JP2007031515A - Manufacturing method of adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an adhesive composition containing a solid compounding agent. <P>SOLUTION: In manufacturing the adhesive composition for adhering a layer of a thermoplastic elastomer composition that makes a thermoplastic resin its continuous phase and an elastomer ingredient its dispersed phase with a layer of a rubber composition, the manufacturing method comprises pre-blending a compounding agent that contains a solid compounding agent that does not melt at a temperature not lower than the extrusion/kneading temperature in a polymer having a melting point not higher than the kneading temperature of the adhesive composition and then continuously kneading the pre-blended masterbatch together with a polymer ingredient for the adhesive composition, a tackifier and the remaining compounding agent with an extruder. The adhesive composition obtained by the above method and the pneumatic tire using it are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an adhesive composition containing a solid compounding agent, and more specifically, a thermoplastic elastomer composition layer and a rubber composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase. It is related with the manufacturing method of the adhesive composition which mix | blended the layer of this, which mix | blended the tackifier, the adhesive composition obtained by the method, 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 an elastomer component as a dispersed phase is used for an air permeation prevention layer of a tire. When such a thermoplastic elastomer composition is used for a pneumatic tire, for example, an adhesive composition obtained by blending a styrenic thermoplastic elastomer with a tackifier resin is adhered to a rubber layer (for example, carcass). Such an adhesive composition is produced by continuously mixing, for example, a styrenic thermoplastic elastomer with a tackifying resin and various compounding agents using a single-screw or twin-screw extruder. However, since the melt viscosity of styrene-based thermoplastic elastomers is low, for example, when a small amount of a solid (powder) compounding agent such as zinc oxide or titanium oxide that does not melt at the extrusion kneading temperature is mixed, the dispersion becomes very poor. There was a problem. In addition, if the amount of this powdery compounding agent is small, there is a problem that the supply amount varies due to the accuracy of the feeder to the extruder, and the powdery compounding agent adheres near the feed part of the extruder. There was a problem to do.

Japanese Patent No. 3217239

  Therefore, the present invention uniformly disperses an adhesive composition containing a solid compounding agent such as powder that does not melt at a temperature below the extrusion kneading temperature in the adhesive composition from which the solid compounding agent is obtained. It aims at providing the manufacturing method of the adhesive composition which can be made.

  According to the present invention, in producing an adhesive composition for adhering a thermoplastic elastomer composition layer and a rubber composition layer having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase, A pre-mixed compound containing a solid compound that does not melt at a temperature below the kneading temperature is pre-mixed with a polymer having a melting point below the extrusion kneading temperature of the adhesive composition, and then the pre-mixed master batch is adhesively bonded. Method for producing adhesive composition by continuous mixing with polymer component for adhesive composition, tackifier and remaining compounding agent in an extruder, and adhesive composition obtained thereby and A used pneumatic tire is provided.

  According to the present invention, it is blended into the adhesive composition, in particular, a solid compounding agent that does not melt at a temperature equal to or lower than the extrusion kneading temperature, and if necessary, other compounding agents are preliminarily added to the extrusion kneading temperature or lower. In a polymer having a melting point of, for example, by premixing using a closed mixer, the compounding agent can be uniformly dispersed in the polymer by making a master batch, so that the compounding agent, particularly a small amount of powdery compounding agent As in the conventional example in which the mixture is mixed directly with an adhesive composition for low viscosity tires and directly mixed into an extruder, the dispersion of the compounding agent increases or the powdered compounding agent is extruded. There is no problem of adhering to the charging port of the machine and preventing it from entering as measured, and the masterbatch makes it possible to obtain a tacky adhesive composition in which the compounding agent is uniformly dispersed by suppressing variation.

  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 components (diene rubber, olefin rubber, halogen-containing rubber, silicon rubber, sulfur-containing rubber, fluorine rubber, thermoplastic elastomer) In the case of using a layer of the thermoplastic elastomer composition, which is preferably dynamically vulcanized to form a dispersed phase, for example, as an air permeation preventive layer (inner liner) of a pneumatic tire, the air permeation preventive layer is used as a rubber layer ( For example, it can be used for bonding with a carcass layer or a tie rubber layer. In the present invention, a solid compounding agent and other compounding agents that do not melt at the extrusion kneading temperature are continuously kneaded together with a polymer component for an adhesive and a tackifier, for example, using a single screw or twin screw extruder. A method of manufacturing is provided.

  According to the present invention, a solid compounding agent such as a powder that does not melt at a temperature lower than the extrusion kneading temperature is mixed with other compounding agents in advance, if necessary, a melting point lower than the extrusion kneading temperature, more specifically a viscosity. Premixed in a premixing polymer having a melting point at a temperature not higher than 30 ° C. by a temperature not higher than the melting point of the polymer component for the adhesive, and this is the remaining compounding agent, tackifier, and adhesive A desired adhesive composition can be produced by continuously kneading together with the polymer for use, for example, with a monoaxial or biaxial extruder.

  The adhesive polymer used in the present invention can be any polymer conventionally used, and specific examples include SBS, SIS, SEBS, EVA, EEA and the like.

  The polymer for premixing the compounding agent is not particularly limited as long as it melts at a temperature not higher than the extrusion kneading temperature. For example, polyolefin such as polyethylene, ethylene-vinyl acetate copolymer, styrenic thermoplastic elastomer (for example, SBS, SIS, SEBS), ethylene-acrylate copolymer, ethylene-ethyl acrylate copolymer, and modified products thereof may be used, and may be the same as or different from the polymer component for the adhesive.

  Examples of solid compounding agents that can be blended in the adhesive composition of the present invention and can be blended in advance with the premixing polymer include zinc oxide, titanium oxide, magnesium oxide, carbon black, silica, and carbonic acid. Calcium, clay, ultramarine, sulfur and zinc stearate can be mentioned. If necessary, a compounding agent that melts at a temperature lower than the extrusion kneading temperature may be preliminarily mixed with the premixing polymer. Although there is no limitation in the compounding quantity, it is about 0.1-30 weight part per 100 weight part of polymer components for adhesives.

  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, and pinene resins. Terpene phenol resin, rosin resin, C5 petroleum resin, C9 petroleum resin, styrene resin, DCPD petroleum 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.

  In addition to the essential components described above, the adhesive composition according to the present invention includes a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, various oils, an anti-aging agent, a plasticizer and other tires, and other general Various additives generally blended for rubber can be blended, and such additives can be blended into the composition by a general method, and the blending amount of these additives is the object of the present invention. As long as it is not contrary, it can be made the conventional general amount.

  When the adhesive composition of the present invention is used in a pneumatic tire, the adhesive composition may be used as a laminate obtained by co-extrusion with the thermoplastic elastomer composition, or the adhesive agent. 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 an elastomer component 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 / 6'T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer ), Polyester resins (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (P T), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimidic acid / polybutyrate terephthalate copolymer Group polyester), polynitrile resins (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer) , Polymethacrylate resins (eg polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resins (eg vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer) (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulose resins (eg, cellulose acetate, cellulose acetate butyrate), Fluorine resin (for example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE)), imide resin (for example, 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), and nitrile-butadiene rubber (NBR). , Hydrogenated NBR, hydrogen Diene rubber such as modified SBR 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 Polymers, olefin rubbers such as acrylic rubber (ACM), ionomers; Br-IIR, CI-IIR, bromide of 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 silicon Silicon rubber such as rubber; such as sulfur-containing rubber such as polysulfide rubber, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber Fluoro rubbers: 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 introducing a thermoplastic resin and a rubber composition into a twin-screw kneader or the like, melt-kneading, and dispersing the rubber component in the thermoplastic resin forming a continuous phase. be able to. When a rubber component is vulcanized, dynamic vulcanization is performed by adding a vulcanizing agent while kneading or by blending a vulcanizing agent in advance with the rubber component.

  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 1-2 and Comparative Example 1
Preparation of Master Batches A and B The ingredients of Formulations A and B shown in Table I were put into a 4 liter pressure kneader, kneaded at a preset temperature of 110 ° C. for 5 minutes and then released to obtain master batches A and B. .

Preparation of adhesive composition Each component of the formulation shown in Table II was put into a single screw extruder, and the adhesive composition mixed at a set temperature of 110 ° C was extruded into a strand shape having a diameter of about 3 mm. To form a pellet. The obtained adhesive composition was sampled 10 times every 10 minutes, and the amount of metal (Zn or Ti) contained in each was measured. The content of the metal was used as the content of the pigment, the standard deviation was determined, and the variations in the composition of the adhesive were compared as shown in Table II.

After completion of the mixing of the adhesive composition, the screw was removed from the extruder, and the degree of contamination near the raw material inlet was visually observed to determine the contamination of the screw near the inlet after mixing according to the following criteria.
○… No dirt at all, clean condition △… Slightly dirty, but the screw surface is visible ×… Stained so much that the metal on the screw surface cannot be seen

  As is clear from the results of Table II, in Comparative Example 1 (when the pigment was directly mixed with the adhesive), the adhesive composition varied greatly, and the pigment adhered to the screw of the mixer after mixing. On the other hand, in Example 1 according to the present invention (when zinc oxide was mixed with SBS in advance to make a master batch), the variation was reduced and there was no screw contamination. Example 2 (Titanium dioxide was previously mixed with SBS) In the case of a masterbatch), the variation was further reduced and screw contamination was eliminated.

  As described above, according to the present invention, a powdery compounding agent that does not melt at a temperature below the kneading temperature such as zinc oxide or titanium oxide is preliminarily premixed in a polymer that melts at a temperature below the kneading temperature. Then, the adhesive composition is produced by masterbatch, so that, for example, as described in JP-A-8-217923, JP-A-11-199713, etc., a thermoplastic resin is used as a continuous phase, A thermoplastic elastomer having a dynamically dispersed rubber (dispersed phase) is useful, for example, as an adhesive when used as an air permeation preventive layer of a pneumatic tire.

Claims (7)

  In producing an adhesive composition for adhering a layer of a thermoplastic elastomer composition having a thermoplastic resin as a continuous phase and an elastomer component as a dispersed phase and a layer of a rubber composition at a temperature below the extrusion kneading temperature. A compound containing a solid compound that does not melt is preliminarily premixed with a polymer having a melting point equal to or lower than the extrusion kneading temperature of the adhesive composition, and then the premixed master batch is prepared as an adhesive composition. A method for producing an adhesive composition, comprising kneading continuously with an extruder together with a polymer component for physical properties, a tackifier and the remaining compounding agent.   The production method according to claim 1, wherein the polymer used for the premixing is at least one polymer selected from the group consisting of polyethylene, ethylene-vinyl acetate copolymer (EVA), and a styrenic thermoplastic elastomer.   2. The solid compounding agent used for the premixing is at least one compounding agent selected from zinc oxide, titanium oxide, magnesium oxide, carbon black, silica, calcium carbonate, clay, ultramarine, sulfur and zinc stearate. Or the manufacturing method of 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 method according to any one of Items 1 to 3.   5. The elastomer component is at least one selected from the group consisting of diene rubbers and hydrogenated products thereof, olefin rubbers, halogen-containing rubbers, silicon rubbers, sulfur-containing rubbers, fluororubbers and thermoplastic elastomers. The manufacturing method of any one of these.   The adhesive composition manufactured by the method of any one of Claims 1-5.   The pneumatic tire which used the adhesive composition of Claim 6 for the adhesion | attachment of an air permeation prevention layer and a tire member of the pneumatic tire which used the layer of the said thermoplastic elastomer composition for the air permeation prevention layer. .