JP2013176998A - Method of manufacturing laminate and method of manufacturing pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that can reduce manufacturing costs and can reduce a load on environment, and also is high in quality, and to provide a method of manufacturing the laminate, and a pneumatic tire.SOLUTION: When a laminate 4 having an air permeation preventive layer 1 including a thermoplastic resin and an adhesive layer 2 arranged on at least one surface of the air permeation preventive layer 1 is molded by a T-die method of multi-layer extrusion, a method of manufacturing a laminate includes a process of imparting ruggedness to a surface of the adhesive layer 2 by using an adhesive composition including a 100 pts.wt. of a polymer and a 10-100 pts.wt. of a filler 5 having a diameter L within a range of 0.25h≤L≤3.0h based on a thickness (h) of the adhesive layer 2, and under such a condition of the molding that a draw-down ratio (DDR) is larger than 1.

Description

  The present invention relates to a laminate manufacturing method and a pneumatic tire manufacturing method.

  A pneumatic tire generally includes an air permeation preventive layer mainly composed of a low gas permeable rubber typified by butyl rubber on the inner surface. However, the air permeation preventive layer mainly composed of low gas permeable rubber is usually laminated on a rubber sheet called tie rubber having a small hysteresis loss, so that the thickness of the entire layer including the tie rubber increases. This is one of the causes that increase the weight of product tires. Thus, it has been proposed to reduce the weight by disposing an air permeation preventive layer using a thermoplastic resin or a thermoplastic elastomer composition in which an elastomer component is dispersed in a thermoplastic resin (Patent Documents 1 to 6).

  When a layer containing a thermoplastic resin is used as an air permeation preventive layer for a tire, it is preferable to dispose the air permeation preventive layer inside the tire as a laminate with an adhesive layer in order to improve adhesion to rubber. When forming such a laminate, a sheet-like or cylindrical laminate is formed by simultaneously laminating the air permeation preventive layer and the adhesive layer by multilayer extrusion of an extruder, and the laminate is temporarily wound. It is preferable to take it and supply it to the tire molding process.

  However, when the laminate is wound with the adhesive layer exposed, the adhesive layer may be peeled off due to the adhesiveness of the adhesive when the laminate is unwound, or the adhesive layer may be tacky in the tire molding process. Due to this, it may be difficult to handle the laminate. Therefore, when winding up the laminate, it is necessary to wind a liner material such as release paper along the laminate.

  However, when a liner material is used, an extra material is required, which increases the manufacturing cost of the laminate, and the discarded liner material becomes an environmental burden. Further, when a liner material is used, wrinkles are likely to occur during winding of the laminate, and the quality of the pneumatic tire may be deteriorated. Therefore, it is desired to eliminate the use of a liner material when winding the laminate.

Japanese Patent No. 3153093 Japanese Patent No. 3212470 JP-A-8-216610 JP-A-8-258506 JP-A-8-259741 JP 2003-26931 A

  The present invention prevents peeling of the adhesive layer at the time of unwinding the laminate of the air permeation preventive layer and the adhesive layer, improves the handleability at the time of molding the tire, and winds up the laminate. A method for producing a laminate, which can eliminate the use of a liner material, thereby reducing the production cost of the laminate, reducing the burden on the environment, and further improving the quality of the laminate, and the laminate It is providing the manufacturing method of the pneumatic tire which used the body as an air permeation prevention layer.

A method for manufacturing a laminate according to one embodiment of the present invention includes:
When forming a laminate including an air permeation preventive layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the air permeation preventive layer by a multilayer extrusion T-die method,
An adhesive composition comprising 100 parts by weight of a polymer and 10 to 100 parts by weight of a filler having a diameter L in the range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer is used. Further, under the molding conditions, the ratio of the area of the die opening to the cross-sectional area of the sheet-like laminate (draw down ratio (DDR): die opening area / product cross-sectional area) is set to be larger than 1. A step of providing irregularities on the surface of the agent layer.

  In the method for manufacturing a laminate, the adhesive layer may include a styrene-butadiene-styrene copolymer polymer and a tackifier.

  In the method for producing a laminate, the thermoplastic resin is a polyamide resin, a polyester resin, a polynitrile resin, a polymethacrylate resin, a polyvinyl acetate resin, a polyvinyl alcohol resin, a polyvinyl chloride resin, or a cellulose resin. It can be at least one selected from the group of resins, fluororesins, and imide resins.

  In the method for producing a laminate, the layer containing the thermoplastic resin further contains an elastomer, the elastomer is dispersed in the thermoplastic resin, and a diene rubber, an olefin rubber, a sulfur-containing rubber, and a fluorine rubber. , And at least one selected from the group of thermoplastic elastomers.

  According to still another aspect of the present invention, there is provided a method for manufacturing a pneumatic tire, comprising: forming a laminate by the method for manufacturing a laminate, and then forming a sheet-like laminate having irregularities on the surface of the adhesive layer. Once wound around the periphery, the sheet-like laminate is unwound from the cell and cut to a predetermined length, and the sheet-like laminate cut to a predetermined length is formed so that the adhesive layer is on the outside An unvulcanized tire having an air permeation preventive layer is formed on the inner surface by laminating tire components on the outer periphery of the drum, and the unvulcanized tire is vulcanized in a mold of the vulcanizer. Sulfurate.

  According to the above method for producing a laminate, when molding a laminate comprising a layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the layer, 100 parts by weight of the polymer and the adhesive Forming the adhesive layer using an adhesive composition containing 10 to 100 parts by weight of a filler having a diameter L in the range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the agent layer Thus, by including a step of imparting irregularities to the surface of the adhesive layer, it is possible to prevent peeling of the adhesive layer at the time of unwinding the laminated body, improve the handleability at the time of tire molding, and The use of a liner material during winding is unnecessary, thereby reducing the manufacturing cost of the laminate, reducing the environmental burden, and further improving the quality of the laminate.

It is a figure which shows roughly the shaping | molding apparatus of the sheet-like laminated body using the T-die method used with the manufacturing method of the laminated body which concerns on one Embodiment of this invention. It is a figure which expands and shows the XY cross section of FIG. It is a figure which expands and shows the cross section of the laminated body 4 of FIG.

  Hereinafter, the manufacturing method of the laminated body which concerns on one Embodiment of this invention, and the manufacturing method of a pneumatic tire are demonstrated concretely.

1. Manufacturing method of laminated body and manufacturing method of pneumatic tire 1.1. Manufacturing method of laminated body The manufacturing method of the laminated body which concerns on one Embodiment of this invention is the layer (air permeation prevention layer) 1 containing a thermoplastic resin, and the adhesive bond layer 2 arrange | positioned on the at least one surface of the layer 1 And 100 to 100 parts by weight of a filler having a diameter L in the range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer 2. The process of providing an unevenness | corrugation on the surface of the adhesive bond layer 2 is included by using the adhesive composition containing these.

  The laminated body which concerns on one Embodiment of this invention is obtained by the manufacturing method of the said laminated body. That is, a laminate according to an embodiment of the present invention includes a layer (air permeation prevention layer) 1 containing a thermoplastic resin, and an adhesive layer 2 that is disposed on at least one surface of the layer 1 and has irregularities on the surface. The adhesive layer 2 includes a filler 5, and the filler 5 includes 100 parts by weight of the polymer and 10 to 100 parts by weight of the filler, and is 0.25 h with respect to the thickness h of the adhesive layer 2. It has a diameter L in the range of ≦ L ≦ 3.0 h.

1.1.1. Production of Laminate 4 Similarly, FIG. 1 schematically shows an apparatus for forming a sheet-like laminate 4 using a T-die method, which is used in a method for producing a laminate according to another embodiment of the present invention. 2 is an enlarged view of the XY cross section of FIG. 1, and FIG. 3 is an enlarged view of the cross section of the laminate 4 of FIG.

  As shown in FIG. 2, the sheet-like laminate 4 is a two-layer laminate of an air permeation preventive layer 1 and an adhesive layer 2. In the present embodiment, the case where the laminate 4 is a two-layer laminate is taken as an example. However, if necessary, the laminate according to the present embodiment has the adhesive layer 2 laminated on both surfaces of the air permeation preventive layer 1. Alternatively, it may be a three-layer laminate. In FIG. 1, the air permeation preventive layer 1 and the adhesive layer 2 are simultaneously extruded and laminated from a T die by an extrusion device, and a sheet-like laminate 4 is obtained. The sheet-like laminate 4 including the air permeation preventive layer 1 and the adhesive layer 2 is taken up by a pair of rolls 21 and 22 and is continuously wound around the cell 23.

  In the method for manufacturing the laminate 4 according to the present embodiment, in the step of forming the sheet-like laminate 4, as shown in FIGS. 2 and 3, the surface of the adhesive layer 2 has irregularities with the filler as a nucleus. To do. In the molding by the T-die method, the ratio of the area of the die opening to the cross-sectional area of the sheet-like laminate (draw down ratio (DDR): die opening area / product cross-sectional area), which is one of the molding conditions, is 1 Set larger. When the drawdown ratio is larger than 1, the sheet-like laminate 4 is stretched and formed in the extrusion direction, so that the laminate 4 is stretched. When the adhesive layer 2 containing the filler 5 is stretched, the portion where the filler 5 is present is not affected by stretching, so the thickness does not change, and the portion where the filler 5 is not present is stretched and the thickness is reduced. To do. Therefore, the unevenness as shown in FIGS. 2 and 3 can be effectively formed in the adhesive layer 2. On the contrary, when the draw down ratio is 1 or less, the unevenness due to stretching is not formed on the surface of the adhesive layer 2, so that the adhesiveness of the adhesive layer 2 cannot be suppressed.

1.1.2. Filler 5
In the manufacturing method of the laminated body which concerns on this embodiment, regarding the above-mentioned T-die shaping | molding, regarding the relationship (refer FIG. 3) of the diameter L of the filler 5 mix | blended with an adhesive composition and the thickness h of the adhesive bond layer 2. 0.25h ≦ L ≦ 3.0h, more preferably 0.5h ≦ L ≦ 2.0h. When L is less than 0.25 h, the unevenness formed may be too small to sufficiently suppress the tackiness of the adhesive layer 2. On the other hand, when L is larger than 3.0 h, the formed irregularities are too large, and not only the adhesion to the rubber at the time of tire molding cannot be secured, but also the filler 5 works as a foreign substance, and the laminate is tired. When used as the air permeation preventive layer 1, the durability may be reduced.

  As the filler 5, particles having a diameter L of 0.25h ≦ L ≦ 3.0h with respect to the thickness h of the adhesive layer 2 are preferable. For example, silica gel beads, carbon beads, glass beads, alumina, fly ash, Shirasu balloon, heavy calcium carbonate and the like can be mentioned, and those having spherical particles are preferable from the viewpoint of durability. The blending amount of the filler 5 is not particularly limited, but is preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the polymer content of the adhesive layer 2. Here, when the blending amount of the filler 5 is less than 10 parts by weight with respect to 100 parts by weight of the polymer content of 2, there is a possibility that the unevenness formed is small and the adhesiveness of the adhesive layer 2 may not be sufficiently suppressed, When the amount exceeds 100 parts by weight, there are too many irregularities to be formed, and there is a possibility that the adhesion to rubber during tire molding cannot be ensured.

  Next, in a tire molding process using the sheet-like laminate, the sheet-like laminate is unwound from the cell 23 and cut into a predetermined length. And by covering the periphery of the molding drum with the sheet-shaped laminate cut to a predetermined length around the molding drum so that the adhesive layer 2 is on the outside, and further sequentially laminating tire constituent members such as carcass materials on the outside, An unvulcanized tire having the air permeation preventive layer 1 on the tire inner surface is molded. This unvulcanized tire is vulcanized in a mold of a vulcanizer and completed as a pneumatic tire.

  As described above, in the method for manufacturing a laminate according to the present embodiment, in the step of forming the sheet-like laminate, the surface of the adhesive layer 2 is formed with irregularities having the filler 5 as a core, thereby forming the laminate. Controlling the tackiness of the adhesive layer 2 having a large adhesive force, can improve the peelability of the adhesive layer 2 during unwinding of the laminate and the handleability during tire molding. Further, when winding the laminate Use of a liner material can be eliminated. Thereby, the manufacturing cost of a laminated body can be reduced and the load to an environment can also be reduced. Further, by winding the laminate without using a liner material, it becomes difficult for wrinkles to occur in the laminate, so that the quality of the laminate is improved, and as a result, a pneumatic tire manufactured using this laminate is improved. Quality can be improved.

1.1.3. Air Permeation Prevention Layer The air permeation prevention layer 1 contains a thermoplastic resin. For example, the air permeation preventive layer 1 is composed of a thermoplastic resin or a thermoplastic elastomer composition. That is, the thermoplastic resin may be used as a single material that does not contain an elastomer component, or may be used as a component of a thermoplastic elastomer composition. Here, the thermoplastic elastomer composition uses a thermoplastic resin as a matrix, and an elastomer component is dispersed in the matrix.

  As the thermoplastic resin constituting the air permeation preventive layer 1, any thermoplastic resin having a Young's modulus exceeding 500 MPa, preferably 500 to 3000 MPa can be used. The total weight is 10% by weight or more, preferably 20 to 85% by weight. As such a thermoplastic resin, for example, polyamide resin [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, nylon 6T, nylon 6 / 6T Polymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer], polyester resin [for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polybutylene terephthalate / tetramethylene Glycol copolymer, PET / PEI Polymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, aromatic polyester such as polyoxyalkylene diimide diacid / polybutylene terephthalate copolymer], polynitrile resin [for example, polyacrylonitrile (PAN) , Polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer], poly (meth) acrylate resin [for example, polymethyl methacrylate (PMMA), polyethyl methacrylate, ethylene ethyl acrylate copolymer (EEA), ethylene acrylic acid copolymer (EAA), ethylene methyl acrylate resin (EMA)], polyvinyl acetate resin [for example, polyvinyl acetate (PVA), ethylene / vinyl acetate copolymer (EVA)], polyvinyl alcohol resin [eg polyvinyl alcohol (PVOH), vinyl alcohol / ethylene copolymer (EVOH)], polyvinyl chloride resin [eg polychlorinated Vinylidene (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer], cellulose resins (eg, cellulose acetate, cellulose acetate butyrate), fluorine resins (eg, polyvinyl fluoride) Vinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE)], imide-based resin [for example, aromatic polyimide (PI)], etc. Can be more than two kinds May be.

  As an elastomer component of the thermoplastic elastomer composition, any elastomer having a Young's modulus of 500 MPa or less or a reinforcing agent, a filler, a cross-linking agent, a softener, an anti-aging agent for improving the dispersibility and heat resistance of the elastomer. It is possible to use an elastomer composition to which a necessary amount of a compounding agent such as an agent and a processing aid is added, and the amount is 10% by weight or more, preferably 10 to 80% by weight, based on the total weight of the polymer components including the resin and elastomer. It is. Examples of such elastomers include diene rubbers and hydrogenated products thereof [for example, NR, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, hydrogenated SBR. ], Olefin rubber [e.g. ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM)], butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber ( ACM), ionomer, halogen-containing rubber [for example, brominated product of Br-IIR, Cl-IIR, isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHC, CHR), chlorosulfonated Polyethylene (CSM), chlorinated polyethylene (C ), Maleic acid-modified chlorinated polyethylene (M-CM)], silicone rubber (for example, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (for example, polysulfide rubber), fluoro rubber (for example, vinylidene fluoride) Rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (eg styrene elastomer, olefin elastomer, polyester elastomer, urethane elastomer) , Polyamide-based elastomer), and the like.

  In addition to the above components, the composition for forming the air permeation preventive layer 1 is a compatibilizer, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator, as long as the necessary properties of the laminate of the present invention are not impaired. Other additives such as a vulcanization acceleration aid, a vulcanization retarder, a plasticizer, a filler, a colorant, and a processing aid may be appropriately blended.

  When the air permeation preventive layer 1 is formed using a thermoplastic elastomer composition, the thermoplastic elastomer composition is prepared by previously mixing a thermoplastic resin and an elastomer (unvulcanized in the case of rubber) with a biaxial kneading extruder or the like. It can be obtained by melt-kneading and dispersing an elastomer component in a thermoplastic resin forming a continuous phase. When the elastomer component is vulcanized, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer. Further, various compounding agents (excluding the vulcanizing agent) to the thermoplastic resin or the elastomer component may be added during the kneading, but are preferably mixed in advance before kneading. The kneading machine used for kneading the thermoplastic resin and the elastomer is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a biaxial kneading extruder. Among them, it is preferable to use a twin-screw kneading extruder for kneading the resin component and the rubber component and for dynamic vulcanization of the rubber component. Further, two or more types of kneaders may be used and kneaded sequentially. As conditions for melt-kneading, the temperature should just be more than the temperature which a thermoplastic resin melts, and it is preferable that the shear rate at the time of kneading is 2500-7500 sec-1. The entire kneading time is from 30 seconds to 10 minutes, and when a vulcanizing agent is added, the vulcanization time after addition is preferably from 15 seconds to 5 minutes. The thermoplastic elastomer composition produced by the above method has a structure in which an elastomer is dispersed as a discontinuous phase in a thermoplastic resin matrix, and is suitable as an air permeation preventive layer 1 of a tire.

1.1.4. Adhesive Layer The adhesive layer 2 is formed using an adhesive composition containing 100 parts by weight of polymer (adhesive polymer) and 10 to 100 parts by weight of filler 5. As described above, the filler 5 has a diameter L in the range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer 2. The adhesive layer 2 can further include an adhesive polymer and a tackifier.

  Examples of the adhesive polymer include ultra high molecular weight polyethylene (UHMWPE), ethylene ethyl acrylate copolymer (EEA), ethylene methyl acrylate resin (EMA), and ethylene acrylic acid copolymer having a molecular weight of 1 million or more, preferably 3 million or more. Acrylate copolymers such as polymer (EAA) and their maleic acid modified products, polypropylene (PP) and its maleic acid modified products, ethylene propylene copolymer and its maleic acid modified products, ethylene octene copolymer and its maleic Acid-modified product, polybutadiene-based resin and its maleic acid-modified product, styrene-butadiene-styrene copolymer (SBS) and its epoxy-modified product, styrene-ethylene-butadiene-styrene copolymer (SEBS) and its epoxy-modified product, Fluorine-based thermoplastic resin, , And the like Riesuteru based thermoplastic resin. In particular, it is preferable to use a styrene-butadiene-styrene copolymer (SBS) and an epoxy-modified product thereof. Examples of the tackifier include coumarone indene resin, terpene resin, terpene phenol resin, rosin, rosin derivative, phenol acetylene resin, and alicyclic saturated hydrocarbon resin. A preferable example of the adhesive layer 2 includes one containing a styrene-butadiene-styrene copolymer polymer and a tackifier.

  The adhesive layer 2 further includes an adhesive appropriately blended with a reinforcing agent (for example, carbon black, silica, clay, mica), a vulcanizing agent, a vulcanization accelerator, an oil, an anti-aging agent, a plasticizer, and a pigment. It may be formed using. The thickness of the adhesive layer 2 is not particularly limited, but it is better that the thickness is smaller in order to reduce the tire weight. For example, the thickness is preferably 5 μm to 150 μm.

1.2. Pneumatic tire A pneumatic tire according to another embodiment of the present invention uses the laminate according to the above embodiment as an inner liner.

  DESCRIPTION OF SYMBOLS 1 ... Air permeation prevention layer, 2 ... Adhesive layer, 4 ... Laminated body, 5 ... Filler, 21, 22 ... Roll, 23 ... Cell

Claims (5)

When forming a laminate including an air permeation preventive layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the air permeation preventive layer by a multilayer extrusion T-die method,
An adhesive composition comprising 100 parts by weight of a polymer and 10 to 100 parts by weight of a filler having a diameter L in the range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer is used. In the molding conditions, the ratio of the area of the die opening to the cross-sectional area of the sheet-like laminate (draw down ratio (DDR): area of the die opening / product cross-sectional area) is set to be larger than 1. The manufacturing method of a laminated body including the process of providing an unevenness | corrugation to the surface of an agent layer.   The manufacturing method of the laminated body of Claim 1 in which the said adhesive bond layer contains a styrene-butadiene-styrene copolymer type | system | group polymer and a tackifier.   The thermoplastic resin is a polyamide resin, a polyester resin, a polynitrile resin, a polymethacrylate resin, a polyvinyl acetate resin, a polyvinyl alcohol resin, a polyvinyl chloride resin, a cellulose resin, a fluorine resin, or an imide. The manufacturing method of the laminated body of Claim 1 or 2 which is at least 1 sort (s) chosen from the group of type | system | group resin. The layer containing the thermoplastic resin further contains an elastomer,
The elastomer is dispersed in the thermoplastic resin, and is at least one selected from the group consisting of diene rubber, olefin rubber, sulfur-containing rubber, fluororubber, and thermoplastic elastomer. 4. A method for producing a laminate according to any one of 3 above.   After forming the laminate by the method for producing a laminate according to any one of claims 1 to 4, the sheet-like laminate provided with irregularities on the surface of the adhesive layer is temporarily wound around a cell, The sheet-like laminate is unwound from the cell and cut to a predetermined length, and the sheet-like laminate cut to a predetermined length is placed around the molding drum so that the adhesive layer is on the outside, Manufacturing a pneumatic tire in which an unvulcanized tire having an air permeation preventive layer is formed on the inner surface by laminating tire constituent members on the outside, and the unvulcanized tire is vulcanized in a mold of a vulcanizer Method.

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