JP3851972B2 - Laminated body and tire using the same - Google Patents

Description

【００３６】
加硫時発泡状況試験
上記の熱可塑性エラストマー組成物と粘接着剤からなる２層フィルムを粘接着剤側をカーカスゴムと合わせて積層させ、１８０℃、１０分間加硫した。
加硫後、粘接着剤が全く発泡していないものを○、発泡が観察されたものを×とした。
【００３７】
タイヤ耐久試験
試験タイヤは以下のようにして作製した。
上記の熱可塑性エラストマー組成物と粘接着剤からなる２層フィルムを、熱可塑性エラストマー組成物側を内側にしてタイヤ成形用ドラム上に円筒に貼りつける。その上に未加硫ゴムからなるカーカス層、ベルト層、トレッド層等の通常のタイヤ製造に用いられる部材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤとする。次いで、このグリーンタイヤを常法に従って、加熱加硫することにより、所望の空気入りタイヤを製造した。
次に耐久試験は、１６５ＳＲ１３スチールラジアルタイヤ（リム１３×４ １／２−Ｊ）を使用し、空気圧を２００kPa として、１５００ccクラスの乗用車に装着して、４名乗車時相当荷重（６５kg／人）を与え、実路上を２万km走行する。
走行後に、タイヤをリムから外してタイヤ内面のライナー層を目視観測する。ライナー層にクラック、目視できるしわ、ライナー層の剥離・浮き上がりがあるものを不合格（×）、ないものを合格（○）と判定する。
【００３８】
実施例１〜７および比較例１〜４
以上の各種粘接着剤組成物を用いた測定および評価結果を表Ｉに示す。
【００３９】
【表１】

【００４０】
【表２】

【００４１】
以上の結果より、二重結合を有するスチレン系共重合体と、イオウ系加硫剤または加硫促進剤を組合せることにより、発泡のない積層体ができ、これは、タイヤとしての耐久性にも優れていることがわかる。
一方、比較例１．２のように、架橋をしないポリマーだけで、粘接着剤組成物を構成した場合や、比較例４のように全くイオウ系加硫剤を入れない場合には、粘接着剤組成物が、積層体加硫時に発泡してしまい、そこが起点となって耐久試験時にフィルム破壊が発生する。
さらに、比較例３のように、イオウ系加硫剤、加硫促進剤の双方を投入した場合には、２軸混練にて、粘接着剤組成物を混合する際に既に架橋が始まりフィルム化すらもできないことが観察された。
【００４２】
【発明の効果】
以上説明したとおり、本発明による粘接着剤組成物を使用すれば、発泡がなく、安定した粘接着剤フィルムが成形でき、また、これを接合層として熱可塑性樹脂フィルムとゴム部材との間の接合に用いた積層体およびタイヤとなせば、その接合部に粘接着剤の粒部分、発泡部分に起因するフィルムクラック等が全くなく、接着強度の高い信頼性の高い製品を得ることができる。[0001]
BACKGROUND OF THE INVENTION
  The present invention is stable without foamingThermoplastic resin film-rubberAn adhesive composition having a specific composition capable of forming a laminate comprisingManufacturing method of laminateAnd a tire using the same.
[0002]
[Prior art]
The inventors of the present invention have previously described a joining portion of a thermoplastic film or a tire facing a thermoplastic film in the manufacture of a pneumatic tire using a belt-like or cylindrical single-layer or multilayer thermoplastic film as an air permeation prevention layer. An adhesive composition comprising a polymer component having a critical surface tension difference of 3 mN / m or less between the rubber component of the tire member and the polymer component of the surface layer of the thermoplastic film, at least partially between the member and the member. An invention relating to a manufacturing method of a pneumatic tire applied was presented (Japanese Patent Application No. 7-108666). In the present invention, as the above-mentioned adhesive composition, an adhesive, a crosslinking agent (vulcanizing agent) and an adhesive selected from unvulcanized rubber-based, urethane-based, acrylic-based, and styrene-based materials are used. What used the imparting agent was used.
However, when a styrene copolymer having a double bond is used for the adhesive, the adhesive will foam when the tire is molded unless a vulcanizing agent is added to the adhesive composition. The film cracks starting from the foamed part, and if the vulcanizing agent is sufficiently added, the polymer and the vulcanizing agent react when mixing the adhesive composition. As a result, the film became too high to be able to remove the film, or even if the film could be removed, the gel content became granular and the film had holes.
[0003]
[Problems to be solved by the invention]
  Therefore, in the present invention, it is interposed between the thermoplastic resin film and the unvulcanized rubber composition, and these are firmly joined, and there is no foaming at the time of molding, and it is stable.Thermoplastic resin film-rubberA laminate comprising:Double bondStyrenic copolymer with adhesive as adhesiveMethod for producing laminate made of thermoplastic resin film-rubber usedProviding further,Using the laminateThe object is to provide a tire.
[0004]
[Means for Solving the Problems]
  According to the present invention,A: A thermoplastic resin obtained by integrating a thermoplastic resin film and C: an unvulcanized rubber composition through B: an adhesive composition containing a styrene copolymer having a double bond during vulcanization In the method for producing a film-vulcanized rubber composition laminate, either one of a sulfur-based vulcanizing agent and a vulcanization accelerator is previously added to the adhesive composition B, and the unvulcanized C A method for producing a thermoplastic resin film-vulcanized rubber composition laminate, wherein the other rubber is mixed in the other rubber composition., AndConcernedA tire using the laminate is provided.
[0005]
  Further, according to the present invention, the thermoplastic resin film is a thermoplastic elastomer composition in which a vulcanized rubber component is dispersed in a thermoplastic resin matrix, and the laminate andUsed thisTires are provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
  In the present invention,A:With thermoplastic filmC:A laminate comprising an unvulcanized rubber composition orUsed thisIn obtaining a tire, it is used as an adhesive film layer interposed between them.B: Adhesive composition containing a styrene copolymer having a double bondIn that,The adhesive compositionIn advanceSulfur-based vulcanizing agentOr either vulcanization acceleratoron the other handIf this adhesive composition is made into a film at the time of use and placed between the two members and integrated with each other during rubber vulcanization, an extremely stable adhesive film can be formed. Also, the one that had not been mixed in the adhesive during the vulcanizationSulfur-based vulcanizing agentOr a vulcanization accelerator,C in which this was mixed: Unvulcanized rubber compositionFrom the sideThe adhesive filmIt has been found that it is possible to move to the side, give sufficient vulcanization, and join firmly.
[0007]
  Used in the adhesive composition according to the present inventionDouble bondExamples of styrene-based copolymers having acid include acid-modified or epoxidized-modified styrene / butadiene / styrene copolymers, styrene / butadiene / styrene copolymers and the like known in the art. Moreover, it mixes in this adhesive composition and is used.As sulfur vulcanizing agent, Powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface treated sulfur, insoluble sulfur, dimorpholine disulfide, alkyl phenol disulfideEtc..These sulfur vulcanizing agentsFor example, about 1 to 4 phr (parts by weight per 100 parts by weight of the adhesive, the same shall apply hereinafter)Can be used.
[0008]
Similarly, as the vulcanization accelerator, a general rubber vulcanization accelerator can be used, for example, 0.5 to 30 phr. Specifically, aldehyde / ammonia (for example, hexamethylenetetramine), guanidine (for example, diphenyl / guanidine), thiazole (for example, 2-mercaptobenzothiazole, and its Zn salt, cyclohexylamine salt, dibenzothiazyl disulfide), Sulfenamide (for example, cyclohexyl / benzothiazylsulfenamide, N-oxydiethylene / benzothiazyl-2-sulfenamide, Nt-butyl-2-benzothiazolesulfenamide, 2- (thymolpolynyl / dithio) benzo Thiazole), thiurams (eg tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide) , Dithioacid salts (for example, Zn-dimethyl dithiocarbamate, Zn-diethyl dithiocarbamate, Zn-di-n-butyl dithiocarbamate, Zn-ethyl phenyl dithiocarbamate, Te-diethyl dithiocarbamate, Cu- Examples thereof include dimethyl / dithiocarbamate, Fe-dimethyl / dithiocarbamate, pipecoline / pipecholyl / dithiocarbamate), and thiourea (for example, ethylene / thiourea, diethyl / thiourea).
[0009]
It is desirable to use a vulcanization acceleration aid (activator) in the adhesive composition. As the vulcanization acceleration aid, a general rubber aid can be used, and examples thereof include zinc white (about 1 to 10 phr), stearic acid, oleic acid (about 0.5 phr to 10 phr) and the like.
[0010]
Moreover, it is preferable to use a tackifier (tackifier) for the adhesive composition.
As the tackifier, any one used for general pressure-sensitive adhesives, adhesives and the like can be used, for example, about 10 to 200 phr. Specifically, for example, (a) rosin resin (gum rosin, tall oil rosin, wood rosin and other rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as maleated rosin), rosin glycerin ester (ester) Gum), rosin esters such as hydrogenated rosin and glycerin ester; and (b) resins having polar groups such as terpene phenol resins, and resins having no polar groups, such as α-pinene, β-pinene, and dipentene (limonene). Terpene resins such as main substances; and natural products such as aromatic hydrocarbon-modified terpene resins and derivatives thereof; and (c) petroleum resins such as aliphatic, alicyclic, and aromatic; and (d) coumarone indene Resin; (e) Polymer resin such as styrene resin such as styrene or substituted styrene, or (f) Al Examples thereof include phenol resins such as killed phenol resins and rosin-modified phenol resins; and (g) condensation resins such as xylene resins.
[0011]
As a thermoplastic resin film material which comprises the laminated body and tire in this invention, the following thermoplastic resins and arbitrary resin mixtures containing these or these can be mentioned, for example.
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 Polymer, nylon 66 / PPS copolymer), polyester resin (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), poly Butylene naphthalate (PBN), liquid crystal polyester, Aromatic polyesters such as reoxyalkylene diimide diacid / polybutyrate terephthalate copolymer), polynitrile resins (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene) Copolymer, methacrylonitrile / styrene / butadiene copolymer), polymethacrylate resin (eg polymethyl methacrylate (PMMA), polymethacrylate ethyl), polyvinyl resin (eg vinyl acetate, polyvinyl alcohol (PVA)) ), Vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PDVC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate Coalescence), cellulosic resins (eg cellulose acetate, cellulose acetate butyrate), fluorine resins (eg polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotetrafluoroethylene (PCTFE), tetrafluoroethylene / ethylene co-polymer) Polymer (ETFE)), imide resins (for example, aromatic polyimide (PI)), and the like.
[0012]
Moreover, as a thermoplastic resin film used for this invention, the film which blended the elastomer with said thermoplastic resin may be sufficient.
As the elastomer component that can be blended with the thermoplastic resin, if it has a composition in a state of being blended with the thermoplastic resin component and has a predetermined air permeability coefficient and Young's modulus as a result, the kind and amount thereof are used. Is not particularly limited.
[0013]
Examples of the elastomer blended with the thermoplastic resin include diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR (high diss BR and low cis BR), NBR, hydrogenation) NBR, hydrogenated SBR), olefin rubber (for example, ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), 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), CR, hydrin rubber (CHR / CHC), chlorosulfonated Polyethylene (CSM), chlorinated polyethylene (CM), male 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 (eg, styrene elastomer, olefin elastomer, ester elastomer, urethane) Elastomers, polyamide-based elastomers), and the like.
[0014]
When the compatibility between the specific thermoplastic resin and the elastomer component is different, it is preferable to add an appropriate compatibilizer as the third component. By mixing a compatibilizer with the system, the interfacial tension between the thermoplastic resin and the elastomer component decreases, and as a result, the rubber particles forming the dispersion layer become finer, so the characteristics of both components are more It will be expressed effectively. Such a compatibilizing agent is generally a copolymer having both or one structure of a thermoplastic resin and an elastomer component, or an epoxy group, a carbonyl group, a halogen group, an amino group capable of reacting with the thermoplastic resin or the elastomer component. A copolymer having a group, an oxazoline group, a hydroxyl group and the like can be taken. These may be selected according to the kind of the thermoplastic resin and the elastomer component to be mixed, and those usually used include styrene / ethylene butylene block copolymer (SEBS) and its maleic acid modified product, EPDM: EPDM / Examples thereof include styrene or EPDM / acrylonitrile graft copolymer and a maleic acid modified product thereof, styrene / maleic acid copolymer, and reactive phenoxin. The amount of the compatibilizing agent is not particularly limited, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer component (total of the thermoplastic resin and the elastomer component).
[0015]
The composition ratio between the specific thermoplastic resin (A) and the elastomer component (B) when blending the thermoplastic resin and the elastomer is not particularly limited, and the balance of film thickness, air permeation resistance, and flexibility is not limited. The weight ratio (A) / (B) is preferably 10/90 to 90/10, more preferably 15/85 to 90/10.
[0016]
The thermoplastic elastomer composition according to the present invention is mixed with the above-mentioned essential polymer component and other polymers such as the compatibilizer polymer as long as the necessary characteristics of the thermoplastic elastomer composition for tire according to the present invention are not impaired. can do. The purpose of mixing other polymers is to improve the compatibility between the thermoplastic resin and the elastomer component, to improve the film molding processability of the material, to improve heat resistance, to reduce costs, etc. Examples of the material used include polyethylene (PE), polypropylene (PP), polystyrene (PS), ABS, SBS, and polycarbonate (PC). Moreover, olefin copolymers, such as polyethylene and polypropylene, the maleic acid modified body, the glycidyl group introduction body, etc. can be mentioned. The thermoplastic elastomer composition according to the present invention further includes a filler, carbon black, quartz powder, calcium carbonate, alumina, titanium oxide, etc., which are generally blended in polymer blends, with a predetermined air permeability coefficient and Young's modulus. As long as it does not impair the above requirements, it can be optionally blended.
[0017]
The elastomer component can also be dynamically vulcanized when mixed with a thermoplastic resin. The vulcanizing agent, vulcanization aid, vulcanization conditions (temperature, time), etc. when dynamically vulcanizing may be appropriately determined according to the composition of the elastomer component to be added, and are not particularly limited. .
A general rubber vulcanizing agent (crosslinking agent) can be used as the vulcanizing agent. Specific examples of the ionic vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like. About [parts by weight per 100 parts by weight of rubber component (polymer)] can be used.
[0018]
Organic peroxide-based vulcanizing agents include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2, Te-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe Examples of thiourea-based vulcanization accelerators such as dimethyldithiocarbamate and pipecoline pipecolyldithiocarbamate include ethylenethiourea and diethylthiourea.
[0019]
Moreover, as a vulcanization | cure acceleration | stimulation adjuvant, the general rubber adjuvant can be used together, for example, zinc white (about 5 phr), stearic acid, oleic acid, and these Zn salts (about 2-4 phr) Etc. can be used.
A thermoplastic elastomer composition is produced by melt-kneading a thermoplastic resin component and an elastomer component (unvulcanized product in the case of rubber) in advance using a twin-screw kneading extruder or the like to form a continuous phase (matrix phase). By dispersing the elastomer component as a dispersed phase (domain) in the thermoplastic resin. When the elastomer component is vulcanized, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer component. 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 component is not particularly limited, and a screw extruder, a kneader, a Banbury mixer, a biaxial kneading extruder, or the like can be used. In particular, it is preferable to use a twin-screw kneading extruder for kneading the thermoplastic resin and the elastomer component and for dynamic vulcanization of the elastomer component. Further, two or more types of kneaders may be used and kneaded sequentially. As conditions for melt kneading, the temperature may be higher than the temperature at which the thermoplastic resin melts. The shear rate during kneading is 1000 to 7500 sec.^-1Is preferred. 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 is then formed into a sheet-like film by extrusion molding or calendar molding. The method for forming a film may be a method for forming a film of a normal thermoplastic resin or thermoplastic elastomer.
[0020]
The film thus obtained has a structure in which the elastomer component (B) is dispersed as a dispersed phase (domain) in the matrix of the thermoplastic resin (A). By adopting a dispersion structure in such a state, thermoplastic processing is possible, and sufficient rigidity can be imparted to the film as the belt reinforcing layer by the sufficient flexibility and the effect of the resin layer as the continuous phase. At the same time, the molding processability equivalent to that of a thermoplastic resin can be obtained regardless of the amount of the elastomer component. Therefore, it can be formed into a film by an ordinary resin molding machine, that is, extrusion molding or calendar molding. It becomes possible.
[0021]
The thermoplastic resin film may be a single layer or a multilayer film provided with adhesive layers of polyolefin-based, aliphatic polyamide-based or urethane-based resins on both surfaces of the film as described in, for example, JP-A-6-40207. Further, as described in Japanese Patent Application No. 7-55929 filed by the applicant of the present application, one of the blends of at least two low-compatible thermoplastic resins produced by extrusion stretch molding It is also possible to use a film in which a flat polymer alignment product made of a low-breathing thermoplastic resin is dispersed in a matrix of another thermoplastic resin.
[0022]
When such a thermoplastic resin film is used as an air permeation preventive layer of a tire, the air permeation coefficient is 25 × 10^-12cc · cm / cm²・ Sec ・ cmHg or less, preferably 5 × 10^-12cc · cm / cm²・ Sec ・ cmHg or less. There is no particular lower limit of the air permeability coefficient, but in fact 0.05 × 10^-12cc · cm / cm²-Sec-cmHg. Air permeation amount is 25 × 10^-12cc · cm / cm²By making it sec or less cmHg, the thickness of the air permeation preventive layer can be made half or less of the thickness of the conventional air permeation preventive layer. On the other hand, the Young's modulus is 500 MPa or less, preferably 10 to 300 MPa, and the thickness is 0.02 to 1.0 mm, preferably 0.05 to 0.5 mm. If the Young's modulus exceeds 500 MPa, it is not preferable because it cannot follow the tire deformation during running.
[0023]
The unvulcanized rubber composition constituting the laminate and the tire in the present invention includes any rubber composition conventionally used as a rubber material for tires, such as NR, IR, BR, SBR, etc. A rubber composition obtained by adding compounding agents such as carbon black, process oil, and vulcanizing agent to diene rubber, halogenated butyl rubber, ethylene-propylene copolymer rubber, styrene elastomer and the like can be obtained.
In particular, since the vulcanizing agent or vulcanization accelerator in the unvulcanized rubber composition moves to the adhesive side and vulcanizes the adhesive, the unvulcanized rubber composition The vulcanizing agent or vulcanization accelerator therein is preferably one that easily migrates during vulcanization.
The rate of transfer varies depending on the solubility in the polymer, the concentration gradient, the molecular weight, etc. In particular, sulfur or a low molecular weight vulcanization accelerator can be sufficiently transferred into the adhesive during vulcanization.
[0024]
  The laminate according to the present invention is manufactured as follows.
  First, the prescribed styrenicAdhesive compositionTo the prescribedSulfur-based vulcanizing agentAlternatively, either a vulcanization accelerator is blended, and a predetermined tackifier and a vulcanization accelerator aid are blended and kneaded sufficiently. Next, this adhesive composition is formed into a film having a thickness of 5 to 100 μm, preferably 10 to 50 μm by extrusion molding, and is combined with a separately molded thermoplastic resin film by lamination. If it is 5 μm or less, it is difficult to form a film, and if it is 100 μm or more,Sulfur-based vulcanizing agentOr it is because a vulcanization accelerator cannot fully transfer into an adhesive. Moreover, this laminated body may obtain the said adhesive composition and a thermoplastic resin composition by a two-layer extrusion method. After this, this thermoplastic resin film /Adhesive composition filmIf the laminated body which consists of these is vulcanized together with a predetermined unvulcanized rubber composition, the laminated body of the present invention is obtained.
[0025]
The tire according to the present invention can also be manufactured by the following general method.
First, a belt-like object in which a predetermined thermoplastic resin film and a predetermined adhesive layer are laminated in advance is stuck in a cylindrical shape on a tire molding drum. On top of that, members used for normal tire production such as a carcass layer, a belt layer, a tread layer and the like made of an unvulcanized rubber composition are sequentially laminated, and the drum is removed to obtain a green tire. Next, this green tire is heated and vulcanized according to a conventional method to obtain a desired tire.
[0026]
【Example】
Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.
[0027]
The following commercial item was used for each compounding component used for the adhesive composition in the following Examples and Comparative Examples.
ESBS (epoxidized SBS): Epofriend 1010 (Daicel)
SBS (Styrene, Butadiene, Styrene): Toughprene 315 (Asahi Kasei)
SEPS (styrene / ethylene / propylene / styrene): Septon 2063 (Kuraray)
Epoxidized ethylene vinyl acetate: Bond First 20B (manufactured by Sumitomo Chemical)
Maleic acid-modified ethylene ethyl acrylate: N polymer A1600 (manufactured by Nippon Petrochemical)
Rosin ester: Pencel AD (Arakawa Chemical)
Sulfur: Powdered sulfur (manufactured by Karuizawa Refinery)
TOTN: Noxeller TOT-N (Ouchi Shinsei Chemical)
CZ: Noxeller CZ-G (Ouchi Shinsei Chemical)
Zinc flower: Zinc flower # 3 (manufactured by Shodo Chemical)
Stearic acid: Bead stearic acid (manufactured by NOF Corporation)
[0028]
Preparation of adhesive composition
The blending components shown in Table I were dry blended, then charged into a biaxial kneader and kneaded at 110 ° C. The kneaded product was extruded into a strand shape, cooled with water, and then pelletized with a resin pelletizer. Thus, the adhesive composition of Examples 1-7 and Comparative Examples 1-4 was prepared.
[0029]
The physical property test (melt viscosity, film moldability, adhesive strength, tack force) of the adhesive composition obtained above and its application test were carried out and evaluated as follows.
[0030]
Melt viscosity test
The melt viscosity of the adhesive is a capillary rheometer (manufactured by Toyo Seiki) at a temperature of 120 ° C. and a shear rate of 250S.^-1It measured on condition of this.
The die used has an orifice with a diameter of 1 mm and a length of 10 mm.
[0031]
Film formability test
A T-shaped die having a width of 400 mm was attached to the tip of an extruder at 110 ° C., and the adhesive was extruded to a thickness of 30 μm to form a film.
At this time, a case where the 30 μm adhesive film could be formed without any problem was indicated as “◯”, and a case where a 30 μm film could not be formed was indicated as “X”.
[0032]
Adhesion test
(1) Film formulation and preparation method
(With film)
<Thermoplastic resin component>
Nylon 11: 30 parts by weight
Nylon 6/66: 10 parts by weight
<Elastomer component>
Br-IPMS: 60 parts by weight
<Vulcanization component>
ZnO: 0.3 part by weight
Zinc stearate: 1.2 parts by weight
Stearic acid: 0.6 parts by weight
(note)
Nylon 11: Rilsan BMN O (manufactured by Atchem)
Nylon 6/66: Amilan CM6001
Br-IPMS: EXXPRO 98-4 (Exxon Chemical)
ZnO: Zinc Hana 3 (manufactured by Shodo Chemical)
Zinc stearate: (manufactured by Shodo Chemical)
Stearic acid: beads stearic acid NY (manufactured by NOF Corporation)
(Preparation of film)
In advance, Br-IPMS and a vulcanizing agent component are kneaded for 4 minutes with a Banbury mixer, and then the elastomer component is pelletized with a rubber pelletizer. Further, the thermoplastic resin component and rubber pellets were dry blended and put into a biaxial kneader set at 230 ° C. A thermoplastic elastomer composition is obtained by vulcanizing the elastomer component while sufficiently kneading the elastomer component and the thermoplastic resin. This thermoplastic elastomer composition was molded into a 100 μm film using a 400 mm wide T-die extruder.
The film thus produced has a Young's modulus of 50 MPa and an air permeability of 17 × 10.^-12cc ・ cm / cm²-It was s.cmHg.
[0033]
(2) Carcass rubber compounding and preparation method
(Carcass rubber compounding)
NR: 65 parts by weight
SBR: 20 parts by weight
BR: 15 parts by weight
Carbon black (FEF): 50 parts by weight
Aroma oil: 8 parts by weight
ZnO: 5 parts by weight
Stearic acid: 3 parts by weight
RD: 1 part by weight
DM: 1 part by weight
Sulfur: 2 parts by weight
(note)
NR: RSS # 1
SBR: Nipol 1502 (manufactured by Nippon Zeon)
BR: Nipol BR1220 (manufactured by Nippon Zeon)
Carbon black (FEF): HTC100 (manufactured by Chubu Carbon)
Aroma oil: Komolex 300 (manufactured by Nippon Oil)
ZnO: Silver galore zinc (made by Toho Zinc)
Stearic acid: LUNAC YA (manufactured by Kao)
RD (Anti-aging agent): NOCRACK 224 (manufactured by Ouchi Shinsei Chemical)
DM (vulcanization accelerator): Noxeller DM (manufactured by Ouchi Shinsei Chemical)
Sulfur: Powdered sulfur (manufactured by Karuizawa Refinery)
(Preparation of rubber sheet for carcass)
A master batch was prepared by mixing the above rubber composition for carcass with a closed mixer and raw materials other than zinc white, vulcanization accelerator and sulfur. The standard mixing time was 3.5 minutes and the discharge temperature was 150 ° C. The remaining compounding agents were added to the master batch with an open roll to prepare an unvulcanized test rubber sheet.
[0034]
(3) Test method
The sample for bonding was a laminate of fabric reinforced rubber / carcass rubber / adhesive / film / cloth reinforced rubber, which was vulcanized at 180 ° C. for 10 minutes, and the vulcanized laminated sheet was strip-shaped with a width of 25 mm. Disconnected. The strip-shaped sample was attached to a peel test apparatus, and the peel strength between the test film and the test rubber was measured by setting the moving speed of the gripping tool of the tester to 50.0 ± 5.0 mm / min. Other tests were in accordance with JIS K6256.
[0035]
Adhesion test
A two-layer film is prepared by laminating a T-die film with an adhesive of Table I on the thermoplastic elastomer film prepared in advance and laminating it with a hot roll at 90 ° C. Then, this two-layer film was attached to the upper sample attachment position of the measuring instrument, and the adhesive force was adhered to the carcass placed on the lower part of the film, and the force when peeling it was taken as the tack force. Measurement was performed under the following conditions using a PICMA tack tester manufactured by Toyo Seiki Seisakusho.

[0036]
Foaming state test during vulcanization
A two-layer film composed of the above thermoplastic elastomer composition and an adhesive was laminated together with the carcass rubber on the adhesive side, and vulcanized at 180 ° C. for 10 minutes.
After vulcanization, the case where the adhesive was not foamed at all was marked with ◯, and the case where foaming was observed was marked with x.
[0037]
Tire durability test
The test tire was produced as follows.
A two-layer film composed of the thermoplastic elastomer composition and the adhesive is attached to a cylinder on a tire molding drum with the thermoplastic elastomer composition side facing inward. On top of that, members used for normal tire production such as a carcass layer, a belt layer, a tread layer and the like made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, this green tire was heated and vulcanized according to a conventional method to produce a desired pneumatic tire.
Next, the durability test uses a 165SR13 steel radial tire (rim 13 × 4 1 / 2-J), with an air pressure of 200 kPa and is mounted on a 1500cc class passenger car. And drive 20,000km on the actual road.
After running, the tire is removed from the rim, and the liner layer on the inner surface of the tire is visually observed. If the liner layer has cracks, visible wrinkles, and the liner layer is peeled or lifted, the liner layer is judged to be rejected (x), and the liner layer is judged to be acceptable (◯).
[0038]
Examples 1-7 and Comparative Examples 1-4
Table I shows the measurement and evaluation results using the various adhesive compositions described above.
[0039]
[Table 1]

[0040]
[Table 2]

[0041]
  based on the above results,Double bondA styrenic copolymer havingSulfur-based vulcanizing agentOr, by combining the vulcanization accelerator, a laminate without foaming can be obtained, and it can be seen that this is excellent in durability as a tire.
  On the other hand, as in Comparative Example 1.2, only with a polymer that is not crosslinked,Adhesive compositionOr as in Comparative Example 4Sulfur-based vulcanizing agentIf you do not enterAdhesive compositionHowever, foaming occurs during the vulcanization of the laminate, and this causes the film to break during the durability test.
  Furthermore, as in Comparative Example 3,Sulfur-based vulcanizing agentWhen both vulcanization accelerators are added, biaxial kneading,Adhesive compositionIt was observed that the cross-linking had already started and even filming was not possible when mixing.
[0042]
【The invention's effect】
As described above, when the adhesive composition according to the present invention is used, a stable adhesive film without foaming can be formed, and this can be used as a bonding layer between a thermoplastic resin film and a rubber member. If it becomes the laminate and tire used for joining between, there will be no film cracks etc. due to the adhesive adhesive grain part, foam part at the joint part, and to obtain a highly reliable product with high adhesive strength Can do.

Claims (3)

  A: A thermoplastic resin obtained by integrating a thermoplastic resin film and C: an unvulcanized rubber composition through B: an adhesive composition containing a styrene copolymer having a double bond during vulcanization In the method for producing a film-vulcanized rubber composition laminate, either one of a sulfur-based vulcanizing agent and a vulcanization accelerator is previously added to the adhesive composition B, and the unvulcanized C A method for producing a thermoplastic resin film-vulcanized rubber composition laminate, wherein the other rubber is mixed in the other rubber composition. The thermoplastic resin film is obtained by kneading an unvulcanized rubber component in a thermoplastic resin component, adding a vulcanizing agent under the kneading, and vulcanizing the rubber component, thereby vulcanizing rubber in the thermoplastic resin matrix. The method for producing a thermoplastic resin film-vulcanized rubber composition laminate according to claim 1, which is a thermoplastic elastomer composition film in which components are dispersed.   A tire using a thermoplastic resin film-vulcanized rubber composition laminate obtained by the production method according to claim 1 or 2.