CN1849362A - Two-step method for dipping synthetic fiber - Google Patents
Two-step method for dipping synthetic fiber Download PDFInfo
- Publication number
- CN1849362A CN1849362A CNA2004800261260A CN200480026126A CN1849362A CN 1849362 A CN1849362 A CN 1849362A CN A2004800261260 A CNA2004800261260 A CN A2004800261260A CN 200480026126 A CN200480026126 A CN 200480026126A CN 1849362 A CN1849362 A CN 1849362A
- Authority
- CN
- China
- Prior art keywords
- fiber
- latex
- rfl
- cord
- dipping
- 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.)
- Granted
Links
- 238000007598 dipping method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 8
- 239000012209 synthetic fiber Substances 0.000 title claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000005060 rubber Substances 0.000 claims abstract description 36
- 229920000126 latex Polymers 0.000 claims abstract description 28
- 239000004816 latex Substances 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- -1 isocyanate compound Chemical class 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 4
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000004636 vulcanized rubber Substances 0.000 abstract description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229920000271 Kevlar® Polymers 0.000 description 6
- 239000004761 kevlar Substances 0.000 description 6
- 102100034213 ATPase family protein 2 homolog Human genes 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 108010091193 spermatogenesis associated factor Proteins 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000006424 Flood reaction Methods 0.000 description 3
- 229920000561 Twaron Polymers 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000004762 twaron Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- AYNPIRVEWMUJDE-UHFFFAOYSA-N 2,5-dichlorohydroquinone Chemical compound OC1=CC(Cl)=C(O)C=C1Cl AYNPIRVEWMUJDE-UHFFFAOYSA-N 0.000 description 1
- RCXHRHWRRACBTK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propane-1,2-diol Chemical compound OCC(O)COCC1CO1 RCXHRHWRRACBTK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000002816 gill Anatomy 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a two-step method for dipping a synthetic fiber wherein the fiber is first dipped with an aqueous pre-dip composition followed by a dip with resorcinol-formaldehyde latex (RFL) composition, characterized in that the pre-dip composition comprises a blocked isocyanate having at least tri-functional isocyanate groups and a latex wherein the ratio by weight of blocked isocyanate and latex is between 9 and 0.7, preferably between 4 and 1. The invention further pertains to a pre-dip composition for dipping a synthetic fiber, comprising a blocked at least tri-functional isocyanate compound and a latex, further comprising water, an emulsifier, and 2-vinyl pyridine copolymer and to a fiber, cord, and composite article of rubber and fiber or cord, wherein the fiber or cord has distributed over at least a surface portion thereof (1) blocked tri-functional isocyanate compound, preferably HDI-trimer; (2) an RFL adhesive; and (3) an in situ vulcanized rubber compound.
Description
The present invention relates to be used for the dipping synthetic fiber two-step approach, wherein said fiber at first with the preimpregnated composite dipping, is used resorcinol-formaldehyde latex (RFL) composition dipping then.
Be used to be adhered to the fiber on the rubber compound, aromatic poly for example, usually through dip treating to strengthen combining of this synthon and rubber.This composition can be used for making matrix material, tire for example, and wherein fortifying fibre combines with the rubber for tire compound.
In the rubber composite manufacturing of (they comprise the fiber reinforced material of fiber, continuous filament yarn, cord or chopped fibres form), the importantly rubber matrix of reinforced composite and the bond properties between the fortifying fibre.
For example, aromatic poly is a kind of fiber that tire is reinforced that is used for.Because the crystal surface of fiber, it is very difficult providing bonding between aromatic poly and rubber.Therefore, effectively the preimpregnation processing is necessary, so that obtain ideal bond properties between fiber and the rubber.The standard method that this preimpregnation is handled is to use epoxy adhesive preimpregnation, uses resorcinol formaldehyde latex (RFL) dipping then, and this method provides the excellent bonds of aromatic poly strongthener and vulcanized rubber.
For example, usefulness epoxide and the polymine adhesion promotor as Kevlar has been proposed.Lyengar has proposed a kind of Kevlar to be adhered to two on rubber step bonding system.First step or preimpregnation should comprise epoxy compounds.(J.Appl.Polym.Sci., 2311, the 11 volumes (1967)).G.E.van Gills (The general Tire and Rubbers Co.) is at United States Patent (USP) 3,872, disclose the glycerine diglycidyl ether solution of use 2% in 939 as bonding layer and surface layer, it comprises 1,3-butadiene-styrene-2-vinylpyridine copolymer and heat reactivity 2,5-two (2,4-dihydroxy-benzene ylmethyl)-4-chlorophenol.
In EP 353473, except using traditional epoxy preimpregnated composite, also used comprise phenyl end capped 4,4 '-preimpregnated composite of diphenylmethanediisocyanate.These solution do not comprise dewater and isocyanic ester outside any other component.We have found that aqueous end-blocking vulcabond preimpregnated composite causes the bond properties of fiber and cord and rubber insufficient.
The preimpregnated composite that comprises triisocyanate and more senior isocyanate compound that is used for trevira is described at JP 57187238.This preimpregnated composite that comprises polyfunctional isocyanate and mixtures of diisocyanates is described in JP 51037174, and the preimpregnated composite that comprises blocked polyisocyanates and clay (for example bentonite) mixture is described at JP 55062269.But, but in these compositions none aspect adhesive rubber very effectively and wherein the none industrialization use.
In fact always to use epoxide, still owing to the increasingly stringent that requires of health care issues and government regulation, it is undesirable using epoxide to Kai Fa adhering technique at present from that time.According to the HSE regulations, it is undesirable that human body is exposed to epoxide.Therefore more and more require to obtain the impregnating process of safety, it does not use toxic materials and equivalent substantially with the tackiness agent based on epoxide.
For this reason, invented the two-step approach that is used for dipping synthetic fiber, wherein fiber is at first with moisture preimpregnated composite dipping, use resorcinol-formaldehyde latex (RFL) composition dipping then, it is characterized in that described preimpregnated composite comprises and has the blocked isocyanate and the latex of trifunctional isocyanates base at least, wherein the weight ratio of blocked isocyanate and latex is between 9 and 0.7, preferably between 4 and 1.
The fiber of dipping keeps and the identical bond properties that uses traditional epoxide preimpregnation to obtain like this, and can avoid this epoxide to handle fully.Therefore, preferred embodiment be to use basically or even the preimpregnated composite that do not contain the derivative of ring-containing oxide fully carry out impregnating process.
In another embodiment, preimpregnated composite can comprise the isocyanate compound and the latex of end capped trifunctional at least, and it further comprises water, emulsifying agent and 2-vinylpyridine copolymer.
The latex part of preimpregnation can be identical or different with the latex part of RFL composition, and be the segmented copolymer of conjugated alkene block and aromatic blocks.This segmented copolymer is being known in the art.Have been found that when latex part when preimpregnation and RFL composition is a vinyl-pyridine segmented copolymer, obtained good especially result.Suitable copolymers comprises 2-vinyl pyridine, vinylbenzene and divinyl residue.Preferably, the unit of 10-20% is the structure of class 2-vinyl pyridine in the described multipolymer.For example, suitable copolymers has general formula [(C
7H
7N)
l(C
8H
8)
m(C
4H
6)
n]
x, l wherein: be 1 (m+n): 9-1 than (weight %): 4, and m: the n ratio is 2: 3-4: 1.Most preferably, about 15: 35: 50 of l: m: n=.
The inventive method can be used for any synthon that are used as fortifying fibre usually at used rubber composites such as tire, travelling belts in principle.This fiber preferably comprises at least a in aromatic poly, polyester and the polyterephthalate.In the present invention, particularly suitable fiber comprises aromatic poly at least, preferably comprises PPTA and/or PPODPTA.
The inventive method is suitable for flooding the wherein fiber of fiber to spin and to use.
Described end capped isocyanic ester has trifunctional isocyanates group at least.The example of this isocyanic ester is 1,6-hexamethylene diisocyanate (HDI) tripolymer etc.Capping group is being known in the art, and is selected from the ketoxime group, as methyl ethyl ketone oxime; Pyrazole derivatives is as 3; Ester is as malonic ester; Hexanolactam and alkylating phenol.Most preferred blocked isocyanate is end capped HDI-tripolymer, for example the end capped hexamethylene diisocyanate trimer of methyl ethyl ketone oxime or 3.Most preferred END CAPPED GROUP is a 3.
Described RFL dipping can comprise emulsifying agent.Suitable emulsifying agent is selected from the emulsifying agent that comprises rubber latex.
Fit closely preimpregnation of the present invention is the composition that comprises following component: 3 of 2.5-4 weight % water-dispersion, the end capped isocyanate compound of 5-dimethyl pyrazole (HDI-tripolymer), the 2-vinylpyridine copolymer (latex) of 1-2.5 weight % and 90-96 weight % water (based on solid weight %).
Necessary is that the weight ratio of blocked isocyanate and latex is between 9 and 0.7.The composition that comprises too much or very few latex can not provide and the suitable bond properties of traditional epoxy preimpregnation.
More specifically, the invention provides method with Kevlar and vulcanizable rubber adhesion, it comprises step: (1) immerses fiber the fiber that applies with generation in the water dispersion that comprises following component: (a) 3 of 2.5-4 weight % water-dispersion, the end capped isocyanate compound of 5-dimethyl pyrazole (HDI-tripolymer), (b) the 2-vinylpyridine copolymer of 1-2.5 weight % and (c) 90-96 weight % water; (2) dry and solidify the fiber of this coating, with the fiber of production preimpregnation; (3) fiber to preimpregnation carries out the RFL adhesive-dipping, to produce impregnation of fibers; (4) dry and solidify this impregnation of fibers to produce impregnation of fibers; (5) but the solidified impregnation of fibers is contacted with vulcanized rubber; (6) solidify this vulcanizable rubber (based on solid weight %).
Relate to fiber and cord in another embodiment of the present invention, wherein fiber and cord have (1) the end capped trifunctional isocyanates that is distributed in its surface portion at least, as the end capped isocyanate compound of the 3 of water-dispersion (HDI-tripolymer); (2) RFL tackiness agent; (3) on-the-spot sulfurized rubber compound.
The composite article of rubber and fiber also is provided, and wherein fiber has (1) the end capped trifunctional isocyanates that is distributed in its surface portion at least, as the end capped isocyanate compound of the 3 of water-dispersion (HDI-tripolymer); (2) RFL tackiness agent; (3) on-the-spot sulfurized rubber compound.
The present invention will be illustrated by following non-limiting examples.
Embodiment 1
Present embodiment provides the test of using the aromatic poly sample, is used in combination the effect of trifunctional blocked isocyanate and 2-vinylpyridine copolymer on Kevlar with proof.
The contrast tackiness agent that is used for Kevlar is the two coatings of epoxy and RFL.Kevlar floods to compare with polyfunctional epoxy resin preimpregnation and RFL surface layer.
Experiment tackiness agent (bonding layer) comprises the Trixene as 3.5 weight % of preimpregnation
BI 7986 (3 end-blocking HDI tripolymer; From Baxenden Chemicals Ltd., UK) with 1.5 weight %Pliocord
VP106S (2-vinylpyridine copolymer latex; From GoodyearChemicals Ltd., USA) (based on solid) and as the RFL of surface layer.
Cord treatments
Aramid cord prepares with 2 strands of yarns.1680dtex PPTA yarn (Twaron
, from Teijin) or 1670dtex PPODPTA yarn (Technora
, from Teijin) twist with the Z direction with 330tpm.By stranding, the multiple twin yarn combines, and twists with the S direction with 330tpm.This former base cord floods in the preimpregnation tackiness agent and in 150 ℃ of dryings 120 seconds, solidifies 90 seconds in 240 ℃, immerses RFL, solidifies 90 seconds in 235 ℃.
The compound that is used to test
Impregnated aramid cord is tested at the compound that is used for passenger tyre layer rubber.Main ingredient is a natural rubber.
Result and discussion
To Trixene
Bl7986 and Pliocord
VP106S assesses as the aromatic poly tackiness agent.Impregnated aramid cord also floods in RFL and tests with the adherent thermotolerance static state is bonding.The results are summarized in Table I.
At present embodiment with thereafter among each embodiment, static release adhesive and bonding thermal test be meant with cord be embedded in rubber and rubber in metal die the solidified test (according to ASTM D4393; SPAF=is with peel adhesion).This matrix material sample then under atmosphere at room temperature under (static state) or the 120 ℃ of atmosphere (thermotolerance) load application separate with cord ply up to rubber, load is wherein represented with newton (N).
Table I
| PPTA | PPODPTA | ||||
| Preimpregnation 1 | Static SPAF N/2cm | Thermotolerance (N) | Static SPAF N/2cm | Thermotolerance (N) | |
| Contrast | 100/0 2 | 290(60) 3 | 280(45) | 200(30) | 210(35) |
| Compare 1 | 100/10 | 210(10) | 195(10) | 180(10) | 190(10) |
| Compare 2 | 90/10 | 250(20) | 240(15) | 180(15) | 185(15) |
| Compare 3 | 40/60 | 260(30) | 230(25) | 175(10) | 180(15) |
| Test 1 | 80/20 | 285(55) | 280(55) | 195(30) | 210(30) |
| Test 2 | 70/30 | 290(60) | 285(55) | 200(30) | 225(30) |
| Test 3 | 60/40 | 285(60) | 280(50) | 195(35) | 220(35) |
| Test 4 | 50/50 | 290(55) | 280(55) | 200(30) | 210(30) |
1HDI-tripolymer/latex dipping (HDI-tripolymer/2-vinyl pyridine (Vp) weight of latex ratio)
2Epoxide dipping rather than HDI-tripolymer/latex dipping
3The coverage % of the value representation stripper surface in the bracket
Embodiment 2
By the application standard cord (is Twaron
1000,1680dtex/2,1Z 330 * 2S 330) and standard rubbers (Dunlop
5320, NR rubber) and the using tyre carcass (weight ratio NR/SBR=70/30) is measured according to no epoxy preimpregnation of the present invention with according to the bond properties of the epoxy preimpregnation of prior art with rubber.
Yarn and cord
Twaron
1000,1680dtex/2,1Z 440 * 2S 440 (being used for motorcycle tyre)
Use two types twisting machinery (i.e. two step twisting=Rezzeni ring twisters and directly stranding=Saurer Allma)
Dipping
Standard prior art dipping (epoxy preimpregnation) (2% trifunctional glycidyl glyceryl ether (epoxide)/RFL)
According to dipping of the present invention (no epoxy preimpregnation) (non-epoxide/RFL)
(HDI tripolymer/Vp weight of latex ratio=75/25, concentration 5%)
In proper order
Preimpregnation; ℃ (9N)-90s * 240,120s * 150 ℃ (9N)
The RFL dipping; 90s * 235 ℃ (9N)
Assessment (SPAF)
Standard rubbers (Dunlop 5320; NR) 150 ℃ * 20 minutes
BS/FS rubber (cra) (NR/SBR) 160 ℃ * 20 minutes
The breaking tenacity of former base and polyfiber yarn immersion cord is shown in Table II
Table II
| The dipping type | Twisting machinery | The former base of breaking tenacity (N) | Breaking tenacity dipping (N) |
| Epoxide/RFL | Two steps | 425 | 423 |
| Non-epoxide/RFL* | Two steps | 425 | 435 |
| Epoxide/RFL | Direct stranding | 410 | 455 |
| Non-epoxide/RFL* | Direct stranding | 410 | 453 |
* according to the present invention
Bond properties
Use NR rubber and NR/SBR rubber are determined the SPAF performance at the epoxide/RFL (prior art) and the non-epoxy/RFL (the present invention) of two steps and direct stranding, and show under all conditions all much at one.All values all 280 and 320N/2cm between.
Coverage
Coverage is determined as follows.After measuring release adhesive, observe surface of peeling off and the ratio of measuring residual rubber.The results are shown in Table III.
Table III
| The dipping type | Twisting machinery | NR rubber | NR/SBR rubber |
| Epoxide/RFL | Two steps | R-R，R-C 65-70％ | R-R 100％ |
| Non-epoxide/RFL* | Two steps | R-R，R-C 60-65％ | R-R 100％ |
| Epoxide/RFL | Direct stranding | R-R，R-C 60-65％ | R-R 100％ |
| Non-epoxide/RFL* | Direct stranding | R-R，R-C 55-60％ | R-R 100％ |
The NR=natural rubber
SBR=vinylbenzene-butene rubber
The fracture of R-R=rubber
Rupture between R-C=rubber and the cord
* according to the present invention
It is suitable with the preimpregnation of prior art epoxide that these presentation of results do not have the preimpregnation of epoxy, therefore can be used as a kind of new adhesive bonding method.
Claims (11)
1. the two-step approach of a dipping synthetic fiber, wherein at first use moisture preimpregnated composite impregnation of fibers, use resorcinol-formaldehyde latex (RFL) composition dipping then, it is characterized in that described preimpregnated composite comprises and has the blocked isocyanate and the latex of trifunctional isocyanates group at least, wherein the weight ratio of blocked isocyanate and latex is between 9 and 0.7, preferably between 4 and 1.
2. method according to claim 1, wherein said preimpregnated composite do not contain the derivative of ring-containing oxide substantially.
3. method according to claim 1 and 2, the latex part of wherein said preimpregnated composite and RFL composition is the segmented copolymer of conjugated alkene block and aromatic blocks.
4. method according to claim 3, wherein said latex part are vinyl-pyridine segmented copolymer.
5. according to any described method in the aforementioned claim, wherein said synthon are to comprise fiber at least a in aromatic poly, polyester and the polyterephthalate.
6. method according to claim 5, wherein said synthon are for comprising aromatic poly at least, preferably comprising the fiber of PPTA and/or PPODPPA.
7. according to any described method in the aforementioned claim, wherein use as-spun fibre.
8. according to any described method in the aforementioned claim, wherein said blocked isocyanate is an end-blocking HDI tripolymer.
9. preimpregnated composite that is used for dipping synthetic fiber, it comprises end capped compound of trifunctional isocyanates at least and latex, and comprises water, emulsifying agent and 2-vinylpyridine copolymer.
10. fiber or cord, wherein this fiber or cord have (1) the end-blocking trifunctional isocyanates compound that is distributed in its surface portion at least, preferred HDI-tripolymer; (2) RFL tackiness agent; (3) on-the-spot sulfurized rubber compound.
11. the composite article of rubber and fiber as claimed in claim 10 or cord.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03020731.0 | 2003-09-12 | ||
| EP03020731 | 2003-09-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1849362A true CN1849362A (en) | 2006-10-18 |
| CN100523057C CN100523057C (en) | 2009-08-05 |
Family
ID=34306758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800261260A Expired - Fee Related CN100523057C (en) | 2003-09-12 | 2004-09-04 | Two-step method for dipping synthetic fiber |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060280942A1 (en) |
| EP (1) | EP1664161A1 (en) |
| JP (1) | JP2007505228A (en) |
| CN (1) | CN100523057C (en) |
| RU (1) | RU2346015C2 (en) |
| WO (1) | WO2005026239A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102619094A (en) * | 2012-03-14 | 2012-08-01 | 浙江海之门橡塑有限公司 | Dip solution and application thereof in aramid fibers |
| CN102634986A (en) * | 2012-04-20 | 2012-08-15 | 北京化工大学 | Method for pretreating fibers |
| CN102634985A (en) * | 2012-03-17 | 2012-08-15 | 马鞍山科英合成材料有限公司 | Closed isocyanate adhesive for gumming fiber framework materials of rubber products, composition of closed isocyanate adhesive, preparation method and application |
| CN102912636A (en) * | 2012-11-01 | 2013-02-06 | 台州宏元工艺有限公司 | Polyamide fibre and aramid fibre gum dipping liquid and production process thereof |
| CN103309471A (en) * | 2012-03-09 | 2013-09-18 | 卡西欧计算机株式会社 | Input pen |
| CN108589305A (en) * | 2018-01-08 | 2018-09-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN113840957A (en) * | 2019-03-01 | 2021-12-24 | 大陆轮胎德国有限公司 | Aqueous impregnating composition |
| CN115287902A (en) * | 2022-07-26 | 2022-11-04 | 湖南鑫振邦新材料有限公司 | Semi-hard thread rope and fabric, elastic product and surface treatment agent thereof |
| CN117757248A (en) * | 2023-12-08 | 2024-03-26 | 杭州普天乐电缆有限公司 | Wear-resistant impact-resistant material for coaxial cable and preparation process thereof |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602006000118D1 (en) * | 2005-06-03 | 2007-10-31 | Hankook Tire Co Ltd | Rubber composition for spikelet tire treads |
| KR100582003B1 (en) * | 2005-06-03 | 2006-05-22 | 한국타이어 주식회사 | Rubber composition for tread of studless tire |
| FR2924133B1 (en) * | 2007-11-26 | 2012-12-14 | Porcher Ind | LONGITUDINAL REINFORCING ELEMENT BASED ON MINERAL OR ORGANIC FIBERS AND METHOD OF OBTAINING THE SAME |
| CN101935948A (en) * | 2010-08-03 | 2011-01-05 | 河南斯维科技有限公司 | Water-borne dispersion of cohesiveness promoter for polyester tire cords and preparation method thereof |
| EP2423186B1 (en) * | 2010-08-30 | 2017-05-31 | LANXESS Deutschland GmbH | New adhesion promoter bsed on carbodiimides, adhesive, aqueous resorcinol-formaldehyde-latex dispersions, fibers with improved adhesion, process for their preparation and use thereof. |
| EP2423247A1 (en) * | 2010-08-30 | 2012-02-29 | Rhein Chemie Rheinau GmbH | New aqueous resorcinol-formaldehyde-latex dispersions, process for their production and their use |
| EP2423185B1 (en) * | 2010-08-30 | 2017-03-01 | Rhein Chemie Rheinau GmbH | New aqueous resorcinol-formaldehyde-latex dispersions, fibers with improved adhesion, process for their preparation and use thereof. |
| EP3085831B1 (en) * | 2013-12-18 | 2020-11-04 | Teijin Limited | Reinforcement fiber cord and method for manufacturing same |
| DE102016210467A1 (en) | 2016-06-14 | 2017-12-14 | Continental Reifen Deutschland Gmbh | Process for producing a reinforcement layer, reinforcement layer and vehicle tires |
| DE102016210468A1 (en) | 2016-06-14 | 2017-12-14 | Continental Reifen Deutschland Gmbh | Process for producing a reinforcement layer, reinforcement layer and vehicle tires |
| DE102017212455A1 (en) | 2017-07-20 | 2019-01-24 | Continental Reifen Deutschland Gmbh | A method of making a vehicle tire and vehicle tires made by the method and use of treated strength members |
| DE102017222894A1 (en) | 2017-12-15 | 2019-06-19 | Continental Reifen Deutschland Gmbh | Process for producing a reinforcing agent for reinforcing rubber products, reinforcements and use of the reinforcing material |
| PT3597686T (en) * | 2018-07-19 | 2020-11-20 | Ems Patent Ag | Submersible bath compositions for treating reinforcement inserts |
| EP3670582B1 (en) * | 2018-12-21 | 2024-03-20 | Indorama Ventures Luxembourg Holding S.A. | Method of manufacturing a reinforcement material |
| EP3702523A1 (en) | 2019-03-01 | 2020-09-02 | Continental Reifen Deutschland GmbH | Aqueous dipping composition |
| EP3702521A1 (en) | 2019-03-01 | 2020-09-02 | Continental Reifen Deutschland GmbH | Aqueous dipping composition |
| EP3702524A1 (en) | 2019-03-01 | 2020-09-02 | Continental Reifen Deutschland GmbH | Aqueous dipping composition |
| CN112832030A (en) * | 2020-12-29 | 2021-05-25 | 北京化工大学 | Environment-friendly gum dipping solution, preparation method and application |
| CN114277573A (en) * | 2021-12-31 | 2022-04-05 | 青岛天邦线业有限公司 | Adhesive and fiber treated by same, textile fabric product, composite material and product |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB816640A (en) * | 1957-03-07 | 1959-07-15 | Ici Ltd | Improvements in or relating to the bonding of polyethylene terephthalate fibres to rubber |
| US3872937A (en) * | 1972-12-18 | 1975-03-25 | Gen Tire & Rubber Co | Composite of polyamide bonded to rubber |
| JPS5137174A (en) | 1974-09-24 | 1976-03-29 | Mitsuboshi Belting Ltd | Horiesuteruseni no setsuchakushorihoho |
| JPS5562269A (en) * | 1978-11-06 | 1980-05-10 | Teijin Ltd | Treatment of rubber reinforcing polyester fiber material |
| DE3043426A1 (en) * | 1980-11-18 | 1982-07-08 | Bayer Ag, 5090 Leverkusen | METHOD FOR IMPREGNATING TEXTILE CORDS |
| JPS57187238A (en) * | 1981-05-15 | 1982-11-17 | Toray Ind Inc | Preparation of polyester fiber material for reinforcing rubber |
| JPS6024131B2 (en) * | 1981-09-16 | 1985-06-11 | 三ツ星ベルト株式会社 | Method of adhering fibers and hydrogenated nitrile rubber compounds |
| US5352755A (en) * | 1984-02-29 | 1994-10-04 | The Baxenden Chemical Co. | Blocked isocyanates |
| US4978409A (en) * | 1988-07-06 | 1990-12-18 | Bando Chemical Industries, Ltd. | Method of bonding fibers to hydrogenated nitrile rubber |
| GB9520317D0 (en) * | 1995-10-05 | 1995-12-06 | Baxenden Chem Ltd | Water dispersable blocked isocyanates |
| JPH09132870A (en) * | 1995-10-31 | 1997-05-20 | Teijin Ltd | Method for treating aromatic polyamide fiber |
| JPH11279949A (en) * | 1998-03-27 | 1999-10-12 | Mitsuboshi Belting Ltd | Treatment of aramide fiber cord and transmission belt using the treated cord |
| JP4556202B2 (en) * | 1998-06-17 | 2010-10-06 | 東洋紡績株式会社 | Method for producing polyester fiber material having improved adhesion to rubber |
| US6329053B2 (en) * | 1999-07-28 | 2001-12-11 | Kolon Industries, Inc. | Polyester multifilamentary yarn for tire cords, dipped cord and production thereof |
-
2004
- 2004-09-04 JP JP2006525726A patent/JP2007505228A/en active Pending
- 2004-09-04 CN CNB2004800261260A patent/CN100523057C/en not_active Expired - Fee Related
- 2004-09-04 RU RU2006112004/04A patent/RU2346015C2/en not_active IP Right Cessation
- 2004-09-04 WO PCT/EP2004/009877 patent/WO2005026239A1/en active Application Filing
- 2004-09-04 US US10/571,671 patent/US20060280942A1/en not_active Abandoned
- 2004-09-04 EP EP04764828A patent/EP1664161A1/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103309471A (en) * | 2012-03-09 | 2013-09-18 | 卡西欧计算机株式会社 | Input pen |
| CN102619094A (en) * | 2012-03-14 | 2012-08-01 | 浙江海之门橡塑有限公司 | Dip solution and application thereof in aramid fibers |
| CN102634985A (en) * | 2012-03-17 | 2012-08-15 | 马鞍山科英合成材料有限公司 | Closed isocyanate adhesive for gumming fiber framework materials of rubber products, composition of closed isocyanate adhesive, preparation method and application |
| CN102634986A (en) * | 2012-04-20 | 2012-08-15 | 北京化工大学 | Method for pretreating fibers |
| CN102634986B (en) * | 2012-04-20 | 2013-08-21 | 北京化工大学 | Method for pretreating fibers |
| CN102912636A (en) * | 2012-11-01 | 2013-02-06 | 台州宏元工艺有限公司 | Polyamide fibre and aramid fibre gum dipping liquid and production process thereof |
| CN108589305A (en) * | 2018-01-08 | 2018-09-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN113840957A (en) * | 2019-03-01 | 2021-12-24 | 大陆轮胎德国有限公司 | Aqueous impregnating composition |
| CN115287902A (en) * | 2022-07-26 | 2022-11-04 | 湖南鑫振邦新材料有限公司 | Semi-hard thread rope and fabric, elastic product and surface treatment agent thereof |
| CN115287902B (en) * | 2022-07-26 | 2024-10-11 | 湖南鑫振邦新材料有限公司 | Semi-hard cotton rope, fabric and elastic product thereof and surface treating agent |
| CN117757248A (en) * | 2023-12-08 | 2024-03-26 | 杭州普天乐电缆有限公司 | Wear-resistant impact-resistant material for coaxial cable and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1664161A1 (en) | 2006-06-07 |
| US20060280942A1 (en) | 2006-12-14 |
| RU2346015C2 (en) | 2009-02-10 |
| RU2006112004A (en) | 2006-08-27 |
| WO2005026239A1 (en) | 2005-03-24 |
| CN100523057C (en) | 2009-08-05 |
| JP2007505228A (en) | 2007-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1849362A (en) | Two-step method for dipping synthetic fiber | |
| EP2719824B1 (en) | Reinforcement cord for reinforcing rubber product, and rubber product using same | |
| EP1757726A1 (en) | Reinforcement polyester cords for rubbers and process for production thereof | |
| KR100422027B1 (en) | Process for producing an adhesive-treated polyester fiber cord | |
| EP3643832A1 (en) | Cord for rubber reinforcement and rubber product obtained using same | |
| EP1854917A1 (en) | Reinforcing polyester cord for rubbers and process for production thereof | |
| JP4565537B2 (en) | Method for producing polyester fiber cord for rubber reinforcement | |
| JP6174387B2 (en) | Reinforcing fiber cord and manufacturing method thereof | |
| CN107438680B (en) | Cord comprising multifilament para-aramid yarn containing non-round filaments | |
| EP3617397B1 (en) | Rubber-reinforcing cord and rubber product using same | |
| EP2952625B1 (en) | Carbon fiber cord for reinforcing rubber product and rubber product using same | |
| EP3085831B1 (en) | Reinforcement fiber cord and method for manufacturing same | |
| EP3754103A1 (en) | Cord for rubber reinforcement and rubber product using same | |
| JP2006214043A (en) | Rubber-reinforcing carbon yarn | |
| WO2007072703A1 (en) | Ply cord for polyester tire cap and process for producing the same | |
| JP2010047868A (en) | Cord for reinforcing rubber | |
| JP2011236534A (en) | Manufacturing method of carbon fiber for rubber reinforcement | |
| JP3762583B2 (en) | Polyester fiber cord manufacturing method | |
| JP3762581B2 (en) | Polyester fiber cord manufacturing method | |
| JP6397310B2 (en) | Carbon fiber cord for rubber reinforcement and method for producing the same | |
| JP4229822B2 (en) | Method for producing aramid fiber cord for belt reinforcement | |
| KR20070022187A (en) | Two-step method for dipping synthetic fiber | |
| JP2011241513A (en) | Manufacturing method of rubber reinforcing fiber | |
| JPH08108492A (en) | Highly rigid aromatic polyamide cord for reinforcing rubber and pneumatic tire using the cord | |
| JPH09207509A (en) | Pneumatic radial tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20130904 |