CN101057024A - Rubber-reinforcing cord, method for manufacturing same, and rubber article using same - Google Patents
Rubber-reinforcing cord, method for manufacturing same, and rubber article using same Download PDFInfo
- Publication number
- CN101057024A CN101057024A CN 200580038644 CN200580038644A CN101057024A CN 101057024 A CN101057024 A CN 101057024A CN 200580038644 CN200580038644 CN 200580038644 CN 200580038644 A CN200580038644 A CN 200580038644A CN 101057024 A CN101057024 A CN 101057024A
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- Prior art keywords
- rubber
- latex
- flexible cord
- resin
- butadiene
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Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 225
- 239000005060 rubber Substances 0.000 title claims abstract description 225
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 229920000126 latex Polymers 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 8
- 239000004816 latex Substances 0.000 claims description 73
- 229920000459 Nitrile rubber Polymers 0.000 claims description 50
- 239000000835 fiber Substances 0.000 claims description 48
- 238000005728 strengthening Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 17
- 230000002787 reinforcement Effects 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 125000005968 oxazolinyl group Chemical group 0.000 claims description 14
- 239000007859 condensation product Substances 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004640 Melamine resin Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920002681 hypalon Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- 239000012783 reinforcing fiber Substances 0.000 abstract 5
- -1 oxazoline compound Chemical class 0.000 description 34
- 238000012360 testing method Methods 0.000 description 26
- 239000000470 constituent Substances 0.000 description 19
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- 239000003365 glass fiber Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
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- 230000014759 maintenance of location Effects 0.000 description 7
- 230000001360 synchronised effect Effects 0.000 description 6
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
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- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 238000004132 cross linking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
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- 206010016256 fatigue Diseases 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Disclosed is a rubber-reinforcing cord (10) containing reinforcing fibers (11). The surface of each reinforcing fiber (11) is provided with a coating film (12). The coating film (12) mainly contains a rubber which includes acrylonitrile as one of the raw materials, and a compound containing an oxazoline group. Also disclosed is a method for manufacturing a rubber-reinforcing cord which comprises a step (i) wherein an aqueous mixture mainly containing a rubber latex, which includes acrylonitrile as one of the raw materials, and a compound containing an oxazoline group is applied to reinforcing fibers, and a step (ii) wherein a coating film is formed on the surface of each reinforcing fiber by drying the aqueous mixture applied to the reinforcing fibers.
Description
Technical field
The present invention relates to a kind of rubber strengthens with flexible cord and manufacture method thereof.In addition, the invention still further relates to a kind of rubber that this rubber strengthens using flexible cord (cord) of burying underground.
Background technology
For rubbers such as adhesive tape or rubber tyres, improve in order to make its intensity or durability, extensively glass fibre or chemical fibre etc. are embedded in matrix (matrix) rubber with fiber as strengthening usually.But reinforcement is not fully oozed with rubber with fiber self and closed usually, and is very poor with the cementability of rubber.So, under situation about not being embedded in the rubber to strengthening carrying out surface treatment with fiber, take place easily to strengthen not bonding with fiber with rubber, the perhaps weak and problem in use peeled off simply of bonding force.
Therefore, in order to improve the cementability of strengthening with between fiber and the base rubber, and in order to prevent to strengthen deterioration, form by overlay film with fiber strengthening with fiber.For example, open the spy and to record in the clear 63-270877 communique to making its dry solidification as strengthening with the glass fibre coating resorcinol formaldehyde condensation product of fiber and the aqueous adhesive that mixes of hydrogenated nitrile-butadiene rubber latex, formation is by overlay film.Open in the clear 63-270877 communique according to the spy and to put down in writing, utilize this glass fibre flexible cord, can improve and be cementability between the base rubber of main component with the hydrogenated nitrile-butadiene rubber.
Strengthen the kind that is needed binding matrix rubber by overlay film or its characteristic with fiber, change adjustment is contained to become to grade.This be because be used to improve base rubber with by of the kind change of the most preferred combinations of the cementability between the overlay film according to base rubber.Thereby, open the glass fibre flexible cord of putting down in writing in the clear 63-270877 communique above-mentioned spy, even for being to be useful for the base rubber of main component with the hydrogenated nitrile-butadiene rubber, but for other base rubber, not necessarily demonstrate high adhesiveness.
But, the known hydrogenated nitrile-butadiene rubber (following be recited as sometimes " H-NBR/ZDMA ") that hydrogenated nitrile-butadiene rubber (following be recited as sometimes " H-NBR ") is arranged and be dispersed with zinc dimethacrylate is the rubber composition of main component.Use the rubber as the base rubber of main component, because heat resistance is very outstanding, so be applicable to that vehicle is with in the purposes such as synchronous band of engine with this H-NBR and H-NBR/ZDMA.
Strengthen using flexible cord as this base rubber and the rubber that demonstrates high adhesiveness, open in the flat 11-241275 communique the spy and to record, possess and in strengthening, contain the 1st coating of resorcinol formaldehyde condensation product and rubber latex and be that crosslinking coagent is the rubber reinforcement flexible cord of the 2nd coating of main component with rubber composition, crosslinking agent and maleimide thereon with flexible cord.
In addition, open in the flat 5-339552 communique (No. 3379069 communique of patent) and to disclose " after the fiber that the polymer dissolution of the water-soluble that will contain the 2-oxazolinyl forms is attached to fibrous material with adhesive composite; the fibrous material that this fibrous material and rubber composition is bonding and the adhering method of rubber " the spy in aqueous medium, and then also disclose " in adhesive composite, adding rubber latex ".
And then, open in the 2004-183121 communique and to disclose " possess that coating is the aqueous adhesive of main component with rubber latex and vulcanization aid on strengthening with fiber, what make that its dry solidification forms is strengthened using flexible cord by the rubber of overlay film " the spy.
At present, particularly in the purposes of automobile, more and more higher to the durability requirement of synchronous band, open the rubber of putting down in writing in the flat 11-241275 communique above-mentioned spy and strengthen using flexible cord, aspect durability, be required further raising.In addition, this rubber is strengthened need forming the 1st coating and the 2nd coating with flexible cord, so the trend that exists operation to become numerous and diverse.
Even opening in the 2004-183121 communique disclosed rubber for above-mentioned spy strengthens also needing further to improve durability for flexible cord.
In addition, in recent years, also being opened to various base rubber, is that the base rubber of main component is cheaper than hydrogenated nitrile-butadiene rubber, and as the base rubber that does not contain halogen, is that the base rubber of main component is often used with the ethylene propylene rubber.Therefore, need not select the kind of matrix and operable reinforcement flexible cord.
Summary of the invention
The present invention is conceived to aforesaid problem points just and proposes.One of purpose of the present invention is to provide a kind of demonstrating with the rubber of the high adhesiveness of base rubber to strengthen with flexible cord and manufacture method thereof.
Study to achieve these goals, discovery such as the inventor as a result is by being coated on rubber and strengthening forming by overlay film with fiber having added the aqueous mixture (aqueous adhesive) that contains the compound that oxazolinyl is arranged, even by overlay film is individual layer, also can obtains demonstrating with the rubber of the high adhesiveness of base rubber and strengthen using flexible cord.The present invention just is being based on the invention of this neodoxy.
Rubber of the present invention strengthens using flexible cord, it is to contain the rubber of strengthening with fiber to strengthen using flexible cord, wherein, be formed with by overlay film on the surface of described reinforcement with fiber, described main component by overlay film comprises with acrylonitrile as the rubber of one of raw material with contain the compound that oxazolinyl is arranged.
In addition, rubber of the present invention is that rubber of the present invention is strengthened being embedded in rubber in the base rubber with flexible cord.
In addition, be used to make rubber and strengthen method of the present invention, comprising: (i) will be coated on the operation of strengthening the usefulness fiber as the aqueous mixture that the compound of the latex (latex) of the rubber of one of raw material and Han You oxazolinyl contains as main component with acrylonitrile with flexible cord; (ii) form by the operation of overlay film on the surface of described reinforcement with fiber by the described aqueous mixture drying that makes coating.
Rubber of the present invention strengthen with flexible cord can utilize form on the flexible cord surface by overlay film, the cementability between improvement and the base rubber dramatically.Thereby, bury this rubber underground and strengthen with the rubber of flexible cord outstanding aspect durability such as warp resistance fatigability, resistance to water, oil resistivity, heat resistance.In addition, the rubber among the present invention is because outstanding aspect durability, so be applicable in the purposes such as synchronous band.
And then, utilize the present invention, can constitute with individual layer and strengthen using fiber, strengthen using flexible cord so make rubber easily, can suppress manufacturing cost.
Description of drawings
Fig. 1 is that expression rubber of the present invention is strengthened the pattern sectional view with an example of flexible cord.
Fig. 2 is a pattern sectional view of representing the flat rubber belting made in an embodiment.
Fig. 3 is a synoptic diagram of representing the bend test device that uses in an embodiment.
The specific embodiment
Below embodiments of the present invention are described.
[rubber strengthens using flexible cord]
Rubber of the present invention is strengthened containing the reinforcement fiber with flexible cord.On the surface of this reinforcement, be formed with by overlay film with fiber.This main component by overlay film comprises: with acrylonitrile as the rubber of one of raw material (below be sometimes referred to as " rubber (A) ") with contain compound that oxazolinyl is arranged (below be sometimes referred to as " oxazoline compound (B) ").Rubber (A) amounts to oxazoline compound (B) and accounts for by more than the 50 quality % of overlay film.
Shang Shu oxazoline compound (B) water relatively is insoluble.At this, " water is insoluble compound relatively " is meant the compound that can form aqueous dispersions.
On state oxazoline compound (B) oxazolinyl can be the 2-oxazolinyl.
Rubber (A) can comprise at least a rubber of selecting from the group of hydrogenated nitrile-butadiene rubber and acrylonitrile-butadiene rubber formation.
Strengthen to be contained resin by overlay film at rubber of the present invention with in the flexible cord.In this case, this resin is at least a for what select the group that constitutes from polyurethane resin, epoxy resin, acrylic resin, phenolic resin, melamine resin and low molecular weight polycaprolactone olefin resin.
Rubber of the present invention is strengthened with in the flexible cord, is contained select the group of condensation product, carbon black, peroxide and isocyanates formation from resorcinol and formaldehyde at least a by overlay film.As peroxide, for example can enumerate cumene hydroperoxide (Cumen Hydroperoxide).As isocyanates, can enumerate organic compound dinitro benzene for example with isocyano group.
Strengthen with in the flexible cord at rubber of the present invention, contained from vinylpyridine rubber, vinylpyridine styrene butadiene terpolymer rubber, butadiene rubber, butadiene styrene copolymer rubber, dicarboxyl butadiene styrene copolymer rubber, ethylene propylene rubber, styrene tar polymer rubber, chlorosulfonated polyethylene rubber, contain select the group that fluorubber and acrylic rubber constitute at least a by overlay film.
[rubber]
Rubber of the present invention is that rubber of the present invention is strengthened being embedded in rubber in the base rubber with flexible cord.
Base rubber can be main component (containing ratio: more than the 50 quality %) with the hydrogenated nitrile-butadiene rubber.In this case, can in hydrogenated nitrile-butadiene rubber, disperse zinc dimethacrylate.In addition, base rubber can be main component (containing ratio: more than the 50 quality %) with the ethylene propylene rubber.
Rubber of the present invention can be synchronous band.
[rubber is strengthened the manufacture method with flexible cord]
Above-mentioned rubber is strengthened can be with following manufacture method manufacturing of the present invention with flexible cord.Wherein, in following manufacture method, can be suitable for the material that reinforcement describes with flexible cord to rubber.
Manufacture method of the present invention comprises that the aqueous mixture that will contain as main component as the compound of latex (latex) of the rubber of one of raw material (below be sometimes referred to as " latex (A) ") and Han You oxazolinyl (above-mentioned “ oxazoline compound (B) ") with acrylonitrile (below be sometimes referred to as " aqueous mixture (C) ") is coated on the operation of strengthening with fiber (operation (i)).At this, aqueous mixture is meant that decentralized medium is the mixture of water-based, for example means that 50 quality % of decentralized medium are above to be the mixture of water.(B) is same as described above for the oxazoline compound.In addition, the rubber of latex (A) is identical with above-mentioned rubber (A).
The Xiang Jiao of latex (A) Yu oxazoline compound (B) amount to more than the 50 quality % of all solids composition (composition beyond the decentralized medium solvent) account for aqueous mixture (C).
In manufacture method of the present invention, then, form by overlay film (operation (ii)) on the surface of strengthening with fiber by described aqueous mixture (C) drying that makes coating.Drying means to aqueous mixture (C) is unqualified, can air dry, can heat drying, and also can drying under reduced pressure, also can make up them.
Suo Shu oxazoline compound (B) water relatively is insoluble.
The oxazolinyl of the oxazoline compound of stating (B) can be the 2-oxazolinyl.
Described latex (A) can comprise at least a latex in the group that the latex of the latex that is selected from hydrogenated nitrile-butadiene rubber and acrylonitrile-butadiene rubber constitutes.
Described aqueous mixture (C) can contain the resin that disperses in described aqueous mixture (C).This resin for example is added in the mixture under the state in being scattered in water.This resin can be for being selected from least a in the group that polyurethane resin, epoxy resin, acrylic resin, phenolic resin, melamine resin and low molecular weight polycaprolactone olefin resin constitute.
Described aqueous mixture (C) can contain at least a in the group that the condensation product that is selected from resorcinol and formaldehyde (below be sometimes referred to as " RF condensation product "), carbon black, peroxide and isocyanates constitute.
Described aqueous mixture (C) contains the latex that is selected from vinylpyridine rubber, the latex of vinylpyridine styrene butadiene terpolymer rubber, the latex of butadiene rubber, the latex of butadiene styrene copolymer rubber, the latex of dicarboxyl butadiene styrene copolymer rubber, the latex of ethylene propylene rubber, the latex of styrene tar polymer rubber, the latex of chlorosulfonated polyethylene rubber, contain at least a in the group that the latex of the latex of fluorubber and acrylic rubber constitutes.
Below rubber of the present invention is strengthened being elaborated with flexible cord and manufacture method thereof.
In the time will strengthening being embedded in the base rubber,, kind or shape are not particularly limited as long as improved the shape stability or the intensity of base rubber with fiber.For example, can utilize glass fibre; Representative vinal in vinylon (vinylon) fiber; Polyester fiber, nylon, aromatic polyamide fibre (ア ラ ミ De) polyamide fibers such as (aromatic polyamides); Polyarylate (Port リ ア リ レ one ト) compound; Polyketone fiber; Carbon fiber; Polyparaphenylene benzo-dioxazole (below be sometimes referred to as " PBO ") fiber etc.Wherein, preferred heat resistance and the outstanding glass fibre of tensile strength.
Kind to the glass in the glass fibre is not particularly limited, and compares with common alkali-free glass, and the high strength glass that tensile strength is outstanding meets the application target that rubber strengthens using flexible cord, and is preferred.
In addition, the formation of fiber is not particularly limited, as the silk (filament) of the minimum component unit of glass fibre usually its average diameter be preferably 5 μ m～13 μ m.In addition, the normally used flexible cord of glass fibre is, with 50～2000 silks and become 1 or many, twist with the fingers to same direction, as the first twist flexible cord, so will many these first twist flexible cords also together, to carrying out whole sth. made by twisting in the opposite direction with first twist side.In addition, can also use and do not carry out flexible cord, the first twist of twisting with the fingers eventually and and be twisted as unidirectional flexible cord eventually or strengthen using the various flexible cords that constitute such as flexible cord of direction of flexible cord, change first twist or the whole sth. made by twisting of the fiber that constitutes by different materials with the core of flexible cord and outer layer segment at rubber.The flexible cord of twisting with the fingers like this is applicable to purposes such as synchronous band.
Use fiber form as strengthening,, be not particularly limited,, can enumerate staple fiber (staple), silk, flexible cord shape, rope (rope) shape or canvas shape etc. as object lesson so long as the form that can be embedded in the base rubber gets final product.
Rubber of the present invention is strengthened at the side coating aqueous adhesive of strengthening with fiber its dry solidification being formed with can be passed through by overlay film in the flexible cord.
The main component of aqueous mixture (C) is that (rubber (A)) is with oxazoline compound (B) for the rubber of latex (A).
The effect of oxazoline compound (B) performance crosslinking agent.Strengthen the special cementability of strengthening with fiber and base rubber that improves grotesquely of ， oxazolinyl Zhong flexible cord at rubber of the present invention.Ci Wai ， oxazolinyl usefulness-C
3H
4NO represents that can think has 3 structures.Wherein, can obtain usually with the 2-oxazolinyl of following chemical formulation, preferred.Oxazoline compound (B) can use the material of various forms such as water-dispersion type, oil-in-water type.
[changing 1]
Oxazoline compound (B) can be for containing the polymer that oxazolinyl is arranged.The object lesson of Zuo Wei oxazoline compound (B) for example can be enumerated エ Port Network ロ ス K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, the K-2030E of Nippon Shokubai Co., Ltd.
Acrylonitrile is better as the fused property of the rubber of one of raw material and base rubber, so can improve the cementability of strengthening with fiber and base rubber effectively.In addition, with acrylonitrile as the rubber of one of raw material outstanding aspect heat resistance or the oil resistivity, strengthen using flexible cord so can make the high rubber of durability.As latex (A), can illustration hydrogenated nitrile-butadiene rubber latex or acrylonitrile-butadiene rubber latex etc.Hydrogenated nitrile-butadiene rubber can be for being dispersed with the rubber of zinc dimethacrylate.It is the rubber of one of raw material that latex (A) contains more than a kind or 2 kinds with the acrylonitrile.
Above-mentioned aqueous mixture (C) can further contain latex (A) latex in addition.For example, as the latex that does not contain the rubber of acrylonitrile in the raw material, can enumerate latex, the chlorosulfonated polyethylene rubber of latex, the styrene tar polymer rubber of latex, the ethylene propylene rubber of latex, the dicarboxyl butadiene styrene copolymer rubber of latex, the butadiene styrene copolymer rubber of latex, the butadiene rubber of latex, the vinylpyridine styrene butadiene terpolymer rubber of vinylpyridine rubber latex, contain the latex of fluorubber and the latex of acrylic rubber.Wherein, aqueous mixture (C) can contain 1 or multiple latex.
Aqueous mixture (C) can also contain resin emulsion or water-dispersion type resin except latex.As resin, can enumerate polyurethane resin, epoxy resin, acrylic resin, phenolic resin, melamine resin, low molecular weight polycaprolactone olefin resin.Wherein, aqueous mixture (C) preferably contains 1 or multiple these resins with the form of emulsion or water-dispersion type resin.
In order further to improve cementability, aqueous mixture (C) also can contain the condensation product (condensation resin) of resorcinol and formaldehyde
Aqueous mixture (C) can contain carbon black.By adding carbon black, can suppress the manufacturing cost that rubber strengthens using flexible cord as cheap inorganic filler.And then, can also improve the cementability that rubber strengthens using flexible cord and base rubber effectively.
In addition, aqueous mixture (C) can also contain other compositions such as inorganic filler beyond the carbon black or plasticizer, age resistor, metal oxide, crosslinking coagent.As inorganic filler, can enumerate silica dioxide granule.
Aqueous mixture (C) also can contain peroxide.By adding peroxide, can promote crosslinked by overlay film and base rubber, so their cementability further improves.Kind to peroxide is unqualified, for example can use organic peroxides such as hydroperoxides or dialkyl peroxide.Wherein, peroxide need select with base rubber in the identical peroxide of reaction speed of the crosslinking agent that mixes.In various peroxide, cumene hydroperoxide (Cumen Hydroperoxide) is outstanding aspect cementability and operability, and is preferred.
In order further to improve cementability, aqueous mixture (C) also can contain isocyanates.Isocyanates has the effect that improves bridging property.
Aqueous mixture (C) can also contain multiple in the condensation resin, carbon black, peroxide, isocyanates of above-mentioned resorcinol and formaldehyde.
Rubber (A) and oxazoline compound (B) be by the rubber of overlay film strengthen with flexible cord by the main component of overlay film, the two total accounts for by more than the 50 quality % of overlay film.In addition, (A) is Ji oxazoline compound (B) is the main component of aqueous mixture (C) to latex.The solid constituent of latex (A) is Yu the quality of the total of oxazoline compound (B) accounts for more than 50% of quality of the decentralized medium composition in addition of aqueous mixture (C).
In addition, aqueous mixture (C) contains a lot of compositions sometimes in decentralized medium (aqueous solvent).But composition not remaining after forming by overlay film is as being treated by the constituent of overlay film.For example in aqueous solvent, contain under the situation of aqueous mixture (C) of a lot of lower alcohols, because the heating of lower alcohol by by the formation of overlay film the time removed fully, do not treat so be not used as constituent, when the main component that judges whether to aqueous mixture (C), do not consider.
Aqueous mixture (C) is preferably in aqueous solvent and disperses by the form of the constituent of overlay film.If be aqueous solvent, good operability then, the concentration management of constituent is easily.And then, compare with organic solvent, alleviate environmental pressure especially.As an example of aqueous solvent, can enumerate water and account for the above liquid medium (liquid medium) of 50 quality %, for example can enumerate water.
In aqueous mixture (C), (A) is Yu the mass ratio of the solid constituent of oxazoline compound (B) is that (A)/oxazoline compound (B)=100/ (2～70) is preferably latex (A)/oxazoline compound (B)=100/ (10～50) to latex to latex.In addition, example as the mass ratio of the solid constituent of the composition that contains in the aqueous mixture (C), (A)/oxazoline compound (B)/carbon black/peroxide=100/ (2～70)/(0～50)/(0～20) is preferably the latex (scope of A)/oxazoline compound (B)/carbon black/peroxide=100/ (10～50)/(10～20)/(5～15) can to enumerate latex.In addition, be identical by the mass ratio of the composition in the overlay film with the mass ratio of above-mentioned solid constituent.
In these, latex (A) Yu the ratio of oxazoline compound (B) be even more important.Very few as fruit oxazoline compound (B), then become insufficient between the overlay film and by crosslinked between overlay film and the base rubber, become at their interface and peel off easily.
On the other hand, too much as fruit oxazoline compound (B), because latex becomes few relatively, so too improved by the hardness of overlay film self, bending is as a result scratched fatigue and is died down.
To on strengthening, applying the method for aqueous mixture (C) and the method for the dry aqueous mixture (C) that has applied with fiber, unqualified, usually will strengthen with fiber impregnation in the tank that adds aqueous mixture (C), after it is mentioned, in drying oven, remove decentralized medium.In addition, unqualified to the drying condition that is used to remove decentralized medium, for example under 80 ℃～160 ℃ atmosphere, expose 0.1～2 minute and get final product.
Fig. 1 strengthens using an example of flexible cord with the rubber that schematically shows such formation.Rubber strengthen with flexible cord 10 comprise strengthen with fiber 11 and cover strengthen with fiber 11 on every side by overlay film 12.There is preferable range in adhesive rate by overlay film 12.In addition, be meant that by the adhesive rate R of overlay film the quality of relative glass fibre in the dried flexible cord shows the quality percentage that is adhered to by overlay film of the quality of much degree, provides with following formula.
R(％)＝((C1-C0)/C0)×100
C0: the dry mass of the glass fibre before the lining, C1: the dry mass of flexible cord of the reinforcement after the lining
Adhesive rate R is preferably 10～30%, so be preferably 12～25%, adhesive rate R is less than under 10% the situation, becoming to be difficult to use by overlay film covers all surfaces of strengthening with fiber.
On the other hand, if adhesive rate R surpasses 30%, then in forming by overlay film, the liquid trickling of aqueous mixture (C) becomes problem easily.And then, blocked up by overlay film, then occur in central part and the equal problem of periphery characteristic that rubber strengthens using flexible cord easily.
To the rubber reinforcement is unqualified with the means that flexible cord is embedded in base rubber, can directly divert known means.The rubber that obtains like this have concurrently base rubber characteristic source high-fire resistance and strengthen the high-durability that has with flexible cord by burying rubber underground.Thereby this rubber is specially adapted to the purposes such as synchronous band of engine.
As base rubber, preferred be suitable for the hydrogenated nitrile-butadiene rubber be main component rubber, be the rubber of main component or be the rubber of main component with little hydrogenated nitrile-butadiene rubber that is dispersed with zinc dimethacrylate with the ethylene propylene rubber.
Embodiment
The present invention is described in detail below to utilize embodiment.
[embodiment 1-1]
Make 3 glass fibres (E glass is formed: the silk of 200 average root diameters, 9 μ m is collected bunchy) and together, the aqueous mixture (C) shown in the coating table 1, with it at the drying oven inner drying 1 minute that is set at 150 ℃.Form by overlay film like this.
[table 1]
| Composition | Content [parts by mass] |
| H-NBR latex (solid constituent: 40 quality %) ( *1-1) | 100 |
| The phenolic resin emulsion (solid constituent: 48 quality %) ( *1-2) | 20 |
| The water dispersion of oxazoline compound ( *1-3) (solid constituent: 40 quality %) | 60 |
(
*1-1) ZETPOL LATEX, Japanese ゼ オ Application corporate system
(
*1-2) ユ カ レ ジ Application KE912-1 (lucky village oiling length of schooling)
(
*1-3) エ Port Network ロ ス K-2030E (Japanese catalyst system)
With the twisting count of 8 times/10cm, first twist forms this by the glass fibre of overlay film.Prepare 11 11 in glass fibres of first twist,, twist with the fingers eventually with them and together, obtain rubber and strengthen using flexible cord with the twisting count of 8 times/10mm.This rubber is strengthened the quality with flexible cord relatively, is 20 quality % by the adhesive rate of overlay film.
Then, this rubber is strengthened estimating with the cementability of the base rubber shown in flexible cord and the table 2.Cementability is by measuring base rubber and strengthening estimating with the peel strength between the fiber.
Below the assay method of peel strength is described.At first, make the test piece (wide 25mm * long 50mm * thick 5mm) that the composition shown in the table 2 constitutes, in this test piece, strengthen using flexible cord along 25 rubber of long limit configuration of test piece, heating made it bonding in 30 minutes under 170 ℃.With the sample that cupping machine stretches and to obtain like this to machine direction, measure base rubber and the reinforcement peel strength when peeling off between the fiber.Utilize this peel strength, evaluation base rubber and the reinforcement cementability between the fiber.And then the destruction face of visualization sample is observed collapse state.That is, judge: strengthen using the flexible cord side at rubber, " the rubber destruction " of the state that base rubber is remaining fully, or base rubber strengthens using " interface peel " of the complete noresidue of flexible cord side at rubber.
[table 2]
| Composition | Content [parts by mass] |
| H-NBR( *2-1) | 70 |
| H-NBR/ZDMA( *2-2) | 30 |
| ZnO | 10 |
| Stearic acid | 1 |
| Carbon black | 30 |
| Trioctyl trimellitate (TOTM) (Trioctyl Trimellitate) | 5 |
| Sulphur | 0.1 |
| 1,3-pair-(tert-butyl hydroperoxide-isopropyl)-benzene (1,3-Bis-(t-butylperoxy-isopropyl)-benzene) | 6 |
(
*2-1) ZETPOL 2020, Japanese ゼ オ Application corporate system
(
*2-2) ZSC 2000L, Japanese ゼ オ Application corporate system
In addition, the durability of evaluation rubber as described below.At first, strengthen using flexible cord 1m as heart yearn the rubber of making in an embodiment, be embedded in the base rubber of rubber reinforcement with the composition shown in the table 2 of the central portion of flexible cord.Like this, at the central portion of rubber reinforcement, make the flat rubber belting of the long 300mm of wide 19mm, band portion with flexible cord.Fig. 2 is to schematically show the sectional view of flat rubber belting part, and flat rubber belting 20 comprises base rubber and the rubber reinforcement flexible cord 22 that is embedded in the base rubber.Flat rubber belting 20 uses bend test device evaluation shown in Figure 3.
Carry out in heat resistant test, the water 3 kinds of bend tests testing in test, the oil, number of bends is 20000 times.Heat resistant test has only air in heating tank 31, the temperature in the heating tank 31 is set at 80 ℃.Test adds entry in the water in heating tank 31, becomes normal temperature.Test adds oil in the oil in heating tank 31, is set at 120 ℃.
Measure preceding tensile strength of bend test and the tensile strength after the bend test, utilize following formula to calculate strength retention.Estimate the durability of rubber based on this strength retention.In addition, " tensile strength " is meant the two ends of clamping (chuck) flat rubber belting, the maximum intensity during stretching till flat rubber belting fracture.
Strength retention (%)=(TENSILE STRENGTH before the TENSILE STRENGTH/test after the test) * 100
Above the results are shown in Table 3.
[table 3]
| Embodiment 1-1 | Embodiment 1-2 | Embodiment 1-3 | Comparative example 1-1 | Comparative example 1-2 | ||
| The composition of aqueous mixture | H-NBR OXZ phenolic resin | H-NBR OXZ carbon black | NBR OXZ RF | H-NBR RF | NBR RF | |
| Adhesive strength (N/cm) | 80 | 110 | 90 | 40 | 35 | |
| Failure mode | Rubber destroys | Rubber destroys | Rubber destroys | Interfacial failure | Interfacial failure | |
| Strength retention (%) | Heat resistant test | 85 | 91 | 84 | 83 | 78 |
| Test in the water | 69 | 82 | 83 | 60 | 73 | |
| Test in the oil | 61 | 64 | 58 | 46 | 40 | |
H-NBR: hydrogenated nitrile-butadiene rubber, NBR: acrylonitrile-butadiene rubber
OXZ: oxazoline compound, RF: resorcinol formaldehyde condensation product
[embodiment 1-2, embodiment 1-3]
In embodiment 1-2 and embodiment 1-3, the aqueous mixture (C) that replacement is used in embodiment 1-1 uses the aqueous mixture (C) shown in the table 4.In addition, similarly making rubber with embodiment 1-1 strengthens using the method evaluation identical with embodiment 1-1 with flexible cord and flat rubber belting.Evaluation result sees Table 3.
[table 4]
| Composition | Content [parts by mass] | |
| Embodiment 1-2 | Embodiment 1-3 | |
| H-NBR latex (solid constituent: 40 quality %) ( *4-1) | 100 | 0 |
| Acrylonitrile-butadiene rubber latex (solid constituent: 41 quality %) ( *4-2) | 0 | 100 |
| The water dispersion of oxazoline compound ( *4-3) (solid constituent: 40 quality %) | 60 | 60 |
| Carbon black water dispersion (solid constituent: 30 quality %) | 20 | 0 |
| RF condensation product (solid constituent: mol ratio=1/1.3 of 8 quality %, R/F) | 0 | 20 |
(
*4-1) ZETPOL LATEX, Japanese ゼ オ Application corporate system
(
*4-2) NIPOL1561, Japanese ゼ オ Application corporate system
(
*4-3) エ Port Network ロ ス K-2030E (Japanese catalyst system)
[comparative example 1-1, comparative example 1-2]
In comparative example 1-1 and comparative example 1-2, the aqueous mixture (C) that replacement is used in embodiment 1-1 uses the aqueous mixture shown in the table 5.Temperature in the drying oven during in addition, with drying coated aqueous mixture in glass fibre is set at 230 ℃.In addition, similarly making rubber with embodiment 1-1 strengthens using the method evaluation identical with embodiment 1-1 with flexible cord and flat rubber belting.Evaluation result sees Table 3.
[table 5]
| Composition | Content [parts by mass] | |
| Comparative example 1-1 | Comparative example 1-2 | |
| H-NBR latex (solid constituent: 40 quality %) ( *5-1) | 65 | 0 |
| Acrylonitrile-butadiene rubber latex (solid constituent: 41 quality %) ( *5-2) | 0 | 65 |
| RF condensation product (solid constituent: mol ratio=1/1.3 of 8 quality %, R/F) | 30 | 30 |
| 25 quality % ammoniacal liquor | 1 | 1 |
| Water | 4 | 4 |
(
*5-1) ZETPOL LATEX, Japanese ゼ オ Application corporate system
(
*4-2) NIPOL1561, Japanese ゼ オ Application corporate system
As shown in table 3, by Tian Jia oxazoline compound, adhesive strength greatly increases.In addition, this trend occurs in the aqueous mixture that contains H-NBR and carbon black (C) significantly.In addition, in the strength retention of bend test, the also additive effect of Ke Jian oxazoline compound.
[embodiment 2-1, embodiment 2-2, comparative example 2-1]
The rubber that to make in embodiment 1-1, embodiment 1-2 and comparative example 1-1 is strengthened bonding or be embedded in the base rubber of the composition shown in the table 6 with flexible cord, respectively as the sample of embodiment 2-1, embodiment 2-2, comparative example 2-1.Each sample is carried out above-mentioned evaluation.
[table 6]
| Composition | Content [parts by mass] |
| EPDM rubber | 70 |
| Acrylonitrile- | 30 |
| Carbon black | 20 |
| Trioctyl trimellitate (TOTM) (Trioctyl Trimellitate) | 5 |
| Sulphur | 0.1 |
| 1,3-pair-(tert-butyl hydroperoxide-isopropyl)-benzene (1,3-Bis-(t-butylperoxy-isopropyl)-benzene) | 6 |
EPDM: ethylene, propylene binary tar polymer
In addition, EPDM is meant the rubber that ethene or propylene and other the 3rd composition polymerizations obtain, a kind of for ethylene propylene rubber.EPDM is outstanding aspect weather fastness, heat-resistant aging, ozone resistance.It is the various vehicle parts, band, bed course (gasket), electric wire, waterproof material, polyolefinic resistance to impact modification material (cushion pad (bumper)) at center etc. that EPDM is widely used in the automobile.
Evaluation result sees Table 7.
[table 7]
| Embodiment 2-1 | Embodiment 2-2 | Comparative example 2-1 | ||
| The composition of aqueous adhesive | H-NBR OXZ phenolic resin | H-NBR OXZ carbon black | H-NBR RF | |
| Adhesive strength (N/cm) | 95 | 140 | 60 | |
| Failure mode | Rubber destroys | Rubber destroys | Interfacial failure | |
| Strength retention (%) | Heat resistant test | 75 | 88 | 80 |
| Test in the water | 79 | 87 | 72 | |
| Test in the oil | 40 | 43 | 33 | |
H-NBR: hydrogenated nitrile-butadiene rubber, OXZ: oxazoline compound,
RF: resorcinol formaldehyde condensation product
As shown in table 7, by Tian Jia oxazoline, adhesive strength increases by leaps and bounds.In addition, in containing the mixture of carbon black (C), demonstrate this trend significantly.In addition, the also additive effect of Ke Jian oxazoline compound in the strength retention of bend test.
Utilizability on the industry
The present invention goes for for the flexible cord of strengthening rubber and uses the rubber of this flexible cord.
Claims (21)
1. a rubber strengthens using flexible cord, and it is to contain to strengthen strengthening using flexible cord with the rubber of fiber, wherein,
Be formed with by overlay film on the surface of described reinforcement with fiber,
Described main component by overlay film comprises: with acrylonitrile as the rubber of one of raw material with contain the compound that oxazolinyl is arranged.
2. rubber according to claim 1 is strengthened using flexible cord, wherein,
The relative water of described compound is insoluble.
3. rubber according to claim 2 is strengthened using flexible cord, wherein,
Suo Shu oxazolinyl is the 2-oxazolinyl.
4. rubber according to claim 2 is strengthened using flexible cord, wherein,
Described rubber comprises at least a rubber in the group that is selected from hydrogenated nitrile-butadiene rubber and acrylonitrile-butadiene rubber formation.
5. rubber according to claim 2 is strengthened using flexible cord, wherein,
Describedly contained resin by overlay film.
6. rubber according to claim 5 is strengthened using flexible cord, wherein,
Described resin is to be selected from least a in the group that polyurethane resin, epoxy resin, acrylic resin, phenolic resin, melamine resin and low molecular weight polycaprolactone olefin resin constitute.
7. rubber according to claim 2 is strengthened using flexible cord, wherein,
Describedly contained at least a in the group that the condensation product that is selected from resorcinol and formaldehyde, carbon black, peroxide and isocyanates constitute by overlay film.
8. rubber according to claim 2 is strengthened using flexible cord, wherein,
Described being contained by overlay film is selected from vinylpyridine rubber, vinylpyridine styrene butadiene terpolymer rubber, butadiene rubber, butadiene styrene copolymer rubber, dicarboxyl butadiene styrene copolymer rubber, ethylene propylene rubber, styrene tar polymer rubber, chlorosulfonated polyethylene rubber, contains at least a in the group that fluorubber and acrylic rubber constitute.
9. rubber, wherein,
The described rubber of claim 2 is strengthened being embedded in the base rubber with flexible cord.
10. rubber according to claim 9, wherein,
Described base rubber is main component with the hydrogenated nitrile-butadiene rubber.
11. rubber according to claim 9, wherein,
In described hydrogenated nitrile-butadiene rubber, be dispersed with zinc dimethacrylate.
12. rubber according to claim 9, wherein,
Described base rubber is main component with the ethylene propylene rubber.
13. rubber according to claim 9, wherein,
It is to be with synchronously.
14. a rubber strengthens using the manufacture method of flexible cord, wherein, comprising:
(i) will be coated on the operation of strengthening with fiber as the aqueous mixture that the compound of the latex of the rubber of one of raw material and Han You oxazolinyl contains as main component with acrylonitrile;
(ii) form by the operation of overlay film on the surface of described reinforcement with fiber by the described aqueous mixture drying that makes coating.
15. manufacture method according to claim 14, wherein,
The relative water of described compound is insoluble.
16. manufacture method according to claim 15, wherein,
Suo Shu oxazolinyl is the 2-oxazolinyl.
17. manufacture method according to claim 15, wherein,
Described latex comprises at least a latex in the group that the latex of the latex that is selected from hydrogenated nitrile-butadiene rubber and acrylonitrile-butadiene rubber constitutes.
18. autofrettage according to claim 15, wherein,
Described aqueous mixture contains the resin that disperses in described aqueous mixture.
19. manufacture method according to claim 18, wherein,
Described resin is to be selected from least a in the group that polyurethane resin, epoxy resin, acrylic resin, phenolic resin, melamine resin and low molecular weight polycaprolactone olefin resin constitute.
20. manufacture method according to claim 15, wherein,
Described aqueous mixture contains at least a in the group that the condensation product that is selected from resorcinol and formaldehyde, carbon black, peroxide and isocyanates constitute.
21. manufacture method according to claim 15, wherein,
Described aqueous mixture contains at least a in the group that the latex of the latex that is selected from vinylpyridine rubber, the latex of vinylpyridine styrene butadiene terpolymer rubber, the latex of butadiene rubber, the latex of butadiene styrene copolymer rubber, the latex of dicarboxyl butadiene styrene copolymer rubber, the latex of ethylene propylene rubber, the latex of styrene tar polymer rubber, the latex of chlorosulfonated polyethylene rubber, the latex that contains fluorubber and acrylic rubber constitutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004327333 | 2004-11-11 | ||
| JP327333/2004 | 2004-11-11 | ||
| JP008612/2005 | 2005-01-17 |
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| CN101057024A true CN101057024A (en) | 2007-10-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709655A (en) * | 2015-07-15 | 2018-02-16 | 日本板硝子株式会社 | Rubber reinforcement line and use its rubber |
| CN107804979A (en) * | 2017-11-08 | 2018-03-16 | 四川省玻纤集团有限公司 | One kind enhancing rubber basalt fibre size and preparation method of being chopped |
| CN117683282A (en) * | 2024-02-02 | 2024-03-12 | 北京超智控信科技有限公司 | Self-melting cladding insulating material for electrified railway positive feeder |
-
2005
- 2005-11-10 CN CN 200580038644 patent/CN101057024A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709655A (en) * | 2015-07-15 | 2018-02-16 | 日本板硝子株式会社 | Rubber reinforcement line and use its rubber |
| CN107709655B (en) * | 2015-07-15 | 2020-05-19 | 日本板硝子株式会社 | Rubber reinforcing cord and rubber product using same |
| CN107804979A (en) * | 2017-11-08 | 2018-03-16 | 四川省玻纤集团有限公司 | One kind enhancing rubber basalt fibre size and preparation method of being chopped |
| CN117683282A (en) * | 2024-02-02 | 2024-03-12 | 北京超智控信科技有限公司 | Self-melting cladding insulating material for electrified railway positive feeder |
| CN117683282B (en) * | 2024-02-02 | 2024-04-09 | 北京超智控信科技有限公司 | Self-melting cladding insulating material for electrified railway positive feeder |
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