JPH0571710B2 - - Google Patents
Info
- Publication number
- JPH0571710B2 JPH0571710B2 JP6844790A JP6844790A JPH0571710B2 JP H0571710 B2 JPH0571710 B2 JP H0571710B2 JP 6844790 A JP6844790 A JP 6844790A JP 6844790 A JP6844790 A JP 6844790A JP H0571710 B2 JPH0571710 B2 JP H0571710B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- liquid
- latex
- isocyanate
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 71
- 239000005060 rubber Substances 0.000 claims description 71
- 239000012783 reinforcing fiber Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 description 62
- 229920000126 latex Polymers 0.000 description 31
- 239000004816 latex Substances 0.000 description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001897 terpolymer Polymers 0.000 description 9
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 229920002681 hypalon Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 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 description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- MKZXROSCOHNKDX-UHFFFAOYSA-N 1,4-dinitrosobenzene Chemical compound O=NC1=CC=C(N=O)C=C1 MKZXROSCOHNKDX-UHFFFAOYSA-N 0.000 description 2
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UIGULSHPWYAWSA-UHFFFAOYSA-N 3-amino-4-[(2-methylpropan-2-yl)oxy]-4-oxobutanoic acid;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)C(N)CC(O)=O UIGULSHPWYAWSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KMGMCLWJFCGWFI-UHFFFAOYSA-N chembl3276923 Chemical compound ON=C1C=CC(=O)C=C1 KMGMCLWJFCGWFI-UHFFFAOYSA-N 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PQCHENNROHVIHO-UHFFFAOYSA-M silver;2-methylprop-2-enoate Chemical compound [Ag+].CC(=C)C([O-])=O PQCHENNROHVIHO-UHFFFAOYSA-M 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
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(Industrial Application Field) The present invention relates to rubber reinforcing fibers. (Prior Art) Reinforcing fibers such as glass fiber yarn are widely used to increase the strength of rubber products such as rubber belts and tires. Rubber products such as rubber belts are subjected to repeated bending stress, resulting in bending fatigue, resulting in decreased performance, and peeling between the reinforcing material and the rubber matrix is likely to occur. In order to prevent such peeling or performance deterioration and obtain a sufficient reinforcing effect, it is necessary to increase the compatibility and adhesive strength between the reinforcing fibers and the rubber. be done. Various compositions of processing agents have been proposed. For example, various processing agents have been proposed, such as a processing agent using a combination of a vinylpyridine-styrene-butadiene terpolymer latex and a water-soluble condensate of resorcinol and formalin, or a processing agent containing rubber latex (Japanese Unexamined Patent Application Publication No. 1983-1999). (See No. 114551). Furthermore, a treatment liquid containing a polyisocyanate, a polynitroso aromatic compound, and an acidic halogen-containing polymer has also been proposed (see Japanese Patent Application Laid-Open No. 14546/1983). Furthermore, a treatment liquid containing a polyisocyanate, a polynitroso aromatic compound, and an acidic halogen-containing polymer has also been proposed (see Japanese Patent Application Laid-Open No. 14546/1983). Further, a first liquid (RFL liquid) containing a water-soluble condensate of resorcin formaldehyde and rubber latex is applied to the rubber reinforcing fibers to form a first layer containing the resorcin formaldehyde condensate and rubber on the fibers, and then the rubber latex is coated with a first layer containing the resorcin formaldehyde condensate and rubber. It is also known to form a second layer containing isocyanate and rubber by treating with an overcoat liquid containing isocyanate (see JP-A-49-14546). Furthermore, it has been proposed to use H-NBR latex as the rubber latex to be contained in RFL (see Japanese Patent Laid-Open No. 270877/1983). (Problems to be Solved by the Invention) Conventional treatment liquids for rubber reinforcing fibers and conventional methods for treating rubber reinforcing fibers have the following problems. (1) Sufficient adhesive strength cannot be obtained. (2) It is difficult to obtain rubber products with sufficient bending strength. (3) Adhesiveness decreases when used at high temperatures. That is,
Heat resistance is insufficient. Recently, with the rise in temperature near automobile engines, heat-resistant rubbers such as chlorosulfonated polyethylene and hydrogenated nitrile rubber have come to be used as rubber for timing belts. Since such heat-resistant rubber has lower adhesion than ordinary rubber, the above-mentioned drawbacks tend to be greater than that of ordinary rubber, and a timing belt that can withstand long-distance running has not been obtained. Treat the rubber reinforcing fibers with RFL liquid, then
Although the above-mentioned problems can be solved to some extent by treating with an overcoat liquid containing rubber latex and isocyanate, this method has the following problems. (1) Adhesive strength decreases over time. (2) In order to obtain sufficient effects, it is necessary to use a large amount of isocyanate; increasing the amount of isocyanate deteriorates the stability of the solution, and it is necessary to prepare a small amount of overcoat solution each time it is used. . (3) The interfacial adhesion between the RFL layer (first layer) and the overcoat liquid (second layer) is poor, and peeling easily occurs between the first and second layers. Although the method of using an RFL liquid containing H-NBR latex is particularly effective when the matrix rubber is H-NBR, this method also has the following drawbacks. That is, it is necessary to use an aqueous emulsion as the rubber latex to be contained in the RFL liquid. Although it is technically possible to produce an aqueous solution containing H-NBR, the complexity of the production process significantly increases costs. The present invention solves the problems of the prior art described above,
The purpose is to provide rubber reinforcing fibers that do not lose adhesive strength over time even when used under high temperature conditions such as being subjected to repeated bending stress, have high heat resistance, and have low manufacturing costs. It is said that (Means for solving the problem) In order to achieve the above object, the present invention includes:
As a rubber reinforcing fiber for reinforcing the matrix rubber, a second layer containing a halogen-containing polymer and an isocyanate is formed on the first layer containing a water-soluble condensate of resorcin formaldehyde and rubber formed on the fiber, A fiber is used in which a third layer containing the same rubber as the matrix rubber is further formed on the second layer. In a preferred embodiment of the present invention, a second compound containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent is used.
layer, or a second layer containing an inert fine powder such as a halogen-containing polymer, isocyanate, vulcanizing agent, carbon black, or silica, or the same rubber, vulcanizing agent, carbon black, or silica as the matrix rubber. A reinforcing fiber formed with a third layer containing an inert fine powder such as the following is used. Next, the present invention will be explained in more detail. In the present invention, the first layer is formed by applying a liquid containing a resorcin formaldehyde condensate and rubber latex (RFL liquid) onto the rubber reinforcing fibers. A water-soluble condensate of resorcin formaldehyde (hereinafter simply referred to as a condensate) is a resorcin and formaldehyde rich in oxymethyl groups obtained by reacting resorcin and formaldehyde in the presence of an alkaline catalyst such as an alkali hydroxide, ammonia, or an amine. Water-soluble initial addition condensates (resols) can be preferably used. In particular, the molar ratio of resorcinol and formaldehyde is 1:0.3 to 2.5.
It is preferable to react at a ratio of . As the rubber latex used in the RFL liquid (first liquid), a latex with a relatively low degree of polymerization that is used as a treatment agent for rubber reinforcing fibers can be suitably used, and there is no limitation, but in particular, butadiene rubber latex, Among vinylpyridine-styrene-butadiene terpolymer latexes (hereinafter referred to as terpolymer latexes), terpolymer latexes are preferred. As a terpolymer latex, the weight ratio of vinylpyridine, styrene, and butadiene is 10 to 10.
20:10~20:60~80 is particularly suitable,
Pyratex (product name, manufactured by Sumitomo Nogatatsuku Co., Ltd.), 0650
(trade name, Nippon Synthetic Rubber Co., Ltd.), Nipol2518FS (trade name, Nippon Zeon Co., Ltd.), etc. can be suitably used. As the butadiene latex, butadiene latex, butadiene-styrene copolymer latex, butadiene-nitrile copolymer latex, etc. are suitable, such as 0700 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.), Nipol LX111, Nipol 1562. (Product name,
(manufactured by Nippon Zeon) etc. can be suitably used. Although the above-mentioned terpolymer latex and butadiene latex can be used alone, it is preferable to use both in combination and in a mixture with chlorosulfonated polyethine (CSM) latex described below. As CSM latex, the chlorine content is 20~
40wt%, preferably 25-35wt%, S content in the sulfon group is 0.5-2.0wt%, preferably 1.1-35wt%
A raw rubber having a Mooney viscosity of 30 to 95 is suitably used. In addition, some of the CSM latex (50wt% or less,
Chloroprene (CR) (preferably 25wt% or less)
Alternatively, it can also be replaced with a latex of hydrogenated nitrile rubber (H-NBR). Rubber reinforcing fiber treatment liquid 1 containing each of the above-mentioned components
The concentrations of terpolymer latex, butadiene latex, CSM latex, and condensate in the liquid are 10 to 30 wt%, 3 to 25 wt%, and 0.5 to 6 wt%, respectively.
Preferably 15-25wt%, 5-15wt%, 1-3wt
%, the total amount of these is 10 to 50 wt%, preferably 20 to 40 wt%, and the amount of the first liquid applied to the reinforcing fibers is 12 to 50 wt% of the fiber weight as solid content.
A suitable amount is 25 wt%, preferably 16 to 22 wt%. Incidentally, a latex stabilizer, an anti-aging agent, etc. may be added to the first liquid if necessary. Although there are no particular limitations on the reinforcing fibers used in the present invention, it is practical to use glass fibers.
For example, glass fibers with a thickness of 9 ÎŒm that are bundled with a sizing agent and about 200 glass fibers can be suitably used. Arrange three such reinforcing fibers and add the first
The liquid is applied in an amount of 12 to 25 wt%, preferably 16 to 22 wt%, according to a conventional method. After the first liquid is applied and dried, the second liquid is applied according to a conventional method. It is desirable to dry the first liquid at a temperature of 200 to 350°C. In the present invention, a second layer containing a halogen-containing polymer and an isocyanate is formed on the first layer thus formed. The second layer can be suitably formed by applying a second liquid as described below. The amount of second liquid applied is 0.5 to 5wt to the reinforcing fiber.
%, preferably 1 to 4 wt%. Preferably at 100-200â after applying the second liquid
Dry in . In addition, 2.54
After applying S or Z twist (pre-twist) of about 0.5 to 4.0 per cm (1 inch), pull together about 2 to 13 more strands and twist in the opposite direction to the pre-twist, about 0.5 to 3.0 per 2.54 cm. It is desirable to apply the second liquid to the yarn by giving it a ply twist. As the second liquid, one containing a halogen-containing polymer and an isocyanate is used. A liquid containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent, preferably a halogen-containing polymer, an isocyanate, a vulcanizing agent, and an inert fine powder such as carbon black or silica, particularly the liquid described below, is suitably used. As the halogen-containing polymer, chlorinated rubber, chloroprene, chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated polyvinyl chloride, chlorosulfonated polyethylene, etc. can be used, but chlorosulfonated polyethylene is particularly preferred. Give results. The chlorosulfonated polyethylene (CSM) latex has a chlorine content of 20 to 40 wt%, preferably 25 to 35 wt%, and an S content of 0.5 to 2.0 wt%, preferably 1.1 to 1.4 wt% in the sulfon group. is appropriate, and the Mooney viscosity of raw rubber is 30 to 95.
Those can be suitably used. Also, the amount of halogen-containing polymer in the second liquid is
1 to 10 wt% as solid content, preferably 2 to 5 wt%
It is appropriate to If this amount is too small, the effect will not be sufficient, and if this amount is too large, the adhesive force will decrease. Isocyanate is added to the second liquid. The amount of isocyanate is suitably 0.5 to 2.0 wt%, preferably 1 to 15 wt%, and can improve adhesion. The amount of isocyanate is sufficient to be about 50% of that of conventional technology, and there is no deterioration in bending fatigue or heat resistance that would occur if too much isocyanate is used, and the stability of the overcoat liquid is increased. do. The weight percent of the total amount of isocyanate and halogen-containing polymer in the second liquid is suitably 3 to 15 wt%, preferably 5 to 10 wt%; if this concentration is too large, the viscosity of the liquid will increase; Unevenness tends to occur, and if this concentration is too low, the amount of adhesion decreases, making it impossible to obtain a sufficient effect. Furthermore, by containing a vulcanizing agent in the second liquid, the adhesion can be further improved and more suitable results can be obtained. Polynitroso aromatic compound A as a vulcanizing agent
(e.g. p-dinitrosobenzene), tetrachlorobenzoquinone, poly p-dinitrosobenzene,
Examples include p,p'-dibenzoyl, benzoquinone dioxime, and p-benzoquinone oxime,
Particularly preferred are tetrachlorobenzoquinone, polyp-dinitrosobenzene, p,p'-dibenzoylbenzoquinone dioxime, and p-benzoquinone dioxime. It is appropriate that the amount of the vulcanizing agent in the second liquid be 0.3 to 3 wt%, preferably about 0.6 to 2.5 wt%.If this amount is too small, the effect will not be sufficient, and the Peeling between the layers is likely to occur. The second liquid further contains litharge, lead maleate,
A lead compound such as lead phthalate can also be added, which has the effect of improving water resistance. The amount of lead compound in the second liquid is suitably 0.5 to 5 wt%, preferably 1 to 3 wt%. Furthermore, even better results can be obtained by adding methacrylate or acrylate as a vulcanization aid to the second liquid. As the methacrylate and acrylate, lead methacrylate, zinc methacrylate, aluminum methacrylate, silver methacrylate, and similar metal salts of acrylic acid can be suitably used. The amount of methacrylate or acrylate to be suspended in the second liquid is 3 to 0.001 wt%, preferably
It is appropriate to set it as 1.5-0.05wt%. Inert fine powder of carbon black, silica, titanium, etc. has a particle size of 10 to 200 mΌ, preferably 20 mΌ.
~100 mΌ can be suitably used. It is practical to knead inert fine powders such as carbon black and silica into the rubber in advance. The amount of inert fine powder such as carbon black or silica is 10 to 50 wt%, preferably 20 to 50 wt%, based on the rubber.
It is appropriate to set it at 40wt%. The strength of the second layer can be increased by adding carbon black or an inert fine powder such as silica. The amount of the second liquid to be applied is suitably 0.5 to 5 wt%, preferably 2 to 4 wt%, based on the solid content, based on the reinforcing fibers. In the present invention, after drying the second layer thus formed, a third layer containing the same rubber as the matrix rubber is formed thereon. Rubbers include chlorosulfonated polyethine, nitrile rubber, and hydrogenated nitrile rubber (H-
NBR), ethylene-propylene rubber (EPDM)
is exemplified. The third layer can be suitably formed by applying the third liquid as described below. The third liquid will be explained below. As the third liquid, it is appropriate to use an organic solvent solution of the same rubber as the matrix rubber. As the organic solvent, toluene, MEK, xylene, trichloroethane, trichloroethylene, etc. can be suitably used. Also, the concentration is 3~20wt
%, preferably 5 to 15 wt%. It is desirable that the third liquid further contains carbon black, inert fine powder such as silica, and a vulcanizing agent. Inert fine powder such as carbon black, silica, titanium, etc. has a particle size of 10 to 200 mΌ, preferably 20 to 200 mΌ.
Use a 100 mΌ sample and suspend it in the third liquid. The amount of inert fine powder such as carbon black and silica is 10 to 50 wt%, preferably 20 to 40 wt% of the rubber.
It is appropriate to do this, and it is practical to knead it into the rubber in advance. By adding these, the strength of the third layer can be increased. As the vulcanizing agent, the vulcanizing agents mentioned in the second liquid or peroxides such as sulfur and dicumyl peroxide can be suitably used, and the vulcanizing aids mentioned in the second liquid are used together. You can also obtain better results. The amounts of the vulcanizing agent and the vulcanizing aid are 0.5 to 15 wt%, 0.1 to 1.5 wt%, preferably 1 to 1.5 wt%, respectively, based on the rubber.
~10wt%, 0.2~1wt%, and the amount of the third liquid applied is suitably 0.5~5wt%, preferably 1~4wt% as a solid content, based on the reinforcing fibers. (Function) A second layer containing a halogen-containing polymer and an isocyanate is formed on the first layer containing a water-soluble condensate of resorcin formaldehyde and rubber formed on a rubber reinforcing fiber for reinforcing the matrix rubber. By forming a third layer containing the same rubber as the matrix rubber on top of the two layers, the adhesive force between the matrix rubber and the reinforcing fibers is increased, and the adhesive force between the rubber and the reinforcing fibers is subjected to repeated stress. Even when used under such conditions, it prevents deterioration over time, reinforcing fibers,
The interfacial adhesion between the second layer, the third layer, and the matrix rubber is increased to prevent peeling. Further, by using a second layer containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent, the amount of isocyanate used can be reduced, and deterioration of flex fatigue resistance and heat resistance that would occur if too much isocyanate is used can be prevented. Further, performance deterioration due to aging of the second liquid itself is prevented. Furthermore, the effects of the present invention can be obtained by containing inert fine powder such as carbon black or silica in the second layer and by containing inert fine powder such as a vulcanizing agent or carbon black or silica in the third layer. Increase it further. (Example) Vinylpyridine, styrene and butadiene
65 parts by weight of vinylpyridine-styrene-butadiene terpolymer latex (Pyratex, trade name, manufactured by Sumitomo Naugatatsu Co., Ltd., terpolymer content 41wt%) containing a ratio of 15:15:70, butadiene latex (0700, Product name, Japan Synthetic Rubber Co., Ltd., 8 parts by weight of butadiene content (57 wt%), 20 wt% of an addition condensate of resorcinol and formaldehyde (resol) is added to a mixture of 15 parts by weight and 12 parts by weight of water, and further anti-aging. As agents, 1 part by weight of a mineral oil emulsion (mineral oil content: 55 wt%) and 1 part by weight of aqueous ammonia (concentration: 18 wt%) were added to obtain a first liquid (RFL liquid). 0.8 parts by weight of zinc methacrylate, 6 parts by weight of chlorosulfonated polyethylene (Hypalon 40, trade name, manufactured by Showa Denko DuPont), polyisocyanate (MR-200, trade name, manufactured by Nippon Polyurethane Co., Ltd.)
1.1 parts by weight, 1.5 parts by weight of p,p'-dibenzoylbenzoquinone dioxime (vulcanizing agent), and toluene were added to obtain a second liquid having a concentration of 10 wt%. In a toluene solution of ethylene-propylene rubber (concentration 7.5 wt%), carbon black with a particle size of 50 mΌ was suspended at 50 wt% relative to the rubber, and 1.0 wt% of sulfur was added.
% was added to obtain a third solution. The first liquid was applied to three glass fiber bundles made of 200 9ÎŒ glass fibers in a conventional manner (solid content: 17 wt%). After drying at 250â for 1 minute,
This glass fiber bundle was given 4.0 Z twists (pre-twist) per 2.54 cm, and 13 of the fiber bundles that had been given this pre-twist were then aligned and subjected to S twists (pre-twist) 2.1 times per 2.54 cm. 2% solids content of the second liquid
After application, it was dried at 140°C for 1 minute, and 2wt% of the third liquid was added as a solid content, heated at 140°C for 1 minute, and dried. A test piece was prepared using the same method. Composition of matrix rubber: 100 parts by weight of ethylene-propylene rubber: 50 parts by weight of carbon black, 5 parts by weight of stearic acid, 2.5 parts by weight of anti-aging agent, 1 part by weight of vulcanizing agent, 1.5 parts by weight of vulcanization accelerator, 5 parts by weight of plasticizer Contains parts by weight. Preparation of test piece The following test piece was prepared using rubber having the above composition. Test piece 1 One of the above reinforcing fibers was sandwiched between rubber sheets with a thickness of 1 mm, a width of 10 mm, and a length of 500 mm, pressed, and heated at 160°C.
Vulcanize for 30 minutes. Test piece 2 The above reinforcing fibers were arranged without gaps between rubber sheets with a thickness of 3 mm, width of 25.4 mm, and length of 100 mm, pressed, and vulcanized at 160°C for 20 minutes. Using this test piece 1, the number of times it was bent until it broke was measured using a bending fatigue tester at room temperature. This test piece 2 was measured at 50mm/
The adhesive force was measured by peeling at a pulling speed of min. The results of the above tests are shown in the attached table. (Comparative example) Using only the first and second liquids of the above example, the third liquid
The same experiment was conducted without using the liquid (Comparative Example 1). A similar experiment was also conducted in the case where the first liquid of the example was used and the second and third liquids were not used at all (Comparative Example 2). The results of these experiments are shown in the attached table.
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ã«åäžããã[Table] (Effects of the invention) Even when used for a long time under conditions that provide repeated bending strength, the decrease in adhesive strength is small, and even when chlorosulfonated polyethylene, hydrogenated nitrile rubber, etc. are used as the matrix rubber, the adhesive strength is large. It has great strength and greatly improves bending fatigue resistance.
Claims (1)
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ç¶ã[Scope of Claims] 1. In a rubber reinforcing fiber for reinforcing matrix rubber, a halogen-containing polymer, an isocyanate, etc. A rubber reinforcing fiber comprising: a second layer containing the same rubber as the matrix rubber; and a third layer containing the same rubber as the matrix rubber formed on the second layer. 2. The rubber reinforcing fiber according to claim 1, wherein the second layer contains a halogen-containing polymer, an isocyanate, and a vulcanizing agent. 3. The rubber reinforcing fiber according to claim 1, wherein the second layer contains a halogen-containing polymer, an isocyanate, a vulcanizing agent, carbon black, or an inert fine powder such as silica. 4. The rubber reinforcing fiber according to claim 1, 2 or 3, wherein the third layer contains the same rubber as the matrix rubber, a vulcanizing agent, carbon black, or inert fine powder such as silica.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2068447A JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2068447A JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03269177A JPH03269177A (en) | 1991-11-29 |
JPH0571710B2 true JPH0571710B2 (en) | 1993-10-07 |
Family
ID=13373970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2068447A Granted JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03269177A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3864097B2 (en) | 2001-03-12 | 2006-12-27 | æ¬ç°æç å·¥æ¥æ ªåŒäŒç€Ÿ | Fiber for reinforcing rubber products |
JP4520069B2 (en) * | 2001-04-18 | 2010-08-04 | æ¥æ¬æ¿ç¡åæ ªåŒäŒç€Ÿ | Treatment agent, rubber reinforcing cord and rubber product |
JP5118299B2 (en) | 2005-12-13 | 2013-01-16 | ãªãŒã·ãŒãŽã£ãŒ ã€ã³ãã¬ã¯ãã¥ã¢ã« ãã£ãã¿ã« ãšã«ãšã«ã·ãŒ | Glass fiber for rubber product reinforcement |
EP2151520B1 (en) * | 2007-05-25 | 2013-09-18 | Nippon Sheet Glass Company, Limited | Rubber reinforcing member and rubber product utilizing the same |
EP2952625B1 (en) * | 2013-01-30 | 2019-03-27 | Nippon Sheet Glass Company, Limited | Carbon fiber cord for reinforcing rubber product and rubber product using same |
-
1990
- 1990-03-20 JP JP2068447A patent/JPH03269177A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH03269177A (en) | 1991-11-29 |
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