comprises ethylene and carbon 3 to 20 atoms
Is a random copolymer of an α-olefin and a non-conjugated polyene.

As the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
Examples thereof include 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among them, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used. These α-olefins are used alone or in combination of two or more.

The non-conjugated polyene used in the present invention is a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II].

[0019]

Embedded image

In the general formula [I], n is 0 to 10
R ¹ is a hydrogen atom or a carbon atom having 1 to 1
R ¹ is an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, Examples include an octyl group, a nonyl group, and a decyl group. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ .

[0021]

Embedded image

In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group for R ³ include the same alkyl groups as the specific examples for the alkyl group for R ¹ above.

Examples of the norbornene compound represented by the general formula [I] or [II] include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, and 5-vinyl-2-norbornene.
(2-propenyl) -2-norbornene, 5- (3-butenyl)
-2-norbornene, 5- (1-methyl-2-propenyl) -2-
Norbornene, 5- (4-pentenyl) -2-norbornene,
5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-
Hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3- Butenyl)
2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene,
5- (3,4-dimethyl-4-pentenyl) -2-norbornene,
5- (3-ethyl-4-pentenyl), 5- (7-octenyl) -2
-Norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2 -Norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among them, 5-vinyl-2
-Norbornene, 5-methylene-2-norbornene, 5- (2-
Propenyl) -2-norbornene, 5- (3-butenyl) -2-
Norbornene, 5- (4-pentenyl) -2-norbornene,
5- (5-Hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

The above norbornene compound such as 5-vinyl
In addition to 2-norbornene, the following non-conjugated polyenes can be used in combination as long as the physical properties aimed at by the present invention are not impaired.

Specific examples of such non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4 -Hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl
Chain non-conjugated dienes such as -1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-
Cyclic non-conjugated dienes such as methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3 And trienes such as -diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Ethylene / α comprising the above components
-Olefin / non-conjugated polyene random copolymer (A)
Has the following characteristics. (I) Molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin): ethylene.
The α-olefin / non-conjugated polyene random copolymer rubber (A) is composed of (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as α-olefin). And the unit derived from
60-95 / 5, preferably 50 / 50-90 / 10,
Preferably 55/45 to 85/15, particularly preferably 6
It is contained in a molar ratio [(a) / (b)] of 0/40 to 80/20.

When the molar ratio is within the above range, a rubber composition which is excellent in heat aging resistance, strength characteristics and rubber elasticity and can provide a crosslinked rubber molded article excellent in cold resistance and processability is obtained. (Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is 0.5 to 50 (g / 100).
g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 (g / 100 g), particularly preferably 1.5 to 25 (g / 1 g).
00g).

When the iodine value is within the above range, a rubber composition having high crosslinking efficiency can be obtained, and a crosslinked rubber molding excellent in resistance to compression set and resistance to environmental deterioration (= heat aging resistance). A rubber composition that can provide a body is obtained. If the iodine value exceeds 50, it is disadvantageous in terms of cost, which is not preferable. (Iii) Intrinsic Viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) measured in decalin at 135 ° C. is 0.5 to 10 dl / g, preferably 0.1 to 10 dl / g.
6 to 8 dl / g, more preferably 0.7 to 6 dl / g
g, particularly preferably 0.8 to 5 dl / g.

When the intrinsic viscosity [η] is within the above range, a rubber composition which is excellent in strength properties and compression set resistance and can provide a crosslinked rubber molded article excellent in processability is obtained.

Further, the ethylene / α-
The olefin / non-conjugated polyene random copolymer rubber (A) may be a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (eg, acid anhydride or ester), a hydroxyl group-containing ethylenically unsaturated compound, or an amino group-containing ethylenically unsaturated. The compound may be graft-modified with a compound, an ethylenically unsaturated compound containing an epoxy group, an aromatic vinyl compound, a vinyl ester compound, vinyl chloride, or the like.

[Methacrylate or allylic crosslinking aid having two or more functional groups (B)] A methacrylate or allylic crosslinking aid having two or more functional groups (B) used in the present invention. Is a methacrylate or allylic compound containing two or more groups active at the time of crosslinking. Specific examples of the methacrylate-based compound containing two or more methacryl groups include 1,4-butanedimethacrylate, 1,3-butanedimethacrylate,
3-propylene-2,2-dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, pentamethylene Glycol dimethacrylate, hexamethylene glycol dimethacrylate,
Methacrylates of polyhydric alcohols such as trimethylolpropane trimethacrylate; methacrylates of polyvalent metals such as zinc dimethacrylate; and the like, but are not limited to these examples. On the other hand, examples of the allyl-based compound having two or more allyl groups include allyl compounds such as diallyl fumarate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, triallyl isocyanurate, and triallyl thymellitate. However, the present invention is not limited to these examples. Of course, a mixture of these can also be used.

The methacrylate or allylic crosslinking assistant (B) having two or more functional groups is ethylene • α-
It is desirable to use 0.1 to 30 parts by weight, particularly 1 to 15 parts by weight, more preferably 2 to 5 parts by weight, per 100 parts by weight of the olefin / non-conjugated polyene random copolymer rubber (A). By using the crosslinking aid in an amount within the above range, it is possible to increase the adhesive strength to the polyamides and to improve the compression set resistance.

[Organic peroxide (C)] Specific examples of the organic peroxide (C) used include dicumyl peroxide, di-t-butyl peroxide, and di-t-
Butylperoxy-3,3,5-trimethylcyclohexane,
t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl
-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
Dialkyl peroxides such as 5-dimethyl-2,5-mono (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene; t-butylperoxyacetate; t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxy neodecanoate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate Peroxyesters; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof. Among them, an organic peroxide having a temperature giving a half-life of 1 minute in the range of 130 to 200 ° C. is preferable, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3 , 5-Trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-
Organic peroxides such as butyl hydroperoxide are preferred.

The organic peroxide (C) is ethylene.α
-0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of the olefin / non-conjugated polyene random copolymer rubber (A) . By using the organic peroxide (C) in an amount within the above range, it is possible to adhere to the polyamide and to produce a molded article having excellent strength properties, abrasion resistance and compression set resistance.

[Other Components] The crosslinkable rubber composition according to the present invention can be used without being crosslinked, but when used as a crosslinked product such as a crosslinked rubber molded product or a crosslinked rubber foam molded product. The characteristics can be exhibited most.

In the crosslinkable rubber composition according to the present invention,
Depending on the intended use of the crosslinked product, etc., conventionally known rubber reinforcing agents, inorganic fillers, softeners, antioxidants, processing aids, vulcanization accelerators, organic peroxides, vulcanization aids, foaming agents , Foaming aid,
Additives such as a colorant, a dispersant, and a flame retardant can be blended within a range that does not impair the purpose of the present invention.

The above-mentioned rubber reinforcing agent is used for the tensile strength of the crosslinked rubber,
It has the effect of increasing mechanical properties such as tear strength and wear resistance. As such a rubber reinforcing agent, specifically,
SRF, GPF, FEF, HAF, ISAF, SAF,
Examples thereof include carbon blacks such as FT and MT, carbon blacks which have been surface-treated with a silane coupling agent, finely divided silicic acid, silica and the like. Specific examples of silica include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, alkoxysilane, or a low-molecular-weight siloxane. The specific surface area of these silicas (BED method)
Is preferably 50 m ² / g or more, more preferably 10 m ² / g or more.
0 to 400 m ² / g.

The type and amount of these rubber reinforcing agents can be appropriately selected depending on the application, but the amount of the rubber reinforcing agent is usually in the range of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 100 For parts by weight,
Up to 300 parts by weight, preferably up to 200 parts by weight.

Specific examples of the above-mentioned inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The type and amount of these inorganic fillers can be appropriately selected depending on the application, but the amount of the inorganic filler is usually 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). In contrast, it is at most 300 parts by weight, preferably at most 200 parts by weight.

As the above-mentioned softener, a softener usually used for rubber can be used. Specifically, petroleum softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tar softening agents such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; Synthetic polymer substances such as resin, atactic polypropylene, and coumarone indene resin can be used. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

The amount of these softeners is appropriately selected depending on the use of the vulcanized product. Examples of the anti-aging agent include amine-based, hindered phenol-based, or sulfur-based anti-aging agents, and as described above, these anti-aging agents are used within a range that does not impair the object of the present invention. Can be

As the processing aids described above, compounds used in ordinary rubber processing can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; ricinoleic acid, stearic acid, palmitic acid and lauric acid And higher fatty acid esters.

Such processing aids are usually ethylene
It is used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the α-olefin / non-conjugated polyene random copolymer rubber (A), but it is appropriately optimized according to the required physical properties. It is desirable to determine the amount.

Further, in addition to the crosslinking aid (B) and the organic peroxide (C), other crosslinking aids such as sulfur; quinone dioxime compounds such as p-quinone dioxime; Can also.

As the above foaming agents, specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate,
Inorganic blowing agents such as ammonium carbonate and ammonium nitrite; nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine; azodicarbonamide, azobisiso Azo compounds such as butyronitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'- Sulfonyl hydrazide compounds such as disulfonyl hydrazide; calcium azide, 4,4-diphenyldisulfonyl azide,
and azide compounds such as p-toluenesulfonyl azide.

These foaming agents are ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 10
0.5 to 30 parts by weight, preferably 1 to 0 parts by weight
It is used in a proportion of up to 20 parts by weight. When the foaming agent is used at the above ratio, the apparent specific gravity is 0.03 to 0.8 g / c.
it is possible to produce a foam m ^3, it is desirable to determine the appropriate optimum amount in accordance with the required physical properties.

Further, if necessary, in combination with a foaming agent,
A foaming aid may be used. The foaming aid acts to lower the decomposition temperature of the foaming agent, promote the decomposition, and make the air bubbles uniform. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.

These foaming aids are ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 1
It is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 00 parts by weight, but it is desirable to appropriately determine an optimum amount according to required physical properties.

In the crosslinkable rubber composition according to the present invention, it can be blended with other known rubbers as long as the object of the present invention is not impaired. Such other rubbers include natural rubber (NR) and isoprene rubber (I
R), butadiene rubber (B)
R), conjugated diene rubbers such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber (CR).

Further, conventionally known ethylene / α-olefin-based copolymer rubbers can also be used, for example, ethylene / propylene random copolymer (EPR), and the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer rubber. An ethylene / α-olefin / polyene copolymer other than (A) (for example, EPDM) can be used.

[Rubber Composition, Polyamide Rubber Laminate and Use Thereof] As described above, the crosslinkable rubber composition according to the present invention can be used without being crosslinked. When used as a crosslinked material such as a rubber foam molded article, the characteristics can be exhibited most.

In order to produce a crosslinked product from the crosslinkable rubber composition according to the present invention, an uncrosslinked compounded rubber is prepared once, and then the compounded rubber is prepared in the same manner as in the case of crosslinking a general rubber. Crosslinking may be performed after molding into an intended shape.

As a cross-linking method, any of a method of heating using a cross-linking agent and a method of irradiation with light, γ-ray, or electron beam may be adopted. First, the crosslinkable rubber composition according to the present invention is prepared, for example, by the following method.

That is, the crosslinkable rubber composition according to the present invention is mixed with an ethylene / α-olefin / non-conjugated polyene random copolymer by an internal mixer (closed mixer) such as a Banbury mixer, a kneader or an intermix. A polymer rubber (A), a methacrylate or allylic compound having two or more functional groups (B), an organic peroxide (C), and if necessary, a rubber reinforcing agent,
After kneading additives such as an inorganic filler and a softener at a temperature of 80 to 170 ° C. for 3 to 10 minutes, using a roll such as an open roll, or a kneader, a crosslinking accelerator and a crosslinking agent are used as necessary. It can be prepared by additionally mixing an auxiliary agent, a foaming agent, and a foaming auxiliary agent, kneading the mixture at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing. In the present invention, the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) can be kneaded at a high temperature with a rubber reinforcing agent, an inorganic filler and the like, but the organic peroxide (C) can be kneaded at a high temperature. When kneading is carried out at the same time, crosslinking (scorch) occurs, and therefore, it is preferable to knead at 80 ° C. or lower when adding simultaneously.

The crosslinkable rubber composition according to the present invention prepared as described above can be formed into a desired shape by various molding methods such as an extrusion molding machine, a calender roll, a press, an injection molding machine and a transfer molding machine. It can be crosslinked at the same time as molding or by introducing the molded product into a crosslinking tank. 1-3 at a temperature of 120-270 ° C
Heating for 0 minutes or light, γ by the method described above.
A crosslinked product can be obtained by irradiating an electron beam or an electron beam. In this crosslinking step, a mold may be used, or the crosslinking may be performed without using a mold. When a mold is not used, the steps of molding and crosslinking are usually performed continuously. The heating method in the crosslinking tank includes hot air, a fluidized bed of glass beads,
A heating tank such as UHF (ultra-high frequency electromagnetic wave) or steam can be used.

The crosslinkable rubber composition according to the present invention is suitably used in the production of polyamide rubber laminates such as automotive hoses, water supply hoses, gas hoses; transmission belts, conveyor belts; and rubber for escalator handrails. Can be

Examples of the automobile hose include a brake hose, a radiator hose, a heater hose, and an air cleaner hose.

Examples of the transmission belt include a V-belt, a flat belt, and a toothed belt. Examples of the transport belt include a light transport belt, a cylindrical belt, a rough top belt, a transport belt with a flange, a transport belt with a U-shaped guide, and a transport belt with a V guide.

The hoses (automobile hoses, water supply hoses, gas hoses), belts (power transmission belts, transport belts), and escalator handrail rubbers according to the present invention can be obtained by using a fiber base material containing polyamides and the above-mentioned book. The rubber composition is produced by laminating the crosslinkable rubber composition according to the present invention, and performing crosslinking and adhesion of the rubber composition.

Polyamides constituting the fiber base material include aliphatic polyamides such as nylon 6, nylon 6,6 and nylon 6,10; polymethaxylylene adipamide (MXD6), polyhexamethylene terephthalamide ( 6T) or semi-aromatic polyamides such as copolymerized polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide and poly-m-phenylene isophthalamide.

These polyamide fibers are used as a fiber substrate in the form of filaments or staple fibers, and are used as a substrate in a known form such as a cord yarn, a spun yarn, a woven fabric, a knitted fabric or a nonwoven fabric. Of course, these substrates may be used in a single layer or in a multilayer of two or more layers.

The fibrous base material to be used may be composed of the above polyamide alone, or may be composed of polyamide and other reinforcing fibers.
For example, glass fiber, PAN-based carbon fiber, pitch-based carbon fiber, alumina fiber, silicon carbide fiber,
It may be composed of a combination with aluminum borate fiber, polyester fiber or the like.

The above-mentioned rubber molded product is obtained by laminating the crosslinkable rubber composition of the present invention on these fiber substrates, applying pressure, and performing crosslinking by the above-mentioned means.

[0064]

The crosslinkable rubber composition according to the present invention comprises:
It is possible to provide a crosslinked rubber molded article which can be bonded to an untreated polyamide and, more specifically, has excellent properties such as compression set resistance, strength properties, heat resistance, weather resistance, and abrasion properties.

Since the crosslinked rubber molded article obtained from the crosslinkable rubber composition according to the present invention has the above-mentioned effects, hoses such as automobile hoses, water supply hoses, gas hoses, etc .; Widely used for belts such as escalator handrail rubber.

[0066]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The composition, iodine value and intrinsic viscosity [η] of the copolymer rubber used in the examples and comparative examples were measured by the following methods. (1) Composition of copolymer rubber The composition of the copolymer was measured by 13C-NMR method. (2) Iodine value of copolymer rubber The iodine value of the copolymer rubber was determined by a titration method. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber was measured in 135 ° C decalin.

Example 1 Ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A) [E
PT (1); ethylene / propylene (molar ratio) = 68 /
32, iodine value = 10, 100 parts by weight of intrinsic viscosity [η] = 2.1 dl / g measured in decalin at 135 ° C., 65 parts by weight of carbon black [manufactured by Tokai Carbon Co., Ltd., trade name: Seast TM6], Softener [Idemitsu Kosan Co., Ltd.
Product name Diana Process Oil TMPS-430] 1
0 parts by weight and 1 part by weight of stearic acid were kneaded with a 1.7 liter Banbury mixer [manufactured by Kobe Steel Ltd.].

The kneading method is as follows.
5-vinyl-2-norbornene random copolymer rubber (A)
Was kneaded for 30 seconds, then carbon black and a softener were added and kneaded for 2 minutes. Thereafter, the ram was raised for cleaning, kneading was further performed for 1 minute, and the mixture was discharged at about 150 ° C. to obtain a rubber compound. This kneading was performed at a filling rate of 70%.

Next, 175 parts by weight of this mixture was rolled to an 8-inch roll (front roll surface temperature: 50 ° C., rear roll surface temperature: 50 ° C., front roll speed: 16 rpm, rear roll speed: 18 rpm). Wound and zinc dimethacrylate (B-1) [Seiko Chemical Co., Ltd., trade name Hicross Z
T], 5 parts by weight, and dicumyl peroxide (C) [trade name: Mitsui DCP-40C, manufactured by Kayaku Akzo Co., Ltd.].
After adding to 8 parts by weight and kneading for 10 minutes, the mixture was separated into sheets to prepare uncrosslinked sheets of 2 mm and 3 mm.

The uncrosslinked sheet of 3 mm was placed on a woven fabric of 6,6-nylon fiber (manufactured by Teijin Shoji Co., Ltd.) and 150
It pressed at 170 degreeC for 15 minutes using the ton press molding machine. A test piece having a width of 25 mm was punched out of the crosslinked rubber-fiber composite thus obtained, and a T-peel test was performed at a tensile speed of 50 mm / min. A 2 mm unvulcanized sheet was pressed at 170 ° C. for 15 minutes using a 100-ton press molding machine to prepare a crosslinked sheet.

The obtained crosslinked sheet was subjected to a tensile test and a compression set test according to the following methods. (1) Tensile test According to JIS K6251, a tensile test was performed at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min, and the strength TB and elongation EB of the crosslinked sheet at break were measured. (2) Compression set test (CS) The prepared crosslinked sheets were laminated according to JIS K6250, and a compression set test was performed according to JIS K6262. This test condition is 150 ° C. × 22 hrs.

Table 1 shows the formulations of Examples and Comparative Examples.
Table 2 shows the results.

[Comparative Example 1]
In the same manner as in Example 1 except that zinc white # 1 (B-2) shown in Table 1 was used instead of the zinc dimethacrylate (B-1) used in the above. Table 2 shows the results.

[Embodiment 2] In Embodiment 1, Embodiment 1
Instead of zinc dimethacrylate (B-1) used in the above, triallyl cyanurate shown in Table 1 [Wako Pure Chemical Industries, Ltd.
(B-3)) was used in the same manner as in Example 1. Table 2 shows the results.

[Embodiment 3] In Embodiment 1, Embodiment 1
In place of zinc dimethacrylate (B-1) used in the above, except that trimethylolpropane trimethacrylate [manufactured by Wako Pure Chemical Industries, Ltd.] (B-4) shown in Table 1 was used.
Performed in the same manner as in Example 1. Table 2 shows the results.

[Embodiment 4] In Embodiment 3, Embodiment 3
The procedure was performed in the same manner as in Example 1 except that 5.1 parts by weight of dicumyl peroxide (C) used in Example 1 was used. Table 2 shows the results
Shown in

[0078]

[Table 1]

[0079]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/14 C08K 5/14 (72) Inventor Masaaki Kawasaki 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Chemicals Co., Ltd. F-term in the company (reference) JK06A JK09 JL09 JL11A YY00A 4J002 BB101 BB151 ED026 EH076 EH106 EH146 EK017 EK037 EK057 EK067 EU186 EU196 FD010 FD020 FD146 FD157 FD320 GF00 GL00 GM00 GM01 GN00

Claims (12)

[Claims] 1. A crosslinkable rubber composition which is a rubber composition capable of bonding to a polyamide and has an adhesive strength of 10 N / cm or more. 2. The rubber composition according to claim 1, wherein the rubber composition is an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
The crosslinkable rubber composition according to claim 1, comprising a methacrylate or allylic compound (B) having two or more functional groups, and an organic peroxide (C). 3. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) per 100 parts by weight,
The methacrylate or allylic compound (B) having two or more functional groups is contained in an amount of 0.1 to 30 parts by weight and the organic peroxide (C) is contained in an amount of 0.1 to 20 parts by weight. A crosslinkable rubber composition according to claim 2. 4. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber according to claim 1, wherein the non-conjugated polyene is at least one kind of norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II]. 4. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
3. The crosslinkable rubber composition according to item 1. Embedded image [In the formula, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] , Embedded image [Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. 5. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) comprises (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin). ) Is in the range of 40/60 to 95/5, (ii) the iodine value is in the range of 0.5 to 50, and (iii) the intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is 0. The crosslinkable rubber composition according to any one of claims 2 to 4, which is in a range of 5 to 10 dl / g. 6. The rubber comprising a laminate of a fiber base material containing polyamides and a layer of the crosslinkable rubber composition according to claim 2 provided on the fiber base material. A polyamide rubber laminate, wherein a layer of the composition is crosslinked and adhered to a fiber substrate. 7. The rubber comprising a laminate of a fiber base material containing polyamides and a layer of the crosslinkable rubber composition according to claim 2 provided on the fiber base material. An automotive, water or gas hose characterized in that the composition layer is crosslinked and adhered to a fibrous substrate. 8. The hose according to claim 7, wherein the automobile hose is a brake hose, a radiator hose, a heater hose, or an air cleaner hose. 9. The rubber comprising a laminate of a fiber base material containing polyamides and a layer of the crosslinkable rubber composition according to claim 2 provided on the fiber base material. A transmission or transport belt, wherein the layer of the composition is crosslinked and adhered to a fibrous substrate. 10. The transmission belt according to claim 9, wherein the transmission belt is a V belt, a flat belt, or a toothed belt.
The belt described in. 11. The conveyance belt is a light conveyance belt, a cylindrical belt, a rough top belt, a conveyance belt with a flange, a conveyance belt with a U-shaped guide, or a conveyance belt with a V guide. The belt according to claim 9, wherein the belt is formed. 12. The rubber, comprising a laminate of a fiber base material containing polyamides and a layer of the crosslinkable rubber composition according to claim 2 provided on the fiber base material. An escalator handrail rubber, wherein a layer of the composition is crosslinked and adhered to a fiber substrate.