JP2010260280A - Laminate, method of manufacturing the same, and pneumatic tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality laminate which reduces manufacturing costs and environment loads, a method of manufacturing the same, and a pneumatic tire. <P>SOLUTION: The method of manufacturing the laminate includes a step of giving irregularities on a surface of an adhesive layer 2 by forming the adhesive layer 2 using an adhesive composition containing 100 pts.wt. of polymers and 5 of 10-100 pts.wt. of fillers having a diameter L in a range of 0.25h≤L≤3.0h as to the thickness h of the adhesive layer, when forming the laminate containing a layer 1 containing a thermoplastic resin and the adhesive layer 2 arranged at least at one side of the layer 1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  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 The object is to provide a pneumatic tire using the body as an air permeation preventive layer.

A method for manufacturing a laminate according to one embodiment of the present invention includes:
In forming a laminate including a layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the layer,
Using 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 A step of forming irregularities on the surface of the adhesive layer by forming the adhesive layer is included.
In the method for producing a laminate, the laminate is molded by a multi-layer extrusion inflation method. Under the molding conditions, the ratio of the diameter of the annular die to the diameter of the tubular laminate (blow-up ratio (BUR): tubular) The laminate diameter / annular die diameter may be greater than 1.
In the method for producing a laminate, the laminate is molded by a multi-extrusion T-die method. 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) may be larger than 1.
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.

The laminate according to another embodiment of the present invention is
A layer containing a thermoplastic resin;
An adhesive layer disposed on at least one surface of the layer and having irregularities on the surface;
Including
The adhesive layer includes 100 parts by weight of a polymer and 10 to 100 parts by weight of a filler, and the filler is in a range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer. It has a diameter L.
In the laminate, the adhesive layer may include a styrene-butadiene-styrene copolymer polymer and a tackifier.
In the above laminate, the thermoplastic resin is a polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl chloride resin, cellulose resin, fluorine It can be at least one selected from the group of resin based resins and imide based resins.
In the laminate, the layer containing the thermoplastic resin further contains an elastomer,
The elastomer is dispersed in the thermoplastic resin, and may be at least one selected from the group of diene rubber, olefin rubber, sulfur-containing rubber, fluororubber, and thermoplastic elastomer.

  In the pneumatic tire according to still another aspect of the present invention, the laminate is used as an inner liner.

  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 cylindrical laminated body using the inflation 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 3 of FIG. 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, a laminate according to an embodiment of the present invention, a manufacturing method thereof, and a pneumatic tire will be specifically described.

1. Laminated body, manufacturing method thereof, and pneumatic tire 1.1. Laminated body and manufacturing method thereof A manufacturing method of a laminated body according to an embodiment of the present invention includes a layer (air permeation preventive layer) 1 containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the layer 1. 2 to 10 parts by weight of a polymer 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 to the surface of the adhesive bond layer 2 by using the adhesive composition containing a part is included.

  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 3 FIG. 1 schematically shows an apparatus for forming a cylindrical laminate 3 using an inflation method used in the method for producing a laminate according to an embodiment of the present invention. FIG. FIG. 3 is an enlarged view of the XY cross section, and FIG. 3 is an enlarged view of the cross section of the laminate 3 of FIG.

  As shown in FIG. 2, the laminate (tubular laminate) 3 has an air permeation preventive layer 1 as an inner layer and an adhesive layer 2 as an outer layer. In FIG. 1, the air permeation preventive layer 1 and the adhesive layer 2 are laminated by being extruded coaxially and simultaneously from an annular die by an extrusion device, and then inflated to form a cylindrical laminate 3. As shown in FIG. 1, the cylindrical laminate 3 including the air permeation preventive layer 1 and the adhesive layer 2 is flatly crushed when passing between the pair of rolls 11 and 12, and the cell in the crushed state. 13 is continuously wound around.

  In the manufacturing method of the laminated body 3 according to the present embodiment, in the step of forming the cylindrical laminated body 3, as shown in FIGS. 2 and 3, the surface of the adhesive layer 2 has unevenness with the filler 5 as a core. Form. In molding by inflation method, the ratio of the diameter of the annular die to the diameter of the cylindrical laminate (blow-up ratio (BUR): cylindrical laminate diameter / annular die diameter), which is one of the molding conditions, is larger than 1. Is preferred. When the blow-up ratio is larger than 1, the cylindrical laminate 3 is formed to swell more than the annular die diameter, so that the cylindrical laminate 3 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. Thereby, the unevenness as shown in FIGS. 2 and 3 can be effectively formed on the surface of the adhesive layer 2. On the contrary, when the blow-up 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. Production of Laminate 4 Similarly, FIG. 4 schematically shows an apparatus for forming a sheet 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. FIG. 5 is an enlarged view of the XY cross section of FIG. 4, and FIG. 6 is an enlarged view of the cross section of the laminate 4 of FIG.

  As shown in FIG. 5, 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. 4, 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 laminate 4, as shown in FIGS. 5 and 6, the surface of the adhesive layer 2 is formed with unevenness with the filler as a nucleus. To do. In the molding by the T-die method, one of the molding conditions is a ratio of the die opening area to the cross-sectional area of the sheet-like laminate (draw down ratio (DDR): die opening area / product cross-sectional area) from 1. Larger is preferred. When the drawdown ratio is greater 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. 5 and 6 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.

1.1.3. Filler 5
In the manufacturing method of the laminated body which concerns on this embodiment, in the above-mentioned inflation shaping | molding and T-die shaping | molding, the relationship between the diameter L of the filler 5 mix | blended with an adhesive composition and the thickness h of the adhesive bond layer 2 (FIG. 3 and FIG. 6), it is preferable that 0.25h ≦ L ≦ 3.0h, and 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 unevenness formed is 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 the tire molding process using the tubular or sheet-like laminate, the tubular or sheet-like laminate is unwound from the cells 13 to 14 and cut into a predetermined length. Then, a cylindrical or sheet-like laminate cut to a predetermined length is placed around the molding drum so that the adhesive layer 2 is on the outside, and further, tire constituent members such as carcass materials are sequentially laminated on the outside. Thereby, the unvulcanized tire provided with 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 a cylindrical or sheet-like laminate, irregularities having the filler 5 as a nucleus are formed on the surface of the adhesive layer 2. By controlling the adhesiveness of the adhesive layer 2 having a large self-adhesive force, it is possible to improve the peelability of the adhesive layer 2 at the time of unwinding of the laminated body and the handleability at the time of tire molding. The use of a liner material can be obviated when taking. 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.

1.1.4. 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 softening agent, 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 (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide rubber), fluoro rubber (eg, vinylidene fluoride) Rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (for example, 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) for the thermoplastic resin or the elastomer component may be added during the kneading, but it is preferable to mix them 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 may be equal to or higher than the temperature at which the thermoplastic resin melts, and the shear rate during kneading is preferably 2500 to 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.

1.1.5. 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 weight of the tire. 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.

2. EXAMPLES Hereinafter, the present invention will be further described by way of examples. However, the scope of the present invention is not limited to these examples.

First, a thermoplastic elastomer composition and various adhesive compositions were prepared, and various cylindrical laminates were molded by using the inflation method. Thereafter, a green tire using each cylindrical laminate as an air permeation preventive layer was prepared and vulcanized to prepare a tire.
In this example, the effect of the present invention was evaluated by changing the blending amount of the filler, and the effect of the present invention was evaluated by the difference in molding conditions.

2.1. Preparation of thermoplastic elastomer composition In the blending ratio (parts by weight) shown in Table 1, a resin, a rubber material, and a crosslinking compound necessary for dynamic crosslinking are mixed at a temperature of 230 ° C. with a twin-screw kneading extruder, and continuously The rubber is finely dispersed in the thermoplastic resin constituting the phase, extruded into a strand shape from the discharge port of the twin-screw kneading extruder, and the strand is pelletized with a cutter to produce a pellet of the thermoplastic elastomer composition did.

(Table 1)

────────────────────────────
Compounding ingredients Compounding amount (parts by weight)
────────────────────────────
Nylon 11 * 1 24
Nylon 6.66 * 2 16
BIMS * 3 60
Zinc flower * 4 0.3
Stearic acid * 5 1.2
Zinc stearate * 6 0.6
────────────────────────────

* 1: BESN O TL manufactured by Arkema

* 2: 5033B made by Ube Industries

* 3: Exxpro MDX89-4 manufactured by ExxonMobil Chemical

* 4: Zinchua No. 3 manufactured by Shodo Chemical

* 5: Bead stearic acid made by Nippon Oil & Fats

* 6: Zhodo Chemical Zinc Stearate

2.2. Preparation of Adhesive Composition To affix the thermoplastic elastomer composition to the inner surface of the tire, a blending ratio (parts by weight) shown in Table 2 is used, and a biaxial kneading extruder is used to add a filler, an adhesive polymer and a tackifier. The mixture was sufficiently kneaded at 100 ° C., extruded into a strand form from the discharge port, and the obtained strand was water-cooled, and then pelletized with a cutter to prepare an adhesive composition pellet. In this example, glass beads were used as the filler. In addition, as the specifications of the adhesive composition, the composition of Example 1 in which the filler is not blended, the composition of Example 1 in which the filler is blended in 50 phr (including 50 parts by weight of the filler with respect to 100 parts by weight of the polymer), Composition of Comparative Example 1 containing 5 phr of filler (containing 5 parts by weight of filler with respect to 100 parts by weight of polymer), Composition of Comparative Example 2 containing 150 phr of filler (100 parts by weight of polymer) Containing 150 parts by weight of filler).

* 1: Daicel Chemical Epofriend AT501
* 2: Asahi Kasei
Toughprene 315

* 3: Pencel AD manufactured by Arakawa Chemical

* 4: Zinchua No. 3 manufactured by Shodo Chemical

* 5: Bead stearic acid made by Nippon Oil & Fats

* 6: Parka Docks 14 made by Kayaku Akzo

* 7: GB731 manufactured by Potters Ballotini (average particle size 32 μm)

2.3. Inflation Molding Using a thermoplastic elastomer composition and various adhesive composition pellets, a general two-layer inflation molding device is used to perform inflation molding of a laminated film at 230 ° C., and the thermoplastic elastomer composition layer and adhesion A cylindrical laminate of the agent layer was obtained. The thickness of the thermoplastic elastomer composition layer was 100 μm, and the thickness of the adhesive layer was 30 μm. Further, as a comparative control, the same adhesive layer as in Example 1 was used, and a cylindrical laminate was formed with a blowup ratio of 1 using a die having a large diameter. did. Each laminate was wound up to 100 m in a roll shape. Table 3 shows the molding conditions for each laminate.

2.4. Self-adhesion of laminated body and peeling evaluation of adhesive layer The cylindrical laminated body wound up by the above molding is stored for one week, and then rolled up to evaluate self-adhesion and peeling state of the adhesive layer. It was. Regarding the self-adhesion evaluation, when it was difficult to unwind and unwind, it was judged as unsatisfactory (x), and when it could be wound without any problem, it was judged as good (◯). Regarding the evaluation of the adhesive peeling state, the case where the adhesive peeled off at the time of unwinding was judged as unsatisfactory (x), and the case where no peeling occurred was judged as good (◯). The results are shown in Table 4.
Conventional Example 1 in which no filler is blended and Comparative Example 3 in which the blow ratio is 1 cannot suppress the tackiness because there is no unevenness of the adhesive layer, and neither self-adhesion evaluation nor evaluation of the adhesive peeling state is possible. (X).
Further, Comparative Example 1 containing 5 phr of the filler was insufficient in the formation of the unevenness of the adhesive layer, so that the tackiness was not sufficiently suppressed, and the self-adhesion evaluation and the evaluation of the adhesive peeling state were acceptable (Δ).
Furthermore, Example 1 with a filler of 50 phr and Comparative Example 2 with a filler of 150 phr were both good (◯) in terms of self-adhesion evaluation and evaluation of the adhesive peeling state.

2.5. Preparation of tire Each tubular laminated film is wound around a tire molding drum so that the thermoplastic elastomer composition is on the drum side and the adhesive composition is on the tire member side, and the tire member is laminated thereon, and a green tire is formed by a conventional method. After molding, vulcanized (conditions: 180 ° C. × 10 minutes) to produce a tire with a tire size of 165SR13.
We also evaluate the handling characteristics of the film in the tire making process, and those that are difficult to handle due to the strong adhesion of the film and those that cause problems in the formation of green tires are not acceptable (×) And those with no problems were evaluated as good (◯). The results are shown in Table 4.
Conventional Example 1 in which no filler was blended, Comparative Example 1 in which the filler was 5 phr, and Comparative Example 3 in which the blow ratio was 1 were highly tacky and difficult to handle, and all evaluations were impossible (x). In Comparative Example 2 containing 150 phr of the filler, evaluation was not possible (x) because the laminate was peeled off from the inner surface of the green tire because the tackiness was too low. Furthermore, Example 1 containing 50 phr of the filler had good handleability and moderate tackiness, and the evaluation was good (◯).

  As described above, according to the present invention, when a laminate including a layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the layer is molded, By using an adhesive composition containing 10 to 100 parts by weight of a filler having a diameter L in the range of 0.25h ≦ L ≦ 3.0h with respect to the thickness h of the agent layer, the surface of the adhesive layer By including a step of imparting irregularities to the surface, adhesion during unwinding of the laminate and delamination of the adhesive layer are suppressed, handling at the time of molding the tire is improved, and further, a liner material when winding the laminate The use of is no longer necessary.

  DESCRIPTION OF SYMBOLS 1 ... Air permeation prevention layer, 2 ... Adhesive layer, 3, 4 ... Laminated body, 5 ... Filler, 11, 12, 21, 22, ... Roll, 13, 23 ... Cell

Claims (11)

In forming a laminate including a layer containing a thermoplastic resin and an adhesive layer disposed on at least one surface of the layer,
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. By this, the manufacturing method of a laminated body including the process of providing an unevenness | corrugation to the surface of the said adhesive bond layer.   The laminate is molded by a multi-layer extrusion inflation method. Under the molding conditions, the ratio of the diameter of the annular die to the diameter of the tubular laminate (blow-up ratio (BUR): cylindrical laminate diameter / annular die diameter) The manufacturing method of the laminated body of Claim 1 whose is larger than one.   The laminate is molded by a multi-layer extrusion T-die method. 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 breakage) The manufacturing method of the laminated body of Claim 1 whose area is larger than one.   The manufacturing method of the laminated body in any one of Claims 1-3 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 in any one of Claims 1-4 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 of diene rubber, olefin rubber, sulfur-containing rubber, fluororubber, and thermoplastic elastomer. 6. A method for producing a laminate according to any one of 5 above. A layer containing a thermoplastic resin;
An adhesive layer disposed on at least one surface of the layer and having irregularities on the surface;
Including
The adhesive layer includes 100 parts by weight of a polymer and 10 to 100 parts by weight of a filler, and the filler is in a range of 0.25 h ≦ L ≦ 3.0 h with respect to the thickness h of the adhesive layer. A laminate having a diameter L.   The laminate according to claim 7, wherein the adhesive layer comprises a styrene-butadiene-styrene copolymer-based 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 laminate according to claim 7 or 8, which is at least one selected from the group of resin based resins. 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 of diene rubber, olefin rubber, sulfur-containing rubber, fluororubber, and thermoplastic elastomer. The laminated body in any one of 9.   A pneumatic tire using the laminate according to any one of claims 7 to 10 as an inner liner.