WO1997013818A1 - Pneumatique et composition adhesive - Google Patents
Pneumatique et composition adhesive Download PDFInfo
- Publication number
- WO1997013818A1 WO1997013818A1 PCT/JP1996/002969 JP9602969W WO9713818A1 WO 1997013818 A1 WO1997013818 A1 WO 1997013818A1 JP 9602969 W JP9602969 W JP 9602969W WO 9713818 A1 WO9713818 A1 WO 9713818A1
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- WIPO (PCT)
- Prior art keywords
- weight
- adhesive
- monomer mixture
- rubber latex
- novolak
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
- C09J109/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Definitions
- the present invention relates to an adhesive composition, and more particularly to an adhesive composition capable of favorably bonding a polyester material or the like to rubber.
- the present invention also relates to a pneumatic tire, and more particularly to a pneumatic tire using a polyester cord as a reinforcing material.
- Polyester material which is a linear polymer having an ester bond in the main chain, represented by polyethylene terephthalate, has high initial elastic modulus and excellent dimensional stability under heat among general-purpose polymer materials. In addition, it is extremely useful as a reinforcing material for rubber articles such as tires, belts, air springs, and rubber hoses in the form of filaments, cords, cables, cord fabrics, canvas, etc.
- a polyester material is used as a reinforcing material for these rubber articles, since the polyester material is dense in molecular structure and has few functional groups, it is necessary to combine the rubber with a material such as nylon or rayon.
- Resorcinol-formaldehyde condensate obtained by resolving reaction to obtain good adhesion and vinylpyridine-styrene-butane
- a composition comprising a rubber latex containing an ene terpolymer hardly provides any adhesion.
- a polyester cord surface was treated with aluminum chloride to add active groups such as 1 OH, 1 COOH, and 1 NH 2 to the surface, or by an isocyanate compound or an epoxy compound.
- active groups such as 1 OH, 1 COOH, and 1 NH 2
- Numerous methods have been proposed for introducing a compound having a hydrogen-bonding ability or a primary-bondable functional group onto the surface of a polyester cord, followed by treatment with an adhesive solution, and an adhesive composition.
- the alkali * amine treatment degrades the strength of the polyester cord.
- isocyanate compounds and epoxy compounds have high reactivity, and react with water as a solvent of the adhesive solution and resorcinol-formaldehyde condensate in the adhesive solution, so that it is extremely difficult to prepare a one-part adhesive solution.
- the adhesion is impaired. For this reason, the bonding process must be performed in two stages, which requires extra equipment and processes, which is not preferable from the viewpoint of resource saving and energy saving.
- treatment with an isocyanate compound or an epoxy compound is also preferable from the viewpoint of environmental conservation, such as scattering of these compounds into the air during bonding, fumes generated during ripening, and the harmfulness of steam to the human body. Absent.
- polyester cords treated with isocyanate compounds and epoxy compounds are hardened and difficult to handle in production.
- the most serious drawback is that these polyester cords are used at high temperatures and under high strain. In such a case, rapid deterioration of adhesion and deterioration of cord strength may occur, which significantly shortens the product life of rubber products using these as a scavenger.
- the reason is that the isocyanate compound and the epoxy compound form a kind of graft polymer on the surface of the polyester due to the primary bond on the polyester surface.
- the adhesive is easily broken by aminolysis due to the vulcanizing agent residue, and it is weak against mechanical input due to the large difference in rigidity between the polyester inside and the surface under high strain.
- Tyres, etc. which are becoming lighter in weight from the viewpoint of energy saving, need to have greater stability against thermal and mechanical inputs and longer fracture life than ever before. It is not preferable to use an isocyanate compound or an epoxy compound.
- polyester adhesives there have been proposed a number of methods and adhesive compositions in which a resin that imparts adhesion and tackiness to the above-mentioned adhesive liquid is added as an adhesion promoter, which can be bonded in a liquid form. Therefore, it is excellent in energy and cost, and the decrease in cord strength due to the bonding process is small.
- a resin that imparts adhesion and tackiness to the above-mentioned adhesive liquid is added as an adhesion promoter, which can be bonded in a liquid form. Therefore, it is excellent in energy and cost, and the decrease in cord strength due to the bonding process is small.
- the tackifying resin to be added here water, which has good workability and environmental friendliness, is used as the main solvent, so many phenolic resins that are easily soluble in water have been proposed. I have.
- the adhesive strength is improved, but when the rubber latex specified in the present invention is not used in the adhesive liquid, the adhesive performance is improved.
- the thermal input during the vulcanization process which is the process of bonding with rubber, causes adhesive deterioration.
- the properties required for an adhesive composition suitable for a polyester material for rubber reinforcement are one-pack form, good storage stability, toxicity, no environmental pollution, and adhesion treatment. That the cord strength does not decrease due to aging, that it has high adhesiveness, and that it can maintain a sufficiently high adhesive strength even in the vulcanization process and the high temperature applied during use. And so on.
- An object of the present invention is to provide a novel adhesive composition satisfying all of the above properties.
- Another object of the present invention is to provide a polyester cord which has been subjected to an adhesive treatment with each of the above-mentioned adhesive compositions as a reinforcing material, and can be used under high speed and high load, that is, under high temperature and high strain.
- An object of the present invention is to provide a pneumatic tire that does not cause a decrease in adhesion and strength. In order to achieve the above object, the present invention has the following configuration.
- the adhesive composition of the present invention comprises a pyridine ring-containing vinyl compound in an amount of 3 to 25% by weight, preferably 5 to 15% by weight, unsubstituted styrene or unsubstituted styrene and aliphatic vinyl.
- a monomer mixture comprising a compound 25 to 80% by weight, preferably 35 to 70% by weight, and a conjugated diene compound 5 to 60% by weight, preferably 15 to 60% by weight (a )
- the weight ratio of the copolymer component (a ′) obtained by the polymerization of the monomer mixture (a) to the copolymer component (b ′) obtained by the polymerization of the monomer mixture (b) is 10%. / 90-80 / 20. Preferably, the ratio is 50 to 50-80, and the monomer mixture (b) is more conjugated than the monomer mixture (a).
- thermosetting resin containing a resole-type condensate obtained by resolving resorcinol and formaldehyde and a novolak-type condensate obtained by reacting resorcinol and formaldehyde to novolak is 1 solid. It is characterized by comprising 4 to 205 parts by weight, preferably 38 to 115 parts by weight.
- split polymerization means “multi-stage feed polymerization”.
- the resol-type condensate is obtained by resolving resorcinol or resorcinol-formaldehyde resin oligomer with formaldehyde in the presence of a basic catalyst, and resolving the rubber latex.
- Solid content of 100 weight 4 to 35 parts by weight, preferably 8 to 15 parts by weight, based on solids is mixed with the novolak-type condensate, formaldehyde in resorcinol, and novolak under a neutral or acidic catalyst.
- the rubber latex is blended with 100 to 170 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the solid content of the rubber latex.
- a copolymer obtained by polymerization from a styrene-butadiene copolymer and a monomer mixture satisfying the composition range of the monomer mixture (b) in the solid content of the rubber latex is 8%. It is preferred that the content be 0% by weight or less.
- the resol type condensate is preferably obtained by a resolving reaction under mixing with the rubber latex, and is a component of a so-called RFL solution.
- the novolak-type condensate is preferably added as an adhesion promoter to a composition comprising the rubber latex and the resol-type condensate.
- the novolak-type condensate has an area ratio of at least 40%, preferably at least 40%, obtained by a component in which 2 to 4 resorcinol nuclei are linked by analysis by gel permeation chromatography (GPC). It is preferably at least 50%.
- the pneumatic tire of the present invention is characterized in that a polyester cord that has been subjected to an adhesive treatment with each of the adhesive compositions is used as a reinforcing material.
- FIG. 1 is an example of a GPC chart of the novolak-type condensate of the present invention.
- the present inventors have conducted various studies on the adhesive deterioration between the reinforcing material and its coating rubber composition (hereinafter referred to as “adhered rubber”) due to thermal stimulation, and found that the vulcanization reaction of the adhesive composition, particularly the rubber latex, Involvement was found to be large.
- the form of the rubber scavenger is not particularly limited, and may be any of a cord, a film, a short fiber, and a non-woven fabric.
- the cord is used as an example of the form of the reinforcing material. The invention will be described in detail.
- the vulcanizing agent and vulcanization accelerator that diffuse from the rubber compound during the vulcanization process.
- the latex in the product vulcanizes, and the resulting hardening of the adhesive layer creates stress concentrations between the cord and the adhesive layer, deteriorating the bond.
- the adhesive composition has a vulcanization inhibiting effect in advance.
- a method of imparting heat resistance by adding a substance, for example, an acid (Japanese Patent Application Laid-Open No. 6-287865), butadiene monomer at the reaction point of the bridge to suppress the vulcanization of the latex itself It has been found that the method of destroying the composition (see Japanese Patent Application Laid-Open No. 3-163181) is effective.
- an adhesive composition containing a novolak-type condensate as an adhesion promoter was obtained.
- Properties required of adhesive compositions for polyester cords for rubber reinforcement, etc., that is, one-part form, good storage stability, toxicity, no environmental pollution, strong cord by adhesive treatment Characteristics such as no reduction in heat resistance, high adhesiveness, and sufficient adhesive strength to be maintained even during the vulcanization process and high temperatures applied during use, that is, sufficient heat resistance. I found that I could add everything.
- This adhesive composition is particularly suitable for bonding between a polyester cord and a rubber to be adhered.
- the reason is that the novolak-type condensate used as an adhesion promoter is a relatively low-molecular low-nucleate compound composed mainly of a linear resin and having 2 to 4 aromatic nuclei in one molecule.
- the dissolution and diffusion properties of the molecules are improved, and it is easy to hot melt the polyester cord by heat treatment in the adhesive treatment process, and has a low molecular weight (low nuclei number) ) Wetting the surface easily, and further mixing well with impurities adhering to the surface, such as various oils used for polyester yarn, and facilitating diffusion, strengthening the adhesion and improving the adhesion to rubber.
- the novolak-type condensate dissolves and diffuses to reinforce the adhesive and also the surrounding rubber, so that if the rubber cracks, ft cracks will spread to the adhesive layer.
- the novolak-type condensate also acts as an adhesive Z tackifier resin (tack firer) in the adhesive layer, giving the cohesive strength and adhesiveness of the adhesive layer, and increasing the adhesive strength. This is to increase.
- thermosetting resins particularly resorcinol-formaldehyde resins, added to Vp-St-Bd-based split copolymer rubber latex, and found that novolak-type molecules having a linear structure were obtained.
- a low nucleate resin having a molecular weight distribution of 2 to 4 nuclei as a main component is effective as a sunset fire ear.
- the general ratio of the adhesive Z tackifying resin to the rubber component is the edge ratio, and in the case of a resin having good compatibility with rubber, it is generally 66 to 150 for rubber 100 (see above). "Pressure-sensitive adhesives", page 138) is preferred.
- thermosetting resin composed of the novolak-type condensate based on 100 parts by weight of a rubber latex solid content, a resol type condensate And the solid content of the thermosetting resin composed of the novolak-type condensate is 14 to
- the adhesive composition consists only of a novolak-type condensate and a rubber latex
- contamination due to sticking to the processing machine occurs, resulting in uneven adhesion.
- the adhesive strength decreases, which is not preferable.
- an adhesive composition comprising a resol-type condensate and a rubber latex (R FL) and a novolak-type condensate, it is possible to avoid the occurrence of a gum-up unique to rubber latex.
- R FL rubber latex
- a resole-type condensate is required.
- novolak-type condensate As the raw material for the resol-type condensate, mix rubber latex, aluminum terephthalate and formalin, and react under a base (see “Emulsion Handbook” p.77) 7, Taiseisha). At this time, the novolak-type condensate is further increased in molecular weight and formed into a three-dimensional network to be a resolation reaction product.
- the amount of the resol-type condensate to be added to the rubber latex is usually 7 to 10 parts by weight of the rubber latex, for example, 100 parts by weight of the solid content of the Vp-St-Bd copolymer rubber latex.
- the reason that the novolak-type condensate is added to the RFL solution is that if the addition is performed during the formation reaction of the resol-type condensate, the novolak-type condensate becomes a polymer S and a three-dimensional network. This is because the effect as an adhesion promoter becomes smaller.
- the addition can be performed before or after the reaction for producing the resol-type condensate is almost completed.
- the pH temporarily drops due to the formation of the methylol group in the reaction intermediate-the methylol group is consumed as the condensation reaction proceeds, the pH rises again, and the reaction is terminated.
- the pH becomes substantially constant. Therefore, in the present invention, the addition was performed using the pH change as an index.
- the amount of the resin in the adhesive composition can be increased in order to strengthen the bonding to textiles, but the compatibility of the adhesive composition with the rubber to be adhered at the interface between the adhesive layer and the rubber to be adhered is preferable. And adhesion decreases.
- the resol-type condensate is a three-dimensional network and is a polymer, but the novolak-type condensate used in the present invention is a linear low-molecular-weight compound and has higher diffusibility and compatibility of molecular chains.
- thermosetting resin in an amount of not less than 35 parts by weight to 100 parts by weight of rubber latex, which is an unprecedented high mixing ratio.
- composition ratio of the copolymer component (a ′) and the copolymer component (b ′) constituting the split copolymer particles in the rubber latex is different is as follows.
- the conjugated diene compound component that gives a double bond in the particles mainly causes a cross-linking reaction by the cross-linking agent that migrates and diffuses from the compounded rubber during the vulcanization process and at other times when used at high temperatures, resulting in a cross-linking reaction.
- the following operation is shown.
- the ridges cause changes in the body ridge and modulus of the adhesive layer before and after crosslinking, and the greater the change, the less the durability of the adhesive force. Since the crosslinking reaction proceeds particularly at high temperatures, adhesive deterioration at high temperatures increases. So from this point, It is preferable that the conjugated diene compound component is small.
- the conventional V-St-Bd copolymer rubber latex having a single composition structure is widely used having a butadiene content of about 70% by weight.
- Rubber latex particles consisting of only the copolymer component ( a ') having a low conjugated gen compound content are less affected by changes in volume and modulus due to cross-linking, and can be expected to have the effect of improving the durability of adhesive strength.
- Compatibility with the applied rubber makes it difficult to mix between the molecular chains of the copolymer in the particles and the applied rubber molecular chains.Since the content of the conjugated gen compound is small, crosslinking is reduced and the adhesive layer is -The interfacial bonding strength between the applied rubbers is low, resulting in a low level of adhesion, especially when the conjugated gen compound content is less than 40% by weight, There is the disadvantage that the solubilization becomes extremely small, there is almost no interfacial bonding force, and the adhesive breaks easily between the adhesive and the applied rubber.
- the present inventor has proposed a copolymer component having a conventional conjugated diene compound content (about 70% by weight) in the same particle in order to improve the adhesive strength and prevent the adhesive strength from being lowered at high temperatures.
- b ′ and a copolymer component (a ′) having a low conjugated-gen content.
- the particles obtained by dividing and polymerizing the monomer mixture (a) having a low conjugated gen compound content and the monomer mixture (b) having a conjugated gen compound content at the conventional level are obtained in the early stage of vulcanization. Since the copolymer particles (b ') in the rubber latex particles are co-vulcanized by the entanglement of the copolymer particles and the rubber polymer molecular chains, the same adhesive-rubber interface bonding force as in the past can be obtained. At the same time, the entire rubber latex particle contains a conjugated compound!
- examples of the pyridine ring-containing vinyl compound include 2-vinylpyridin, 3-butylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like. More than one species can be used. Preferably, it is 2-vinylpyridine.
- the unsubstituted styrenes include styrene, a-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, and 4-t-butylstyrene. And hydroxymethylstyrene, and one or more of them can be used.
- it is styrene.
- aliphatic vinyl compound examples include ethylenically unsaturated acid monomers such as acrylic acid and methacrylic acid, ethylenically unsaturated acid anhydride monomers such as maleic anhydride, and ethylenically unsaturated acids such as methyl methacrylate.
- acid monomers such as acrylic acid and methacrylic acid
- ethylenically unsaturated acid anhydride monomers such as maleic anhydride
- ethylenically unsaturated acids such as methyl methacrylate.
- ester monomers examples include ester monomers, ethylene, acrylonitrile, aliphatic vinyl compound monomers such as vinyl chloride, and the like, and one or more kinds can be used.
- conjugated diene compound examples include aliphatic conjugated diene compound-based monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene, and one or more kinds can be used.
- it is 1,3-butadiene.
- the adhesive composition In the monomer mixture (a) of the Vp-St-Bd-based split copolymer rubber latex according to the present invention, if the content of the vinyl compound containing a pyridine ring is less than 3% by weight, the adhesive composition On the other hand, the adhesive strength of the whole product is lowered, which is not preferable. On the contrary, if it exceeds 25% by weight, the vulcanization reaction of latex is accelerated, which is not preferable.
- the content of the unsubstituted / substituted styrene or the unsubstituted / substituted styrene and the aliphatic vinyl compound is less than 25% by weight, the strength of the rubber latex particles is reduced, and the strength of the adhesive layer is reduced.
- the rubber latex particles will be too hard, the flexibility will be reduced, and the adhesive strength will be drastically reduced when the product is used under high strain.
- the content of the conjugated diene compound is less than 5% by weight, the crosslinking force is reduced and the adhesive strength is reduced.
- the content is more than 60% by weight, the crosslinking is increased and the heat resistance is lowered, which is not preferable. .
- the adhesive force of the entire adhesive S decreases as described above, and exceeds 25% by weight.
- the adhesive becomes brittle, which is not preferable.
- the content of the unsubstituted / substituted styrene or the unsubstituted / substituted styrene and the aliphatic vinyl compound is less than 5% by weight, the strength of the rubber latex particles and the adhesive layer is reduced, and the adhesive strength is reduced. Conversely, if it exceeds 45% by weight, the co-vulcanizability of the adhesive layer and the rubber to be applied is reduced, and the adhesive strength is also lowered, which is not preferable.
- the content of the conjugated gen compound is less than 40% by weight, the crosslinking is too small and the adhesive strength is reduced. Conversely, if the content is more than 83% by weight, the adhesive strength is unfavorably reduced. .
- the weight ratio of the copolymer component (a ′) to the copolymer component (b ′) is 190-80 / 20, a monomer mixture having three or more compositions is divided. It can be polymerized.
- the weight ratio between the copolymer component (a ′) and the copolymer component (b ′) is specified to be 10/90 to 80/20, but the copolymer (a ′) If the weight ratio is too small, the effect of improving the heat-resistant adhesive strength is small compared to the conventional Vp—St—Bd copolymer rubber latex, and conversely, the copolymer (a ') increases. If it is too long, the initial adhesive strength will decrease.
- the composition of the manufactured rubber latex particles is measured by NMR (nuclear magnetic resonance) method, and the polymerization composition ratio is determined from the peak area of the chart.Ai, the viscoelastic behavior of the polymer is measured, and the It can be determined by a method for determining the polymerization composition ratio.
- the solid content of the Vp—St—Bd-based split copolymer according to the present invention is required to be 20% by weight or more based on the solid content of the rubber latex. This is because the effect of using this latex cannot be obtained.
- the latex in the present invention is prepared by a known split polymerization method.
- the split polymerization method include a two-stage polymerization method and a power feed polymerization method, and there is no particular limitation on the method of adding the monomer.
- the method include a batch addition method, a split addition method, and a continuous addition method.
- a method which can obtain a latex containing the copolymer (a ′) and the copolymer (b ′) in one particle as in the invention can be used.
- the monomer mixture (a) or (b) is added thereto. Further, an electrolyte such as sodium phosphate and peroxides are added as an initiator to carry out polymerization. Thereafter, after reaching a predetermined conversion, the other monomer mixture (b) or (a) is added, and the polymerization is continued. Thereafter, after reaching a predetermined conversion, a load transfer agent is added to stop the polymerization, and the remaining monomer is removed, thereby obtaining a rubber latex having a structure composed of polymers having different composition ratios.
- an emulsifier such as potassium rosinate in water
- an electrolyte such as sodium phosphate and peroxides
- novolak-type condensate As the novolak-type condensate, a commercially available product (for example, manufactured by Indospec Co., Ltd .: trade name Penacolite R50, manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikanol 700 (s)) and a synthetic product obtained by the following method, etc. be able to.
- a commercially available product for example, manufactured by Indospec Co., Ltd .: trade name Penacolite R50, manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikanol 700 (s)
- a synthetic product obtained by the following method, etc. be able to.
- resorcinol was dissolved in water, formaldehyde was added, and heat treatment was performed at a constant temperature in a temperature range of 100 to 110 ° C. for a fixed time in a range of 6 to 8 hours. Reactant.
- condensates may be used alone or in combination of two or more, and may be a novolak-type condensate of a phenol derivative other than resorcinol with formaldehyde.
- the obtained reaction product is extracted in a solvent such as toluene or xylene to extract a compound having a low molecular weight such as a resorcinol monomer or a dinuclear resorcinol-formaldehyde condensate.
- Novola with different molecular weight distribution A check-type condensate was prepared.
- the molecular weight distribution of these novolak-type condensates can be measured by the area ratio based on GPC.
- thermosetting resin has a solid content of less than 14 parts by weight with respect to the copolymer rubber latex solid content of 100 parts by weight according to the present invention
- the amount exceeds 205 parts by weight the adhesive force between the adhesive composition and the rubber to be adhered decreases, which is not preferable.
- the amount is less than 38 parts by weight or more than 115 parts by weight the blending amount of the novolak-type condensate or the resol-type condensate of the thermosetting resin component is not in a preferable range, which is not preferable.
- the amount is 38 to 115 parts by weight, the balance between the rubber latex and the both condensates is achieved, and the effect of the present invention is remarkable.
- thermosetting resin is in the range of 14 to 205 parts by weight with respect to 100 parts by weight of the rubber latex, if necessary, the resorcinol-formaldehyde condensate may be used.
- Other thermosetting resin components or resorcinol-formaldehyde resin containing a third component may be added.
- the content of the aliphatic vinyl compound is preferably 15% by weight or less. Is reduced, and the effect of the present invention is reduced. When the content of the aliphatic vinyl compound is 5% by weight or less, the effect of the present invention can be more clearly obtained.
- the monomer mixture (b) has a higher content of the conjugated diene compound than the monomer mixture (a), because the adhesion is inferior.
- the rubber latex component may contain a component other than the split copolymer according to the present invention in an amount of 80% by weight or less.
- the content should be 70%.
- the content is not more than% by weight, the effect of the present invention is more apparent and preferable.
- the adhesive composition is applied to the cord.
- the adhesive is strong, and the processing machine is soiled, and the adhesive strength tends to decrease due to the deterioration of the adhesive application condition.
- it exceeds 35 parts by weight the adhered rubber and adhesive The adhesion of the layers tends to decrease, which is not preferable.
- the adhesiveness of the adhesive applied to the polyester cord or the like is optimal, and the adhesive such as a jig or a machine adheres to the cord or the cord after a long time elapses. Adhesion can be suppressed, and the surface condition of the adhesive is good, and high adhesive strength can be obtained.
- the content of the novolak-type condensate is less than 10 parts by weight of the solid content relative to 100 parts by weight of the solid content of the rubber latex, the adhesion promoting effect on the adhesive force is slight, and conversely If the amount exceeds 170 parts by weight, the adhesion between the adhesive composition and the rubber to be adhered is unpreferably reduced. In particular, when the content is 30 parts by weight or more and 100 parts by weight or less, the effect of promoting adhesion is remarkable, which is preferable.
- the resol-type condensate is preferably obtained while mixing with the rubber latex during the resolving reaction, but this reduces the adhesiveness of the adhesive composition and suppresses the generation of scale and gum in the adhesion treatment step. That's why.
- the method of reacting a resorcinol-formaldehyde condensate obtained by resolving with mixing with rubber latex is as follows: a resorcinol-formaldehyde condensate raw material (resorcinol, a resorcinol having a relatively low molecular weight) in an alkaline solution. (Formaldehyde, formalin condensate) and latex. Resorcinol-formaldehyde is not mixed with latex at the beginning of the reaction.
- the novolak-type condensate is added to the RFL solution as an adhesion promoter, but as described above, this prevents the novolak-type condensate from having a high molecular weight and functions as an adhesion promoter. It is to maintain.
- the resin was analyzed by GPC to obtain an area ratio of 40% or more, and preferably 50% or more, obtained by a component having 2 to 4 resorcinol nuclei linked together. Indicates that the adhesive strength is good.Also, by GPC analysis, it is preferable that the beak area ratio of the monomer is 25% or less for maintaining the adhesive strength including heat resistance. I understood.
- the method of attaching the adhesive composition to the cord includes a method of dipping the cord in the adhesive composition, a method of applying the adhesive composition with a brush, and a method of spraying the adhesive composition.
- An appropriate method can be selected according to the conditions.
- the heat treatment subsequent to the drying is performed at a temperature equal to or higher than the glass transition temperature of the polymer of the cord, preferably, equal to or higher than the melting temperature of the polymer, and equal to or lower than the melting temperature of the polymer. It is preferable to apply at the temperature.
- the reason for this is that if the polymer has a low glass transition temperature, the molecular mobility of the polymer is poor, and the adhesive / tackifying resin in the adhesive composition and the polymer cannot sufficiently interact with each other. At a temperature exceeding the polymer's [melting temperature-20 ° C], the rubber latex in the fiber material or adhesive composition tends to deteriorate. is there.
- the adhesive composition of the present invention is preferably a polyester material.
- Polyester is a polymer having an ester bond in the main chain. More specifically, at least 80% of the repeating units in the main chain are ester bonding.
- polyesters include an esterification reaction of glycols such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyethylene glycol, and pentaerythritol, and dicarboxylic acids such as terephthalic acid, isophthalic acid, and dimethyl form thereof. Alternatively, it is obtained by condensation by a transesterification reaction.
- glycols such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyethylene glycol, and pentaerythritol
- dicarboxylic acids such as terephthalic acid, isophthalic acid, and dimethyl form thereof.
- it is obtained by condensation by a transesterification reaction.
- polyester polyethylene terephthalate
- Such polyester material may be in any form such as cord, cable, filament, filament chip, cord fabric, canvas and the like. Also, the material may be pre-processed by electron beam, microwave, corona discharge, plasma treatment or the like.
- the adhesive composition of the present invention may further comprise, in addition to the above polyester fibers, aliphatic polyamide fibers such as rayon, vinylon, 6-nylon, 6,6-nylon, 4,6-nylon, It can be used for all materials typified by aromatic polyamide fiber represented by Lentelephthalamide, carbon fiber and glass fiber.
- the epoxy compound or the isocyanate compound is used in the polymerization and spinning process of fibers typified by polyester fiber, aromatic polyamide fiber, carbon fiber, etc., or post-processed, or electron beam, microwave, plasma treatment
- the adhesive composition of the present invention can also be applied to a fiber material which has been preliminarily processed as described above.
- the form of these fiber materials is also cord, cable, filament, and fiber. Any of illuminated chips, cord fabric, canvas, etc. may be used.
- the adhesive composition of the present invention can be applied to all rubber products such as tires, conveyor belts, belts, hoses, air springs, and the like.
- the solid content in the examples was measured in accordance with the method for measuring the non-volatile content of the adhesive in the method for measuring JIS K6833 “Other adhesives”.
- the monomer mixture (a) having the composition shown in Tables 5 to 9 and Table 11 and 0.2 part by weight of t-dodecylmercaptan as a chain transfer agent are charged and emulsified. Thereafter, the temperature is raised to 50 ° C., and 0.5 parts by weight of potassium persulfate is added to initiate polymerization. After the reaction rate of the monomer mixture (a) reached 80 to 90%, the monomer mixture (b) shown in Tables 5 to 9 and Table 11 was added to t-dodecyl mercaptan 0 Add 2 parts by weight and continue the polymerization. After the conversion reaches 95%, 0.1 part by weight of hydroquinone is added to stop the polymerization. Next, unreacted monomers were removed under reduced pressure to obtain a copolymer rubber latex.
- the monomer mixture (b) having the composition shown in Table 6 and 0.2 part by weight of t-decyl mercaptan are charged and emulsified. Then, after heating to 50 ° C, potassium persulfate 0.5 S Add parts and start polymerization. After the conversion of the monomer mixture (b) reached 80 to 90%, the monomer mixture (a) having the composition shown in Table 6 was added to 0.2 part by weight of t-decyl mercaptan. And further continue the polymerization. After the conversion reaches 95%, 0.1 part by weight of hydroquinone * is added to stop the polymerization. Next, unreacted monomers were removed under reduced pressure to obtain a copolymer rubber latex.
- a monomer mixture having the composition shown in Tables 5 and 7 and 0.5 part by weight of t-dodecylmercaptan are charged and emulsified. Thereafter, the temperature was raised to 50 ° C., and 0.5 part by weight of potassium persulfate was added to initiate polymerization. After the conversion reaches 90%, 0.1 part by weight of hydroquinone is added to stop the polymerization. Next, unreacted monomers were removed to obtain a copolymer latex.
- Styrene-butadiene copolymer rubber latex (trade name: JSR210, solid content concentration: 40%) of Nippon Synthetic Rubber Co., Ltd. was used.
- SBR latex was mixed with the composition shown in Table 10.
- Vp—St—Bd-based split copolymer rubber latex of Example 1 prepared in (i) and the Vp—St—Bd copolymer rubber latex of Comparative Example 1 prepared in (Hi) were table
- the composition shown in FIG. 10 was mixed.
- Vp—St—Bd copolymer rubber latex used in Examples 43 and Comparative Example 34 was prepared using an autoclave equipped with a stirrer having a capacity of 5 liters and purged with nitrogen. Charge 130 parts by weight of deionized water, 7.0 parts by weight of polyoxyethylene lauryl ether, and 0.05 part by weight of sodium ethylenediaminetetraacetate. To this, a monomer mixture of each composition and t-dodecyl mercaptan were added as described below to carry out polymerization, the concentration was adjusted, and a rubber latex having a solid concentration of 40% was obtained.
- the monomer mixture (a) having the composition shown in Table 11 and 0.1 part by weight of t-dodecylmercaptan are charged and emulsified. Then, after the temperature was raised to 5 (TC), 0.5 parts by weight of potassium persulfate was added to initiate polymerization. After the reaction rate of the monomer mixture (a) reached 80 to 90%, Then, 0.15 parts by weight of a monomer mixture (b) having the composition shown in Table 11 and 0.1% by weight of t-decyl mercaptan are added, and the polymerization is further continued. Then, the polymerization was stopped by adding 0.1 part by weight of the copolymer, and the unreacted monomers were removed under reduced pressure to obtain a copolymer rubber latex.
- Table 11 Monomer mixture of the composition shown in Table 1 and t-dodecyl mercaptan 0.35 weight Charge and emulsify. Thereafter, the temperature is raised to 50 ° C., and 0.5 parts by weight of potassium persulfate is added to initiate polymerization. After the conversion reaches 95%, 0.1 part by weight of hydroquinone is added to stop the polymerization. Next, unreacted monomers were removed under reduced pressure to obtain a copolymer rubber latex.
- a resol type condensate raw material mixture having the composition shown in Table 1 was prepared, and allowed to stand at 25 ° C for 8 hours.
- the rubber latex obtained in (1) above was mixed with each part by weight, and the mixture was mixed at 25 ° C. After aging for 16 hours, an RFL solution was obtained.
- the novolak-type condensate is a commercially available product (Penacolite R50, trade name, manufactured by Indospek Co., Ltd., Sumikanol 700,000 (s), trade name, manufactured by Sumitomo Chemical Co., Ltd.) and a synthetic product obtained by the following method (Examples 3 to 7). Was used.
- the novolak-type condensate obtained by the above condensation reaction in order to prepare the novolak-type condensates of Examples 4, 5, and 6 having different molecular weight distributions, the monomer and low molecular components were extracted with toluene.
- the novolak-type condensate obtained by the above condensation reaction was concentrated (azeotropic distillation) as described below. Extracted at a temperature of 106.
- Example 4 of Table 5 when toluene is distilled off by distillation, a novolak-type condensate shown in Example 4 of Table 5 can be obtained.
- Example 6 in Table 5 having less low molecular weight components can be obtained by repeating the above extraction operation twice more and then distilling off toluene by distillation.
- Example 7 having a composition in which the high molecular weight component (5 or more nuclei) was reduced from the novolak type condensate of Example 6, the solubility of the novolak type condensate component having a higher molecular weight in water was poorer. As described above, it can be obtained by utilizing precipitation with low-temperature water.
- Example 6 the novolak-type condensate of Example 6 was heated to 95 ° C., diluted with 100 parts by weight of water at 95 ° C., cooled to 5 ° C., and left standing for one day to precipitate. The material is allowed to settle, and the supernatant is decanted.
- the solid content concentration was measured by the above-described method, and water was added as necessary to adjust the solid content concentration to 50%. The addition was carried out at a temperature of 95 ° C and cooled to room temperature.
- the pH of the novolak resorcinol-formaldehyde condensate (solid content: 50%) of the varieties shown in Table 1 is adjusted to the composition shown in Table 2 with caustic soda solution to obtain an adhesion promoter solution. This solution is added to the RFL solution obtained in (2) with the composition shown in Table 1 to prepare an adhesive composition.
- resorcinol was used as a caustic soda solution with the composition shown in Table 3, and this aqueous solution was added to the RFL solution obtained in (2) with the composition shown in Table 1 to make contact.
- An adhesive composition is prepared.
- a novolak-type condensate having a solid content of 50% was converted into a caustic soda solution having the composition shown in Table 2, and this aqueous solution was added to 350 parts by weight of the rubber latex obtained in (1) and adhered by adding 350 parts by weight.
- An agent composition is prepared.
- the composition was immersed, then dried at 150 ° C. for 1.5 minutes, and then treated under an atmosphere kept at 240 ° C. for 2 minutes.
- the cord was excavated from the vulcanizate obtained in (6-1), and the resistance when the cord was separated from the vulcanizate at a speed of 30 cmZ was measured. .
- the results are shown in Tables 5 to 11.
- the adhesive composition treatment code obtained in (5) is embedded in an unvulcanized rubber composition having the composition shown in Table 4, and vulcanized under a pressure of 20 kgZcm 2 at 190 ° C. for 30 minutes.
- a polyethylene terephthalate tire cord having a twist structure of 1,500 d2, a number of upper twists of 40 cm, and a number of lower twists of 40 times / 10 cm was produced. This cord was immersed in each adhesive composition, dried at 150 at 1.5 minutes, and heat-treated at 240 ° C. for 2 minutes to perform an adhesive treatment.
- ISC-R50 is an abbreviation for Indospec, Penacolite R50
- Rubber latex solid content is shown in 1 ⁇ 5 ⁇ .
- each of the examples is superior in the initial adhesive strength, the heat-resistant adhesive strength, and the tire (high-speed) durability as compared with the specific compression examples.
- Comparative Example 5 is an example in which there is no resol-type condensate as compared with Example 1.
- Example 7 is an example in which five or more nuclei of a novolak-type condensate were reduced.
- Example 8 is an example in which the composition is the same as that of Example 1, but the order of introduction of the monomer mixture is reversed when preparing the rubber latex.
- Comparative Example 6 is an example in which novolak-type condensate was not blended with respect to Example 8.
- Example 9 is an example different from Example 1 in the method of preparing the resol-type condensate.
- Comparative Example 7 is an example in which novolak-type condensate is not blended with Example 9.
- Comparative Example 8 is a novolak-type condensate (IS)
- Example 10 is an example in which a novolak-type condensate was added to Comparative Example 8.
- Examples 11 and 12 and Comparative Examples 5 and 9 are based on 100 parts by weight of rubber latex solids. Thus, it is an example that it is appropriate to set the compounding range of the resol type condensate to 4 to 35 parts by weight.
- Comparative Example 10 is an example in which the total amount of resorcinol-formaldehyde resin was 84 parts by weight, the same amount as in Example 1. It can be seen that novolak-type condensates are required to obtain high adhesive strength even if the total amount is the same.
- the compounding amount of the novolak-type condensate was 10 to 170 parts by weight based on 100 parts by weight of the solid content of rubber latex. This is an example that shows this.
- the novolak-type condensate has a component in which 2 to 4 resorcinol nuclei are linked, and the area ratio by GPC analysis is 40% or more, preferably 50% or more. This is an example that is necessary to obtain high adhesive strength, including heat resistance. Furthermore, the analysis by GFC also shows that the peak area ratio due to the monomer component is 25% or less, and the component where the resorcinol nucleus is linked to 5 or more nuclei is 50% or less.
- the weight S ratio of the copolymer obtained from the monomer mixture (a) and the copolymer obtained from the monomer mixture (b) was 10 to 9%. It is an example that the value of 0 to 800 is necessary to obtain an effect with the same or higher initial adhesive force and to suppress a decrease in the heat-resistant adhesive force.
- Comparative Examples 12 to 16 and 18 are examples using rubber latex particles obtained by polymerizing a monomer mixture having a single composition.
- Comparative Example 12 had a polymer composition ratio equal to the composition of the copolymer (b ′) of Examples 16 to 19, and Comparative Example 18 had a polymer composition ratio of Examples 16 to 19.
- Comparative Example 13 has a polymer composition ratio equal to the composition of the whole particles of Example 16 and Comparative Example 13 has a polymer composition ratio equal to that of the copolymer (a ') of Example 19; The ratio is equal to the total particle composition of Example 19.
- Comparative examples 14 and 16 are the same as those of comparative example 12 and copolymer component (a ') whose polymer composition ratio is equal to the composition of copolymer component (b') of Examples 16 to 19 etc. Comparative Example 14 having a composition ratio equal to that of Example 16 was mixed.
- the copolymer component (a ′) is equal to the weight ratio of the Z copolymer component (b ′), and Comparative Example 16 has a mixing ratio of the copolymer component (a ′) / copolymer of Example 19 It is equal to the ratio of the components (b ').
- Examples 20 to 28 and Comparative Examples 19 to 22 show that the monomer mixture of the monomer mixture (a) has a lower butadiene content than that of the single S-isomer mixture (b), In this example, the content is 3 to 25% by weight, 25 to 80% by weight of styrene, and 5 to 60% by weight of butadiene.
- Examples 29 to 34 and Comparative Examples 23 to 26 show that the monomer mixture (b) has a butadiene content higher than that of the monomer mixture (a), In this example, the content is 5 to 25% by weight, styrene 5 to 45% by weight, and butadiene 40 to 83%.
- Examples 2, 35 to 39, and Comparative Examples 27 to 30 show that the effects can be obtained if the Vp—St_Bd-based split copolymer rubber latex of the present invention is contained in an amount of 20% by weight or more. This is an example.
- Comparative Examples 27 to 29 show styrene butadiene copolymer rubber latex
- Examples 38 and 39 show polymerization obtained from a monomer mixture satisfying the composition range of simple noble mixture (b).
- ⁇ Examples 40 to 43 are examples of Vp-St-Bd copolymer rubber latex obtained by split polymerization. This is an example in which a part of the styrene monomer of the unit mixture (a) and the monomer mixture (b) is replaced with another copolymerizable monomer unit (aliphatic vinyl compound). It can be seen that substitution is possible if the amount does not impair the gist of the present invention.
- the specific examples 31 to 34 are vinylpyridine-styrene butadiene copolymer particles obtained by subjecting the monomer mixture (a) and the monomer mixture (b) to division polymerization. This is an example in which it can be seen that is necessary.
- the adhesive deterioration due to the vulcanization reaction is suppressed, so that the decrease in the adhesive force at high temperatures such as during the vulcanization step or during product use is suppressed.
- the effect can be obtained.
- the effect of the novolak-type condensate used in the adhesive composition of the present invention as an adhesive and tackifying resin can improve the adhesive strength between the reinforcing material and the rubber.
- the adhesive composition of the present invention is a one-part form for adhering rubber and its reinforcing material, has good storage stability, has no toxicity, has no environmental pollution, and has a reduced fiber strength due to the adhesion treatment. And high adhesiveness, and can maintain a sufficiently high adhesive force even at a high temperature applied during a working process and during use, that is, an effect such as having sufficient heat resistance can be obtained.
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- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/849,668 US5863987A (en) | 1995-10-13 | 1996-10-14 | Adhesive compositions and pneumatic tire |
DE69621221T DE69621221T2 (de) | 1995-10-13 | 1996-10-14 | Klebstoffzusammensetzung und luftreifen |
EP96933637A EP0798356B1 (en) | 1995-10-13 | 1996-10-14 | Adhesive composition and pneumatic tire |
JP51492397A JP3791695B2 (ja) | 1995-10-13 | 1996-10-14 | 接着剤組成物 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7/265559 | 1995-10-13 | ||
JP26555995 | 1995-10-13 | ||
JP7/331786 | 1995-12-20 | ||
JP33178695 | 1995-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997013818A1 true WO1997013818A1 (fr) | 1997-04-17 |
Family
ID=26547038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/002969 WO1997013818A1 (fr) | 1995-10-13 | 1996-10-14 | Pneumatique et composition adhesive |
Country Status (6)
Country | Link |
---|---|
US (1) | US5863987A (ja) |
EP (1) | EP0798356B1 (ja) |
JP (1) | JP3791695B2 (ja) |
DE (1) | DE69621221T2 (ja) |
ES (1) | ES2175134T3 (ja) |
WO (1) | WO1997013818A1 (ja) |
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JP2005075920A (ja) * | 2003-08-29 | 2005-03-24 | Nippon A & L Kk | ゴムと繊維の接着剤用共重合体ラテックス |
JP2005075921A (ja) * | 2003-08-29 | 2005-03-24 | Nippon A & L Kk | ゴムと繊維の接着剤用共重合体ラテックス |
JP2005263887A (ja) * | 2004-03-17 | 2005-09-29 | Bridgestone Corp | 接着剤組成物及びその製造方法、並びに樹脂材料、ゴム部材及びタイヤ |
WO2011102003A1 (ja) * | 2010-02-19 | 2011-08-25 | 日本エイアンドエル株式会社 | 接着剤用共重合体ラテックス |
WO2011125224A1 (ja) * | 2010-04-09 | 2011-10-13 | 日本エイアンドエル株式会社 | 接着剤用共重合体ラテックス |
WO2012133745A1 (ja) | 2011-03-31 | 2012-10-04 | 株式会社ブリヂストン | タイヤ |
WO2013118785A1 (ja) | 2012-02-06 | 2013-08-15 | 株式会社ブリヂストン | 空気入りラジアルタイヤ |
JP2016069526A (ja) * | 2014-09-30 | 2016-05-09 | 東レ株式会社 | 繊維・ゴム用接着剤および繊維・ゴム用接着剤の製造方法 |
WO2021002182A1 (ja) * | 2019-07-02 | 2021-01-07 | 日本エイアンドエル株式会社 | 接着剤用共重合体ラテックスおよび接着剤組成物 |
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WO2021220989A1 (ja) | 2020-04-30 | 2021-11-04 | 株式会社ブリヂストン | 有機繊維コード用接着剤組成物、有機繊維コード‐ゴム複合体及びタイヤ |
WO2021221075A1 (ja) | 2020-04-30 | 2021-11-04 | 株式会社ブリヂストン | 有機繊維コード用接着剤組成物、ゴム-有機繊維コード複合体及びタイヤ |
WO2022137703A1 (ja) | 2020-12-23 | 2022-06-30 | 株式会社ブリヂストン | 有機繊維用接着剤組成物、有機繊維-ゴム複合体及びタイヤ |
WO2022137861A1 (ja) | 2020-12-23 | 2022-06-30 | 株式会社ブリヂストン | 接着剤組成物、並びに、これを用いた樹脂材料、ゴム物品、有機繊維-ゴム複合体およびタイヤ |
WO2023090030A1 (ja) | 2021-11-17 | 2023-05-25 | 株式会社ブリヂストン | 接着剤組成物、有機繊維、有機繊維-ゴム複合体材料、ゴム物品及びタイヤ |
WO2023090008A1 (ja) | 2021-11-17 | 2023-05-25 | 株式会社ブリヂストン | 接着剤組成物、有機繊維材料、ゴム物品、有機繊維-ゴム複合体及びタイヤ |
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EP1690702B1 (en) * | 1998-12-28 | 2012-05-30 | Bridgestone Corporation | Adhesive composition, resin material, rubber article and pneumatic tire |
US6312824B1 (en) * | 1999-08-27 | 2001-11-06 | E. I. Du Pont De Nemours And Company | Copolyester elastomer compositions and fusion bonded articles |
US6358605B1 (en) * | 2000-02-10 | 2002-03-19 | Brady Worldwide, Inc. | Label for use on rubber products |
US20050158531A1 (en) * | 2002-02-27 | 2005-07-21 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing glass fiber treatment agent, rubber-reinforcing cord using the fiber treatment agent, and rubber product |
WO2004058909A1 (fr) * | 2002-12-27 | 2004-07-15 | Conception Et Developpement Michelin S.A. | Composition adhesive pour le collage direct d'un composite polyester ou vinylester pregelifie a du caoutchouc cru |
RU2321608C1 (ru) * | 2004-03-30 | 2008-04-10 | Ниппон Шит Гласс Компани, Лимитед | Композиция для покрытия корда, корд для армирования резины, изготовленный с покрытием из указанной композиции, и изделие из резины, изготовленное с применением указанного корда |
CA2643774C (en) * | 2006-03-31 | 2011-08-23 | Central Glass Company, Limited | Coating liquid for coating glass fiber and rubber-reinforcing glass fiber using the same |
US20090044893A1 (en) | 2007-08-14 | 2009-02-19 | Ralf Mruk | Pneumatic Tire |
US20090139630A1 (en) * | 2007-11-30 | 2009-06-04 | Ralf Mruk | Pneumatic tire |
TWI512068B (zh) * | 2010-04-19 | 2015-12-11 | Nippon A & L Inc | 接著劑用共聚物乳膠 |
US10626546B2 (en) | 2012-06-24 | 2020-04-21 | Gates Corporation | Carbon cord for reinforced rubber products and the products |
RU201047U1 (ru) * | 2020-02-25 | 2020-11-24 | Вадим Эдуардович Карташян | Полиэфирная кордная ткань (20 пду) |
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- 1996-10-14 JP JP51492397A patent/JP3791695B2/ja not_active Expired - Fee Related
- 1996-10-14 US US08/849,668 patent/US5863987A/en not_active Expired - Lifetime
- 1996-10-14 EP EP96933637A patent/EP0798356B1/en not_active Expired - Lifetime
- 1996-10-14 ES ES96933637T patent/ES2175134T3/es not_active Expired - Lifetime
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WO2023090030A1 (ja) | 2021-11-17 | 2023-05-25 | 株式会社ブリヂストン | 接着剤組成物、有機繊維、有機繊維-ゴム複合体材料、ゴム物品及びタイヤ |
WO2023090008A1 (ja) | 2021-11-17 | 2023-05-25 | 株式会社ブリヂストン | 接着剤組成物、有機繊維材料、ゴム物品、有機繊維-ゴム複合体及びタイヤ |
Also Published As
Publication number | Publication date |
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EP0798356B1 (en) | 2002-05-15 |
EP0798356A1 (en) | 1997-10-01 |
DE69621221D1 (de) | 2002-06-20 |
EP0798356A4 (en) | 1998-08-26 |
US5863987A (en) | 1999-01-26 |
JP3791695B2 (ja) | 2006-06-28 |
DE69621221T2 (de) | 2003-02-06 |
ES2175134T3 (es) | 2002-11-16 |
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