JP2007031508A - Adhesive composition for air permeation preventing layer of pneumatic tire and pneumatic tire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To facilitate the manufacturing operations of the air permeation preventing layer of a pneumatic tire. <P>SOLUTION: An adhesive composition is provided, which is used for adhering the air permeation preventing layer with the tire rubber layer of the pneumatic tire that uses, as the air permeation preventing layer, a thermoplastic elastomer composition that makes a thermoplastic resin its continuous phase and an elastomer component its dispersed phase. The adhesive composition for the air permeation preventing layer contains a polymer, a tackifier and, as a colorant, a white, gray or chromatic dye or pigment of an amount that gives a light transmittance of 10-60% when a 0.1 mm thick layer is formed. Its manufacturing method and the pneumatic tire using it are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive composition for an air permeation preventive layer of a pneumatic tire and a pneumatic tire using the same, and more specifically, to prevent air permeation of the pneumatic tire by coloring the adhesive composition. The present invention relates to an adhesive composition capable of facilitating quality judgment when producing a laminate of a layer and an adhesive layer, and a pneumatic tire using the same.

  For example, Patent Document 1 describes a technique in which a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and rubber as a dispersed phase is used for an air permeation preventive layer of a tire. When such a thermoplastic elastomer composition is used in a pneumatic tire, for example, it is adhered to a rubber layer (for example, carcass) using an adhesive composition in which a tackifying resin is blended with a styrene thermoplastic elastomer composition. Yes. For example, such an adhesive composition can be extruded simultaneously with a thermoplastic elastomer using a single or twin screw extruder and extruded into a cylindrical shape to form a seamless inner liner member. it can.

  However, since the adhesive composition is transparent, when the surface of the thermoplastic elastomer composition layer is thinly covered during cylindrical extrusion, it is difficult to know how thick it is, and the purge resin Therefore, there is a problem that it cannot be determined whether or not the purge resin has been replaced. In addition, since this adhesive layer is thin, it is difficult to confirm the presence of the adhesive layer after vulcanization of the pneumatic tire, and there are problems in terms of failure analysis and quality control.

Japanese Patent No. 3217239

  Therefore, the present invention eliminates the above-mentioned problems when producing a pneumatic tire by extruding the air permeation preventive layer of the pneumatic tire at the same time as the adhesive composition. It aims at facilitating quality control at the time of manufacture of the agent layer.

  According to the present invention, an air permeation preventive layer and a tire rubber layer of a pneumatic tire using a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase as an air permeation preventive layer are bonded to each other. In the adhesive composition, the adhesive composition has a light transmittance of 10 to 60% (JIS) as a colorant with a polymer and a tackifier as a colorant of 0.1 mm. A pressure-sensitive adhesive composition for a tire air permeation preventive layer containing a white or gray or chromatic dye or pigment in an amount to be measured according to the light transmittance measurement method of K7361-1 and pneumatic using the same Tires are provided.

  According to the present invention, an air permeation preventive layer and a tire rubber layer of a pneumatic tire using a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase as an air permeation preventive layer are bonded to each other. In preparing the adhesive layer, the light transmittance is 10 to 60% (JIS K7361) when the layer is 0.1 mm thick as a colorant together with the polymer for the adhesive and the tackifier. The amount of white, gray, or chromatic dye or pigment that is measured in accordance with the light transmittance measurement method of No. 1 is blended to facilitate quality determination of the adhesive layer during the production of pneumatic tires. A method is provided.

  According to the present invention, in a pneumatic tire using a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase as an air permeation preventive layer, the viscosity for adhering the air permeation preventive layer and the tire rubber layer. In the adhesive composition, white, gray, or chromatic dye or pigment is added as a colorant, and when this composition is formed into a layer having a thickness of 0.1 mm, the light transmittance is 10 to 60%. Thus, the above problem can be solved.

  The present inventors, for example, in an adhesive composition containing a styrenic thermoplastic elastomer, by blending a white or gray or chromatic pigment or dye, particularly a metal compound pigment, the thickness at the time of molding. The present inventors have found that an adhesive composition that can easily manage and analyze the above can be obtained.

  That is, in the present invention, by coloring the adhesive, it can be distinguished from the purge resin at the time of cylindrical extrusion, so that the substitution can be confirmed, and the thickness variation at the extrusion site can be judged by the color variation. The height can be adjusted. By making the coloring other than black, the tire rubber can be easily distinguished and quality control and analysis can be facilitated. In particular, when a metal compound pigment is blended, when the adhesive part is analyzed after being molded and vulcanized into the tire, the presence and thickness of the adhesive are determined not only by an optical technique using a microscope but also by atomic mapping such as EPMA. This is advantageous because it enables accurate analysis.

  Examples of the colorant used in the present invention include zinc oxide, titanium oxide, barium sulfate, iron oxide, nickel titanium yellow, chromium titanium yellow, cobalt yellow, cyanine blue, cobalt aluminate, Pigments and natural dyes such as ultramarine blue (lapis lazuli, azurite, ultramarine), cobalt stannate (cerulean blue), chromium oxide, and cobalt phosphate (carotenoids such as gardenia, paprika and anato), chalcone systems such as safflower, akane and cochineal , Anthraquinones such as lac, anthocyanins such as perilla, red cabbage, purple potato, grapes, flavones such as cacao, cocoon and cucumber, and indigo such as indigo) and their synthetic products or synthetic dyes (congo red, aniline) Black Renburu, Orange II, etc.) can be mentioned dyes such as these can be used alone or in any mixtures. Commercially available colorants, dyes and pigments can be used.

  The adhesive composition produced by the method of the present invention is a thermoplastic resin (for example, polyamide, polyester, polynitrile, etc.) as described in, for example, JP-A-8-217923 and JP-A-11-199713. Poly (meth) acrylate, polyvinyl, cellulose, fluorine, imide resin, etc.) as a continuous phase, and elastomer (diene rubber, olefin rubber, halogen-containing rubber, silicon rubber, sulfur-containing rubber, fluorine rubber, thermoplastic elastomer) A rubber layer to which the air permeation preventive layer is adhered when the layer of the thermoplastic elastomer composition which is preferably dynamically vulcanized and used as a dispersed phase is used as an air permeation preventive layer (inner liner) of a pneumatic tire, for example. (For example, it can be used for bonding with a carcass layer or a tie rubber layer). In the present invention, there is provided a composition produced by continuously kneading a pigment or dye and other compounding ingredients together with a polymer component for an adhesive and a tackifier, for example, using a single screw or twin screw extruder. To do.

  When the pigment or the like is a solid material such as a powder that does not melt at a temperature below the extrusion kneading temperature, if necessary, together with other compounding agents, a melting point below the extrusion kneading temperature, more specifically, Is premixed in a premixing polymer having a melting point at a temperature not higher than 30 ° C. higher than the melting point of the polymer component for the adhesive, and this is mixed with the rest of the compounding agent, the tackifier and the adhesive A desired adhesive composition can be produced by continuous kneading with a polymer for an adhesive, for example, with a single-screw or twin-screw extruder.

  As the polymer for the adhesive used in the present invention, any conventionally used polymer can be used, and specifically, SBS, SIS, SEBS, SIBS, EVA, EEA, EMA, and the like can be given. .

  The polymer to be premixed with the compounding agent is not particularly limited as long as it is a polymer that melts at the extrusion kneading temperature and is compatible with the adhesive adhesive polymer. For example, polyolefin such as polyethylene, ethylene-vinyl acetate copolymer Styrenic thermoplastic elastomers (for example, SBS, SIS, SEBS, SIBS) can be used and may be the same as or different from the polymer component for the adhesive.

  There are no particular limitations on the tackifier used in the adhesive composition of the present invention, and general tackifiers can be used. Specific examples include terpene resins, modified terpene resins, pinene resins, and terpenes. Examples thereof include phenol resin, rosin resin, C5 petroleum resin, C9 petroleum resin, DCPD petroleum resin, styrene resin, coumarone resin, alkylphenol resin and the like. These blending amounts are not particularly limited, and are about 10 to 200 parts by weight per 100 parts by weight of the polymer component for the adhesive.

When the adhesive composition of the present invention is used for a pneumatic tire, the adhesive composition may be used as a laminate coextruded with the thermoplastic elastomer composition, or the adhesive composition. You may use what apply | coated the composition to the said thermoplastic elastomer composition layer.
The thermoplastic elastomer composition used for the air permeation preventive layer has a thermoplastic resin as a continuous phase and a rubber composition as a dispersed phase. Examples of the thermoplastic resin include polyamide resins (for example, nylon 6 (N6 ), Nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66) , Nylon 6/66/610 copolymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer ), Polyester resins (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET , Aromatic polyesters such as polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimidic acid / polybutylate terephthalate copolymer ), Polynitrile resin (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer), poly Methacrylate resin (for example, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resin (for example, vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer ( VOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulosic resins (eg cellulose acetate, cellulose acetate butyrate), fluorine Resins (eg, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE)), imide resins (eg, aromatic polyimide (PI)) On the other hand, the elastomer component includes natural rubber, synthetic polyisoprene rubber (IR), epoxidized natural rubber, styrene-butadiene rubber (SBR), polybutadiene rubber (BR), nitrile-butadiene rubber (NBR), Hydrogenated NBR, Hydrogenated S Diene rubber such as BR and its hydroxy compound; ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer Olefin-based rubber such as coalescence, acrylic rubber (ACM), ionomer; bromide of Br-IIR, CI-IIR, isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CO, ECO, GCO, GECO), halogen-containing rubbers such as chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified chlorinated polyethylene (M-CM); methyl vinyl silicone rubber, dimethyl silicone rubber, methyl Phenyl vinyl silicone rubber Fluorine rubbers such as sulfur rubbers such as polysulfide rubber, vinylidene fluoride rubbers, fluorine-containing vinyl ether rubbers, tetrafluoroethylene-propylene rubbers, fluorine-containing silicon rubbers, and fluorine-containing phosphazene rubbers And thermoplastic elastomers such as styrene elastomers, olefin elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and the like.

  The method for producing the thermoplastic elastomer composition is obtained by adding a thermoplastic resin and an elastomer component to a biaxial kneader or the like, melt-kneading, and dispersing the rubber component in the thermoplastic resin forming a continuous phase. Can do. When a rubber component is vulcanized, dynamic vulcanization is performed by adding a vulcanizing agent under kneading or by previously blending a vulcanizing agent with an elastomer component.

  In addition to the above-mentioned essential components, the adhesive composition and rubber composition according to the present invention include other reinforcing agents (fillers) such as carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking acceleration. Additives, various oils, anti-aging agents, plasticizers, and other additives that are generally compounded for tires and other general rubbers can be blended. It can be vulcanized into a composition and used to vulcanize or crosslink. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

Examples 1-3 and Comparative Examples 1-2
Sample preparation Each component of the formulation shown in Table I was put into a single screw extruder, the adhesive composition mixed at a set temperature of 110 ° C was extruded into a strand with a diameter of about 3 mm, and formed into a pellet with a strand cutter did. The obtained adhesive composition was sampled 10 times every 10 minutes, and the amount of metal contained in each was measured. The results are shown in Table II.

  As is clear from the results in Table II, Comparative Example 1 was a case where no pigment was added to the adhesive, and was transparent and the color shade could not be distinguished. Example 1 was a case where zinc oxide was added, and the color became milky white, indicating variations in thickness. In Example 2, when titanium dioxide was added, the color became milky white and the thickness variation was clearly recognized. In Example 3, when ultramarine was added, the color became blue and the thickness variation was clearly recognized. In Comparative Example 2, when titanium dioxide was added excessively, light was not transmitted at all, and the thickness could not be determined.

  According to the present invention, a white, gray, or chromatic dye or pigment is blended as a colorant in the adhesive composition used when producing an air permeation preventive layer of a pneumatic tire from a thermoplastic elastomer composition. By co-extrusion, the thickness variation of the adhesive can be easily judged visually, and it is easy to judge when replacing the purge agent, so quality control in the manufacturing process of pneumatic tires is easy And contribute to the production of excellent products.

Claims (8)

  An adhesive composition for adhering an air permeation preventive layer and a tire rubber layer of a pneumatic tire using a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase as an air permeation preventive layer In the above, the adhesive composition is white or gray in an amount such that the light transmittance becomes 10 to 60% when the layer is 0.1 mm thick as a colorant together with the polymer and the tackifier. A pressure-sensitive adhesive composition for a tire air permeation preventive layer, comprising a chromatic dye or pigment.   The adhesive composition according to claim 1, wherein the colorant is a metal compound pigment.   The colorant is zinc oxide, titanium oxide, barium sulfate, iron oxide, nickel titanium yellow, chromium titanium yellow, cobalt yellow, cyanine blue, cobalt aluminate, ultramarine blue (lapis lazuli, azurite, ultramarine), cobalt stannate (cerulean blue) ), At least one pigment selected from chromium oxide and cobalt phosphate. The adhesive composition according to claim 1 or 2.   The thermoplastic resin is at least one thermoplastic resin selected from the group consisting of polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluorine resin, and imide resin. Item 4. The adhesive composition according to any one of items 1 to 3.   The elastomer component is at least one rubber selected from the group consisting of diene rubber and hydrogenated products thereof, olefin rubber, halogen-containing rubber, silicon rubber, sulfur-containing rubber, fluorine rubber and thermoplastic elastomer. 5. The adhesive composition according to any one of 4 above.   A pneumatic tire, wherein an air permeation preventive layer made of a thermoplastic elastomer composition and a tire rubber layer are bonded using the adhesive composition according to any one of claims 1 to 5.   A pneumatic tire using a laminate obtained by co-extrusion of the adhesive composition according to any one of claims 1 to 5 and a thermoplastic elastomer composition as an air permeation preventive layer.   An adhesive layer for adhering an air permeation preventive layer and a tire rubber layer of a pneumatic tire using a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase as an air permeation preventive layer. In preparation, a white or gray color or a chromatic color with a light transmittance of 10 to 60% when a 0.1 mm thick layer is used as a colorant together with a polymer for an adhesive and a tackifier. A method for facilitating quality judgment at the time of manufacturing a laminate of an adhesive layer for an air permeation preventive layer of a pneumatic tire by blending a dye or pigment.