JP5631800B2 - tire - Google Patents

Description

  The present invention relates to a tire, and more particularly to a tire related to improvement of heat-resistant adhesion in a reinforcing material.

  Polyethylene terephthalate (PET) has high strength per weight and is inexpensive, so it is used as a general-purpose cord for tire reinforcement. When a cord made of organic fibers such as PET is used as a tire reinforcing material, generally, after the cord is dipped in an adhesive such as a resorcin / formalin / latex (RFL) adhesive, Coat and apply to tire as rubber-cord composite. However, since the surface of polyester fiber such as PET has few reactive sites due to its chemical structure, it is difficult to ensure the adhesive force between the filament and the adhesive in the composite process of cord and rubber. there were.

  As a technique for further improving the adhesion between PET and rubber, for example, Patent Document 1 discloses a two-bath treatment in which PET is once immersed in an epoxy adhesive and then immersed again in an RFL adhesive. Yes. Further, improvement of epoxy adhesives has also been studied. For example, Patent Document 2 discloses a water-soluble polymer, an organic polyisocyanate containing a structure in which aromatics are methylene-bonded, and a plurality of active hydrogens. An epoxy-based adhesive composition containing an aqueous urethane compound obtained by reacting a compound having a thermal decomposition with a component containing a heat dissociable blocking agent is disclosed.

JP 2000-355875 A JP 2001-98245 A

  According to the two-bath treatment proposed in Patent Document 1 and the epoxy adhesive composition proposed in Patent Document 2, the adhesion between PET and rubber can be improved. However, when using a tire in a high-speed environment or a high-load environment, stronger adhesion under the input of dynamic strain, particularly heat-resistant adhesion, is required between the polyester fiber and rubber. The establishment of new technology was expected.

  Therefore, an object of the present invention is to provide a tire having improved durability by using a polyester cord improved in heat-resistant adhesion with rubber as a reinforcing material.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a conventional method by twisting a predetermined polyester filament into a cord and then performing an adhesive treatment with a predetermined epoxy adhesive composition. As a result, it was possible to realize a dramatic improvement in dynamic adhesiveness (heat resistant adhesiveness) that could not be achieved, and by using this as a reinforcing material for tires, the durability of the tires could be improved, leading to the completion of the present invention. It was.

That is, the tire of the present invention is a tire in which a rubber-cord composite made of polyester cord and rubber is used as a reinforcing material,
The polyester cord is subjected to an adhesive treatment with an adhesive composition after twisting polyester filaments,
The polyester filament is a fiber made of polyester having an intrinsic viscosity of 0.85 or more, the main repeating unit of which is ethylene terephthalate, and the amount of terminal carboxy groups in the fiber is 20 equivalents / ton or more, and X-ray small angle diffraction A long period of 9 to 12 nm, a polyester fiber formed by attaching a surface treatment agent having an epoxy group to the fiber surface, and
The adhesive composition comprises (A) an ethylenic addition polymer containing a 2-oxazoline group or a (blocked) isocyanate group, or a thermoplastic polymer polymer comprising a urethane polymer containing a hydrazino group. (B) a reaction product of (B) a water-soluble polymer comprising a copolymer comprising maleic anhydride units and isobutylene units or a derivative thereof; and (C) diphenylmethane diisocyanate and a thermally dissociable blocking agent for isocyanate groups. , A condensate of resorcin and formaldehyde obtained by a novolak reaction, a condensate of chlorophenol, resorcin and formaldehyde, a compound comprising an epoxy cresol novolac resin, or an organic polyisocyanate having a structure in which aromatics are bonded with methylene Multiple active hydrogens An aqueous urethane compound obtained by reacting a thermally dissociative blocking agent to the compound and the isocyanate groups with and is characterized in that it comprises, and (D) an aliphatic epoxide compound.

In the tire of the present invention, it is preferable that the polyester cord is further subjected to an adhesive treatment with a resorcin / formaldehyde / latex adhesive composition. In the present invention, the adhesive composition further includes at least one selected from the group consisting of (E) a metal salt, (F) a metal oxide, and (G) a rubber latex. Can do. Furthermore, in this invention, it is preferable that the terminal carboxy group amount of the fiber surface of the said polyester fiber is 10 equivalent / ton or less, and the crystal | crystallization size of the fiber horizontal axis direction of the said polyester fiber is 35-80 nm < ² >. preferable. Furthermore, the amount of terminal methyl groups in the fiber of the polyester fiber is preferably 2 equivalent / ton or less, and the titanium oxide content in the fiber of the polyester fiber is preferably 0.05 to 3.0. The epoxy index on the fiber surface of the polyester fiber is preferably 1.0 × 10 ⁻³ equivalent / kg or less.

  The tire of the present invention preferably has a carcass ply extending in a toroidal shape between a pair of left and right bead portions as a skeleton, and at least one layer of a belt disposed on the outer side in the radial direction of the crown portion of the carcass, An at least one cap layer disposed on the outer side in the tire radial direction of the belt and covering the entire width of the belt; and at least a pair of layer layers covering both ends of the belt in the width direction, wherein the reinforcing material includes the cap It can be used for either or both of the layer and the layer layer.

  According to the present invention, with the above-described configuration, it is possible to realize a tire with improved durability.

It is a width direction sectional view showing an example of the tire of the present invention. It is process drawing which shows the preparation methods of the cord for tire reinforcement in an Example. It is sectional drawing which shows the rubber test piece used for the dynamic adhesion test in an Example. It is a schematic explanatory drawing which shows the dynamic adhesion test method in an Example.

Hereinafter, preferred embodiments of the present invention will be described in detail.
FIG. 1 is a cross-sectional view in the width direction showing an example of the tire of the present invention. The illustrated tire has a pair of left and right bead portions 11 and a pair of sidewall portions 12 in which the bead cores 1 are embedded, and a tread portion 13 connected to both sidewall portions 12, and spans between the pair of left and right bead cores 1. One carcass ply 2 extending in a toroidal shape and reinforcing these parts is provided. Further, on the outer side in the tire radial direction of the crown portion of the carcass ply 2, two layers of belts 3 a and 3 b made of rubberized layers of reinforcing cords arranged to be inclined with respect to the tire circumferential direction, and substantially in the tire circumferential direction. Belt reinforcing layers 4 and 5 made of rubberized layers of organic fiber cords arranged in parallel are arranged. An insert 6 is disposed outside the carcass ply 2 in the bead portion 11.

  In the tire of the present invention, a rubber-cord composite composed of a polyester cord formed by twisting a specific polyester filament and then subjected to an adhesive treatment using a specific adhesive composition and rubber is used as a reinforcing material. It has a feature in that. Specifically, in the tire of the present invention, a specific polyester filament having a specific epoxy-based surface treatment agent attached to the fiber surface is used as a polyester filament used as a reinforcing material, and a specific epoxy is used as an adhesive composition. A system adhesive composition is used. By adopting such a configuration, it is possible to obtain a polyester cord with improved adhesion to rubber, which has been difficult to secure in the past, especially when high heat is generated when high load dynamic strain is repeatedly input. It is possible to dramatically improve the adhesion between the rubber and the polyester cord. Therefore, in this invention, it became possible to implement | achieve the tire which improved durability by applying this polyester cord to the reinforcing material.

First, the polyester filament used in the present invention will be described.
The polyester filament used in the present invention is a fiber made of polyester having an intrinsic viscosity of 0.85 or more, the main repeating unit of which is ethylene terephthalate, the amount of terminal carboxy groups in the fiber being 20 equivalents / ton or more, and X The long period by the small-angle diffraction is 9 to 12 nm, and is made of a polyester fiber having a surface treatment agent having an epoxy group attached to the fiber surface.

  The intrinsic viscosity of the polyester fiber needs to be 0.85 or more, and preferably 1.10 or less. More preferably, a polyester fiber having an intrinsic viscosity of 0.90 to 1.00 is used. When the intrinsic viscosity is less than 0.85, the strength of the polyester fiber is not sufficient, and in particular, the strength reduction in the tire vulcanization process cannot be sufficiently suppressed.

  Moreover, in the said polyester fiber, the amount of terminal carboxy groups of the whole polymer is 20 equivalent / ton or more, and it is necessary for the surface treating agent which has an epoxy group to adhere to the fiber surface. Conventionally, in a polyester fiber used for tire reinforcement, it has been a general technique to keep the carboxy group of a polymer at 15 equivalent / ton or less for the purpose of improving its heat deterioration resistance. However, since the polyester fiber for tire reinforcement has a high need for maintaining adhesion to rubber in addition to maintaining the strength of the fiber, the long period by X-ray small angle diffraction is 9 to 12 nm as in the polyester fiber according to the present invention. The present inventors have found that a carboxy group amount of 20 equivalents / ton or more is most suitable for tire reinforcement when the surface is subjected to epoxy treatment. The upper limit of the amount of carboxy groups in the polymer is preferably 40 equivalents / ton or less, and more preferably 21 to 25 equivalents / ton.

  Here, the surface treatment agent having an epoxy group attached to the surface of the polyester fiber contains an epoxy compound which is one or a mixture of two or more epoxy compounds having two or more epoxy groups in one molecule. Those are preferred. More specifically, halogen-containing epoxies are preferred, and examples include those obtained by synthesis with epichlorohydrin polyhydric alcohols or polyhydric phenols, and compounds such as glycerol polyglycidyl ether are preferred. The adhesion amount of the surface treatment agent containing such an epoxy compound to the fiber surface is in the range of 0.05 to 1.5 mass%, preferably 0.10 to 1.0 mass%. The surface treatment agent may be mixed with a smoothing agent, an emulsifier, an antistatic agent, other additives and the like as necessary.

  Furthermore, in the said polyester fiber, it is necessary for the long period by X-ray small angle diffraction to be 9-12 nm. The long period by X-ray small angle diffraction here means the space | interval of the crystal | crystallization in the polyester polymer of a fiber longitudinal direction. This long period in the polyester fiber according to the present invention is characterized by a short point, and the number of tie molecules connecting the crystals increases, resulting in a high cooperation maintenance rate when used as a tire reinforcing fiber. You can keep it. Further, by setting the long period in the above range, the physical properties of the fibers can be made suitable for high modulus and low shrinkage tire reinforcing fibers. In general, the lower limit of the long period range is 9 nm. Suitably, the long period by the X-ray small angle diffraction of the said polyester fiber shall be the range of 10-11 nm.

  In the present invention, the amount of terminal carboxy groups on the fiber surface (raw yarn surface) of the polyester fiber is preferably 10 equivalents / ton or less. The carboxy group amount of the whole polymer in the polyester fiber according to the present invention is required to be 20 equivalents / ton or more as described above, but the carboxy group amount on the fiber surface is an epoxy compound attached to the fiber surface. It is preferable that it is below 10 equivalent / ton or less by reaction with this. Thus, when the carboxy group in the polymer reacts with the epoxy group on the fiber surface, the polyester resin according to the present invention has extremely excellent adhesive performance. At this time, if the amount of terminal carboxy groups on the fiber surface is excessively large, heat resistance and adhesiveness tend to decrease.

Further, the polyester fiber is preferably crystal size of the fiber transverse direction is in the range of 35~80nm ^2. The polyester fiber according to the present invention has a short period of 12 nm or less, which is the interval between crystals on the longitudinal axis of the fiber. However, in order to obtain a high-strength fiber, the size of the crystal is also necessary. The crystal size in the horizontal axis direction is preferably grown to 35 nm ² or more. However, even if the crystal size is too large, the fiber becomes stiff and the fatigue property is lowered. Therefore, the crystal size is preferably 80 nm ² or less. The crystal size in the fiber horizontal axis direction is more preferably in the range of 40 to 70 nm ² . As described above, the crystal grows in the horizontal axis direction of the fiber, so that the tie molecules easily develop in the horizontal axis direction of the fiber, so that a three-dimensional structure is constructed in the vertical and horizontal direction of the fiber for tire reinforcement. It becomes a particularly suitable fiber. Furthermore, by taking such a three-dimensional structure, the loss factor tan δ of the fiber is lowered. As a result, the amount of heat generated under repeated stress can be suppressed, and the adhesion performance after applying repeated stress can be kept high, which makes the fiber particularly preferable for tire reinforcement applications.

  Furthermore, in the said polyester fiber, it is preferable that the amount of terminal methyl groups in the fiber is 2 equivalent / ton or less, More preferably, a terminal methyl group shall not be contained. This is because the methyl group in the polyester polymer has low reactivity and does not react with the epoxy group at all, and therefore tends to inhibit the reaction between the carboxy group and the epoxy group effective for improving the adhesiveness. If the polymer constituting the fiber has no or few terminal methyl groups, high reactivity with the epoxy group in the surface treatment agent is ensured, and high adhesion and surface protection performance can be ensured. It becomes possible.

  Furthermore, in the said polyester fiber, it is preferable that the titanium oxide content in a fiber is 0.05-3.0 mass%. When the titanium oxide content is less than 0.05% by mass, the smoothing effect for dispersing the stress acting between the roller and the fiber in the stretching process or the like tends to be insufficient. There is a risk of increasing the strength. On the other hand, when the content of titanium oxide is more than 3.0% by mass, the titanium oxide acts as a foreign substance inside the polymer to obstruct stretchability, and the strength of the finally obtained fiber tends to decrease. .

Furthermore, in the said polyester fiber, it is preferable that the epoxy index in the fiber surface is 1.0 * 10 < ^-3 > equivalent / kg or less. In particular, the epoxy index per kg of the polyester fiber is preferably 0.01 × 10 ^{−3 to} 0.5 × 10 ⁻³ equivalent / kg. When the epoxy index of the fiber surface is high, there is a tendency that there are many unreacted epoxy compounds. For example, a large amount of viscous scum is generated in the twisting process, and the processability of the fiber decreases. At the same time, there arises a problem that causes a decrease in product quality such as twisted yarn spots.

  The strength of the polyester fiber is preferably in the range of 4.0 to 10.0 cN / dtex. If the strength is too low or too high, the end result tends to be inferior in durability in rubber. For example, if production is performed with a very high strength, yarn breakage tends to occur in the yarn making process, and there is a tendency for quality stability as industrial fibers to occur. Moreover, it is preferable that the dry heat shrinkage rate at 180 ° C. of the fiber is in the range of 1 to 15%. If the dry heat shrinkage is too high, the dimensional change during processing tends to be large, and the dimensional stability of a molded product using fibers tends to be inferior.

The polyester cord used in the present invention is subjected to an adhesive treatment with a specific epoxy adhesive composition after twisting. Next, the adhesive composition used in the present invention will be described.
The adhesive composition used in the present invention is a heat composed of (A) an ethylenic addition polymer containing a 2-oxazoline group or (blocked) isocyanate group, or a urethane polymer containing a hydrazino group. A plastic polymer, (B) a water-soluble polymer comprising a copolymer comprising maleic anhydride units and isobutylene units or a derivative thereof, and (C) a thermally dissociable blocking agent for diphenylmethane diisocyanate and isocyanate groups Reaction product of the product, a condensate of resorcin and formaldehyde obtained by a novolak reaction, a condensate of chlorophenol, resorcin and formaldehyde, a compound comprising an epoxy cresol novolac resin, or a structure in which aromatics are methylene-bonded Organic polyisocyanates An aqueous urethane compound obtained by reacting a thermally dissociative blocking agent to the compound and the isocyanate groups with a plurality of active hydrogen, include those containing, and (D) an aliphatic epoxide compound.

  (A) The thermoplastic polymer is a main chain having an acrylic polymer, a vinyl acetate polymer, an ethylenic addition polymer such as a vinyl acetate / ethylene polymer, or a urethane-based polymer mainly composed of a linear structure. Of high molecular weight polymer. Further, when the main chain of the thermoplastic polymer is composed of an ethylenic addition polymer, the thermoplastic polymer is substantially composed of a monomer-derived unit having one carbon-carbon double bond. It is preferable that the carbon-carbon double bond having a hydrogen group at the allyl position having sulfur reactivity to be introduced is 10% or less in terms of the monomer composition ratio. The functional group having crosslinkability as a pendant group of the thermoplastic polymer is an oxazoline group or a (blocked) isocyanate group. Further, the thermoplastic polymer is preferably a polymer having a relatively high molecular weight region mainly composed of a linear structure, and particularly preferably has a weight average molecular weight of 10,000 or more in terms of polystyrene. . Furthermore, the thermoplastic polymer is preferably a molecule having a relatively low to medium molecular weight region, and particularly preferably has a molecular weight of 9,000 or less. Furthermore, the thermoplastic polymer is preferably composed of an ethylenic addition polymer containing a 2-oxazoline group as a pendant group. Furthermore, the thermoplastic polymer is a polyurethane polymer in which the main chain of the thermoplastic polymer is a polyurethane polymer mainly composed of a linear structure and contains a hydrazino group as a pendant group.

  The thermoplastic polymer is contained in the adhesive composition for the purpose of increasing the flexibility of the adhesive composition matrix that contains an aliphatic epoxide compound and a water-soluble polymer or aqueous urethane compound and tends to be hard. It is a thermoplastic resin. In rubber articles containing sulfur, if the main chain skeleton of the thermoplastic polymer is sulfur-reactive, the thermal degradation of the adhesion accompanying sulfur crosslinking increases, so in the present invention, the thermoplastic polymer is And a carbon-carbon double bond having a hydrogen atom at the allylic position. In addition, when the main chain skeleton of the thermoplastic polymer contains a crosslinkable functional group bonded as a pendant group, in particular, a group having a crosslinkable active hydrogen or carbonyl group on the surface of the synthetic resin, In addition to obtaining a bond between the coating layer of the adhesive composition and the surface of the synthetic resin, molecular flow at high temperatures is suppressed by intramolecular crosslinking and the like, and the adhesive strength at high temperatures is improved. An excessive amount of the crosslinking group is not preferable because the chemical heat resistance is lowered. The amount of the crosslinkable functional group contained in the thermoplastic polymer depends on the molecular weight of the main chain skeleton of the thermoplastic polymer, the type and molecular weight of the crosslinkable functional group as a pendant group. In general, the amount of the crosslinkable functional group is preferably in the range of 0.01 mmol / g to 6.0 mmol / g with respect to the total dry weight of the thermoplastic polymer.

  As described above, the thermoplastic polymer is mainly composed of a thermoplastic organic polymer widely used in various applications as an adhesive, a pressure-sensitive adhesive, a paint, a binder, a resin modifier, a coating agent, etc. The chain structure does not substantially contain a carbon-carbon double bond having a hydrogen atom at the allylic position as a reaction point of a crosslinking agent such as sulfur, and has a crosslinkable functional group as a pendant group. The thermoplastic polymer may have a carbon-carbon double bond when it has a structure other than the main chain, such as a side chain, but this double bond has low reactivity with sulfur. For example, an aromatic carbon-carbon double bond which is more stable by a resonance structure is preferable. In particular, industrially, as the thermoplastic polymer, an ethylenic addition polymer such as an acrylic polymer, a vinyl acetate polymer, and a vinyl acetate / ethylene polymer can be preferably used. In addition, thermoplastic organic polymers such as urethane polymer having a relatively high molecular weight region mainly composed of a linear structure are also present in the molecule due to the intermolecular secondary formed by urethane bonds or urethane bonds having high cohesive energy. It can be preferably used because of its high cohesive fracture resistance due to bonding and good durability.

Hereinafter, the main chain of the thermoplastic polymer will be described separately for (i) an ethylenic addition polymer and (ii) a urethane polymer.
(I) When the main chain of the thermoplastic polymer is an ethylenic addition polymer, the ethylenically unsaturated monomer having one carbon-carbon double bond and 2 carbon-carbon double bonds It is composed of at least one monomer-derived unit, and preferably, an addition-reactive carbon-carbon double bond is 10 mol% or less in terms of monomer composition based on the charged amount of all monomers. A polymer, preferably 0 mol%.

  In the case of a thermoplastic polymer having a main chain composed of an ethylenic addition polymer, the monomer constituting the main chain skeleton and an ethylenically unsaturated monomer having one carbon-carbon double bond, For example, α-olefins such as ethylene, propylene, butylene and isobutylene; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, monochlorostyrene, vinyltoluene, vinylnaphthalene, styrene and sodium sulfonate Ethyl carboxylic acids such as itaconic acid, fumaric acid, maleic acid, acrylic acid, methacrylic acid, butenetricarboxylic acid and salts thereof; acid anhydrides such as maleic anhydride and itaconic anhydride; methyl (meth) acrylate; Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) a Esters of unsaturated carboxylic acids such as methoxypolyethylene glycol laurate, 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate; itaconic acid monoethyl ester, fumaric acid monobutyl ester, maleic acid Monoesters of ethylenic dicarboxylic acid such as monobutyl ester; Diesters of ethylenic dicarboxylic acid such as itaconic acid diethyl ester and fumaric acid dibutyl ester; acrylamide, maleic acid amide, N-methylolacrylamide, N- (2-hydroxy Amides of α, β-ethylenically unsaturated acids such as ethyl) acrylamide, methacrylamide, N-methylol methacrylamide, N- (2-hydroxyethyl) methacrylamide, maleic amide; 2-hydroxyethyl (meth) Hydroxyl group-containing monomers such as acrylate and polyethylene glycol mono (meth) acrylate; Unsaturated nitriles such as acrylonitrile, methacrylonitrile, fumaronitrile and α-chloroacrylonitrile; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Vinyl ketone; Vinyl amide; , Halogen-containing α, β-unsaturated monomers such as vinylidene chloride, vinyl fluoride, vinylidene fluoride; vinyl compounds such as vinyl acetate, vinyl valerate, vinyl caprylate, vinyl pyridine; 2-isopropenyl-2 -Addition polymerizable oxazolines such as oxazoline; heterocyclic vinyl compounds such as vinylpyrrolidone; unsaturated bond-containing silane compounds such as vinylethoxysilane and α-methacryloxypropyltrimethoxysilane These may be used alone or in combination of two or more. It is preferable to obtain a thermoplastic polymer by radical addition polymerization of these monomers.

  In addition, as monomers constituting the main chain skeleton and containing two or more carbon-carbon double bonds, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 -Conjugated diene monomers such as halogen-substituted butadienes such as dimethyl-1,3-butadiene and chloroprene. Non-conjugated diene monomers include vinyl nobornene, dicyclopentadiene, 1 Non-conjugated diene monomers such as 1,4-hexadiene and the like may be used, and these may be used alone or in combination of two or more.

  A thermoplastic polymer having a main chain skeleton composed of an ethylenic addition polymer is a single polymer containing an ethylenically unsaturated monomer having one carbon-carbon double bond and two or more carbon-carbon double bonds. Preferably, a polymer having a sulfur-reactive carbon-carbon double bond in a monomer composition ratio of 10 mol% or less based on the charged amount of all monomers, preferably 0 mol%.

  The glass transition temperature of the thermoplastic polymer obtained by radical addition polymerization of the above monomer is preferably −90 ° C. or higher and 180 ° C. or lower, more preferably −50 ° C. or higher and 120 ° C. or lower, and still more preferably 0. It is not lower than 100 ° C and lower than 100 ° C. The reason for this is that when the glass transition temperature of the thermoplastic polymer is less than -90 ° C, the creep property at high temperature use becomes large, and when it exceeds 180 ° C, it becomes too hard. This is because the relaxability is reduced and the cord fatigue under high strain such as when using a tire is lowered.

  Examples of the functional group having crosslinkability introduced as a pendant group into the thermoplastic polymer obtained by radical addition polymerization include oxazoline group, epoxy group, aziridine group, carbodiimide group, bismaleimide group, blocked isocyanate group, hydrazino group. Group and epithio group. The reason for introducing the crosslinkable functional group is that the adhesiveness is improved by a cross-linking reaction with other adhesive composition components and adherend components that are in contact with the thermoplastic polymer.

  There is no particular limitation on the method of introducing a functional group having crosslinkability into a polymer obtained by radical addition polymerization to obtain a thermoplastic polymer. For example, an addition polymerizable monomer having an oxazoline, an addition polymerizable monomer having an epoxy group, an addition polymerizable monomer having a maleimide, an addition polymerizable monomer having a blocked isocyanate group, and an epithio group A method of copolymerizing an addition polymerizable monomer or the like when polymerizing the polymer obtained by the radical addition polymerization can be employed. (JP 2001-98245 [0061])

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立に水素、ハロゲン、アルキル、アラルキル、フェニルまたは置換フェニルであり、Ｒ^５は付加重合性不飽和結合を持つ非環状有機基である）により表される。 The addition polymerizable monomer having oxazoline as a pendant group has the following general formula:

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl, and R ⁵ is an acyclic organic group having an addition polymerizable unsaturated bond. Is).

  As monomers having oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. Among these, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

（式中、Ｒ^６は水素原子またはメチル基であり、Ｘは−ＯＢＯ−（但し、Ｂはハロゲン原子またはアルキル基で置換されていてもよい炭素原子数２〜１０のアルキレン基である）または−ＮＨ−であり、Ｙは芳香族ジイソシアネートのイソシアネート残基であり、Ｚはケトオキシムの水素残基である）で表される化合物が好ましい。 As an addition polymerizable monomer having a blocked isocyanate group as a pendant group, the following general formula:

Wherein R ⁶ is a hydrogen atom or a methyl group, and X is —OBO— (where B is an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom or an alkyl group) or -NH-, Y is an isocyanate residue of an aromatic diisocyanate, and Z is a hydrogen residue of ketoxime).

  The addition polymerizable monomer having a blocked isocyanate group as a pendant group can be obtained by subjecting a polymerizable monomer having an isocyanate group such as 2-methacryloyloxyethyl isocyanate to an addition reaction with a known blocking agent. Known blocking agents that block isocyanate groups include, for example, phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, phenols such as p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; aromatic secondary amines such as diphenylamine and xylidine; phthalimides; ε-caprolactam, δ -Lactams such as valerolactam; caprolactams such as ε-caprolactam; active methylene compounds such as malonic acid dialkyl ester, acetylacetone, acetoacetic acid alkyl ester; acetoxime, methyl ethyl Ketoximes, oximes such as cyclohexanone oxime; basic nitrogen compounds such as 3-hydroxypyridine and acidic sodium sulfite, and the like.

  As the above thermoplastic polymer, a thermoplastic polymer having an oxazoline group, which has good storage stability of the crosslinkable functional group during long-term storage, is preferably used.

  The thermoplastic polymer made of the above-mentioned ethylenic addition polymer is preferably water-dispersible or water-soluble because water that causes little environmental pollution can be used as a solvent. Particularly preferred is a water dispersible resin.

  (Ii) When the thermoplastic polymer is a urethane polymer, in the present invention, the main structure of the thermoplastic polymer is mainly polyisocyanate and two or more active hydrogens. It is a high molecular polymer having in its molecule a large number of bonds resulting from the reaction of isocyanate groups such as urethane bonds and urea bonds obtained by polyaddition reaction with a compound having an active hydrogen and active hydrogen. Not only bonds resulting from the reaction between isocyanate groups and active hydrogen, but also ester bonds, ether bonds, amide bonds, and uretdiones, carbodiimides, etc., produced by the reaction between isocyanate groups, contained in the active hydrogen compound molecule. Needless to say, it is a polymer that also contains.

  Moreover, a hydrazino group is mentioned as a crosslinkable functional group as a pendant group introduce | transduced into the urethane type polymer obtained by the said polyaddition polymerization. A hydrazino group is preferred because of its good adhesion.

  In addition, it is preferable that the thermoplastic polymer composed of the urethane polymer is water-based because water that causes less environmental pollution can be used as a solvent.

  As the polyisocyanate used for the synthesis of the urethane polymer in the present invention, conventionally used aromatic, aliphatic, and alicyclic organic polyisocyanates can be used. For example, toluene diisocyanate, diphenylmethane diisocyanate, 1 , 6-hexamethylene diisocyanate, 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyldiphenyl, 4,4 '-Diisocyanate, dianisidine isocyanate, m-xylene diisocyanate, hydrogenated xylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylene diisocyanate, isophor Diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexyl diisocyanate, lysine isocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, urethane-modified toluene diisocyanate, allophanate-modified toluene diisocyanate And isocyanate compounds such as burette-modified toluene diisocyanurate, isocyanurate-modified toluene diisocyanate, urethane-modified diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, acylurea-modified diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate. The present invention is not limited. Moreover, these may be used independently and may use 2 or more types together.

  The compound having two or more active hydrogens used for the synthesis of the urethane polymer in the present invention includes two or more hydroxyl groups, carboxyl groups, amino groups, mercapto groups, etc. Generally known polyethers, polyesters, polyether esters, polythioethers, polyacetals, polysiloxanes, etc., preferably polyethers or polyesters having two or more hydroxyl groups at the molecular ends. These compounds having two or more active hydrogens preferably have a molecular weight of 50 to 5,000.

  Specifically, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol 2,2-dimethyl-1,3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1, 2-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2- Methyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-2 5-hexanediol, 1,2-octanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, propylenediol, glycerin, trimethylolpropane, 1,2,6-hexane Low molecular polyols such as triol, hydrogenated bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A; 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,5 , 6-trimethoxy-3,4-dihydroxyhexanoic acid, low molecular polyols such as carboxy group-containing polyols such as 2,3-dihydroxy-4,5-dimethoxypentanoic acid.

  Polyether polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, ethylene oxide / propylene oxide copolymer, THF / ethylene oxide copolymer, THF / propylene oxide copolymer; dimethylol as high molecular weight polyols; Propionic acid, polyethylene adipate, poly (propylene adipate), poly-ε-caprolactone, and polyester polyols that are copolymers thereof; polyether polyols, polycarbonate polyols such as polycarbonate compounds, hydrocarbon backbone polyols, These polyadducts and the like can be mentioned, but are not limited thereto. Moreover, these may be used independently and may use 2 or more types together.

  As the compound having two or more active hydrogens used in the polyurethane polymer, it is preferable that at least one compound contains an aromatic or a compound having a structure in which an aromatic is methylene-bonded. . This is because adhesion to a polyester material or the like can be obtained by including a structure in which aromatics are bonded with methylene. A compound having a structure in which aromatics are connected by a bond other than methylene is also preferred because of the same effect.

  The specific method for synthesizing the urethane polymer having a hydrazino group as a pendant group is not particularly limited. Specifically, for example, first, a urethane polymer having a terminal isocyanate obtained by reacting a compound having two or more active hydrogens with an excess amount of polyisocyanate by a polyaddition reaction or the like is produced. After neutralization with a neutralizing agent such as a secondary amine, water is added to cause phase inversion, and chain extension and terminal isocyanate blocking are performed with polyfunctional carboxylic acid polyhydrazide.

  The reaction between the above-mentioned compound having two or more active hydrogens and an excess amount of polyisocyanate is carried out at room temperature or at a temperature of about 40 to 120 ° C. by a conventionally known single-stage or multi-stage isocyanate addition reaction method. It can be carried out. In the above reaction, a known catalyst such as dibutyltin dilaurate, stannous octoate or triethylamine, a reaction control agent such as phosphoric acid, adipic acid or benzoyl chloride, and an organic solvent which does not react with an isocyanate group may be used. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate; amide solvents such as N-methylpyrrolidone; toluene; xylene and the like Is mentioned.

  As a neutralizing agent used in the above reaction, ammonia, trimethylamine, triethylamine, tripropylamine, triethanolamine, monoethanolamine, N-methylmorpholine, morpholine, 2,2-dimethylmonoethanolamine, N, N- Examples include amines such as dimethyl monoethanolamine, sodium hydroxide, potassium hydroxide and the like. Examples of the polyfunctional carboxylic acid polyhydrazide used in the above reaction include oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide (ADH), sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumarate Acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 4,4'-oxybisbenzenesulfonylhydrazide, trimesic acid trihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH) Enocoic acid dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide, polyacrylic acid hydrazide, acrylamide-acrylic acid hydrazide copolymer, and the like. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH) are preferably used.

  Moreover, well-known chain extenders, such as N-alkyl dialkanolamines; dihydrazide compounds, such as diamine, a polyamine, N-methyldiethanolamine, can also be used as needed.

  The polymer obtained by polyaddition reaction of the above polyisocyanate and a compound having two or more active hydrogens preferably has a glass transition temperature of −90 ° C. or higher and 180 ° C. or lower, Preferably they are -50 degreeC or more and 120 degrees C or less, More preferably, they are 0 degreeC or more and 100 degrees C or less. This is because when the glass transition temperature of the urethane polymer is less than -90 ° C, the creep property at high temperature use increases, and when it exceeds 180 ° C, it becomes too hard, so the stress relaxation characteristic of soft thermoplastic resins This is because the property is reduced. Further, it is not preferable because cord fatigue under high strain such as when using a tire is lowered.

  The molecular weight of the urethane-based thermoplastic polymer thus obtained is Mw (weight average molecular weight) = 10,000 or more, more preferably 20,000 or more in terms of polystyrene converted by gel permeation chromatography. . The reason for this is that if the molecular weight is small, the improvement effect of absorbing the strain caused by the adhesion of the urethane polymer adhesive with the adhesive composition cannot be obtained. In addition, when an organic solvent is contained in the aqueous dispersion of the obtained urethane polymer, it can be distilled off under reduced pressure and heating conditions as necessary.

  (B) The water-soluble polymer is soluble in water or an aqueous solution containing an electrolyte. The water-soluble polymer contains a carboxyl group in the molecule. The main chain of the water-soluble polymer having a carboxyl group is an isobutylene-maleic anhydride copolymer or a derivative thereof. Furthermore, the water-soluble polymer according to the present invention may be a salt of the above compound. The water-soluble polymer can be used by dissolving in water, but it can also be used by dissolving it as a salt that is a neutralized product of a basic substance. Specific examples of the water-soluble polymer are isobutylene-maleic anhydride copolymers or neutralized products of these basic substances.

  The basic substance for neutralizing the water-soluble polymer is not particularly limited as long as it is a basic substance. For example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide are used. Ammonia; amines such as methylamine, ethylamine, propylamine, dimethylamine, triethylamine, monoethanolamine, diethanolamine; carbonates of alkali metals such as sodium carbonate and potassium carbonate; alkali metals such as sodium acetate and potassium acetate Acetic acid salt: Examples include alkali metal phosphates such as trisodium phosphate, among which sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, and triethylamine are preferably used. Particularly preferably, ammonia, trimethylamine, triethylamine and the like having a boiling point of 150 are scattered from a base containing an alkali metal component that has an action of hydrolyzing and degrading a resin material such as polyester and the like in a heating step after being applied to the resin material. A volatile base having a temperature of not higher than 100 ° C., particularly not higher than 100 ° C. is preferred.

  The structure of the water-soluble polymer is not particularly limited, and may be linear, branched, or two-dimensionally or three-dimensionally cross-linked. A polymer having only a linear or branched structure is preferred. As a characteristic of this polymer, it is preferable that the main chain is not spread as much as possible when blended with an aqueous solution of the adhesive composition or the like, but spreads as much as possible. By spreading the main chain in this way, the heat distortion resistance of the adhesive composition can be improved by the interaction between the carboxyl group and the adhesive matrix. In addition, when the water-soluble polymer is partially water-soluble, for example, even if it does not spread sufficiently, such as a colloidal dispersion, an effect can be obtained if it is partially compatible with the adhesive composition matrix. Can do. The water-soluble polymer is preferably composed of a monomer-derived unit having substantially one carbon-carbon double bond. The reason for this is that if the main chain skeleton is sulfur-reactive, the thermal deterioration of the adhesion accompanying sulfur cross-linking increases, and the molecular chain spreads and improves the compatibility in water. The water-soluble polymer is preferably a polymer having a relatively high molecular weight range, preferably has a weight average molecular weight of 3,000 or more, particularly preferably 10,000 or more, more preferably 80,000 or more. It is.

  The compound (C) is contained in the adhesive composition mainly for the purpose of promoting the adhesion to the resin material that is one adherend of the adhesive composition. The reason for including such a compound in the adhesive composition is as follows. A synthetic resin material such as a polyester resin as a base material is composed of a flat linear polymer chain, and this polymer chain has a π-electron atmosphere derived from aromatics contained therein. Therefore, when the component of the adhesive composition includes a molecular structure having aromatic π electrons on the molecular side surface, the π between the molecular structure portion and the π electronic atmosphere portion of the polymer chain of the resin. Due to the electronic interaction, effects such as adhesion of the adhesive composition to the resin surface and diffusion of the resin between the polymer chains can be easily obtained.

  Further, the polar functional group of the compound (C) is preferably a group that reacts with a carboxyl group, an epoxy group that is a crosslinkable component, a (blocked) isocyanate group, and the like contained in the adhesive composition. Specific examples include crosslinkable functional groups such as epoxy groups and (blocked) isocyanate groups, hydroxyl groups, amino groups, and carboxyl groups.

  The molecular structure of the compound (C) is preferably linear without branching. The molecular structure is preferably methylene diphenyl or polymethylene polyphenyl having a relatively linear molecular structure. The molecular weight of the molecular structure part in which the aromatics are methylene-bonded is not particularly limited, but is preferably 6,000 or less, more preferably 2,000 or less. This is because when the molecular weight exceeds 6,000, the molecular weight becomes too high, and the diffusibility to the base material becomes small although the anchoring effect is almost constant. In addition, the compound having a structure in which an aromatic compound having a polar functional group is bonded to a methylene bond is preferably a molecule having a relatively low to medium molecular weight range and a molecular weight of 9,000 or less. Furthermore, the compound having a structure in which an aromatic compound having a polar functional group is bonded with methylene is preferably aqueous (water-soluble or water-dispersible).

  Such a compound (C) is a reaction product obtained by blocking diphenylmethane diisocyanate with a heat dissociable blocking agent, a condensate of resorcin and formaldehyde obtained by a novolak reaction, a chlorophenol / resorcin / formaldehyde condensate, or an epoxy It is a cresol novolac resin having a group.

  Examples of the reaction product of diphenylmethane diisocyanate and a thermally dissociable blocking agent for isocyanate groups include reactants blocked with a known blocking agent that blocks isocyanate groups. Specifically, commercially available blocked polyisocyanate compounds such as Elastron BN69 and DELION PAS-037 can be used.

  Further, as a condensate of chlorophenol, resorcin and formaldehyde, specifically, as a resorcin / formaldehyde condensate obtained by a novolak reaction, a resorcin / formaldehyde obtained by a novolak reaction described in Examples of WO97 / 13818 As a formaldehyde condensate, a condensate of chlorophenol, resorcin, and formaldehyde, Denabond, Denabond-AL, Denabond-AF, etc. of Nagase Kasei Kogyo Co., Ltd. can be used.

  As the epoxy cresol novolak resin, commercially available products such as Araldite ECN1400 from Asahi Ciba Co., Ltd. and Denacol EM-150 from Nagase Chemical Industries, Ltd. can be used. Since this epoxy novolac resin is also an epoxide compound, it acts as an intermolecular crosslinking component of adhesive molecules that suppress fluidization of the adhesive composition at high temperatures. A compound obtained by sulfomethylating a phenol and a formaldehyde condensate is a compound obtained by heating and reacting a sulfomethylating agent before, during, or after the condensation reaction of a phenol and formaldehyde. Examples of the sulfomethylating agent include sulfurous acid, bisulfite and a salt of a basic substance. Specifically, sulfomethylated modified products of phenols and formaldehyde condensates described in Examples of Japanese Patent Application No. 10-203356 can be used.

  As the compound (C), organic polyisocyanates having a structure (molecular structure) in which aromatics are methylene-bonded (hereinafter also referred to as “aromatic methylene-bonded structure”), a compound having a plurality of active hydrogens, You may use the aqueous | water-based urethane compound obtained by making it react with the heat dissociable blocking agent with respect to an isocyanate group. This water-based urethane compound is included mainly for the purpose of promoting the adhesion of the adhesive composition to the synthetic resin, and not only as an adhesive improvement agent but also as a flexible crosslinking agent. It can also be expected to inhibit fluidization of molecular chains at high temperatures. An aqueous urethane compound is a urethane reaction product obtained by reacting an organic polyisocyanate compound having a structure in which aromatics are methylene-bonded, and two or more structures in a molecule having aromatics methylene-bonded in the molecule. It is preferable to have.

  The reason why the aqueous urethane compound preferably contains a benzene ring or a structure having a methylene-bonded aromatic group in the molecule is as follows. Synthetic resin materials such as polyethylene terephthalate, which are the base material, consist of flat polymer chains, and the space between or between these polymer chains has a π-electron atmosphere derived from aromatics contained in the polymer chains. doing. Therefore, if the aqueous urethane compound contains a molecular structure having aromatic π electrons on the side surface, the molecular structure portion will adhere to the resin surface of the substrate due to π-electron interaction, Effects such as dispersion between molecular chains are easily obtained.

  The aromatic methylene bond structure is preferably methylene diphenyl or a polymethylene polyphenyl structure if it has a relatively linear molecular structure. The molecular weight of the aromatic methylene bond structure moiety is not particularly limited, but is preferably 6,000 or less, and more preferably 2,000 or less. This is because, when the molecular weight is higher than 6,000, the diffusibility to the base material becomes small although the anchoring effect is almost constant.

  In addition, an isocyanate compound having one aromatic methylene bond structure in the molecule, such as blocked methylene diphenyl diisocyanate, is expected to have a water-based urethane compound acting on the base material in order to expect a throwing effect between the base material and the adhesive layer. It is necessary to crosslink with other adhesive composition components. However, the water-based urethane compound having an aromatic methylene bond structure portion bonded at multiple positions in the molecule is not cross-linked or formed into an adhesive composition at a position other than the aromatic methylene bond structure portion acting on the substrate. This is preferable because mechanical anchoring and an adhesion promoting effect with relatively little loss can be obtained. Needless to say, a compound adhesion promoter having one aromatic methylene bond structure in the molecule can be added to the aqueous urethane compound to the adhesive composition of the present invention.

  Moreover, it is preferable that the aqueous | water-based urethane compound which is an adhesive improvement agent has a 2 or more thermally dissociable blocked isocyanate group in a molecule | numerator. This is because it can react with the active hydrogen present in the vicinity of the surface of a resin material such as polyethylene terephthalate as a base material, other adhesive composition components, or the rubber to be adhered, and adhesion can be promoted by crosslinking. The aqueous urethane compound preferably has a group capable of forming a salt or a hydrophilic group such as a hydrophilic polyether chain. This is because water that is hygienic advantageous can be used as a solvent.

  Examples of the thermally dissociable blocked isocyanate group blocking agent compound include known blocking agents for blocking the aforementioned isocyanate group.

  As a method for introducing a group capable of forming a salt or a hydrophilic group such as a hydrophilic polyether chain, for example, as a method for introducing an anionic hydrophilic group, after reacting a polyisocyanate and a polyol, the terminal A method of reacting a part of an isocyanate group with a salt of an organic acid having an active hydrogen, such as a sodium salt of aminosulfonic acid such as taurine, N-methyltaurine, N-butyltaurine, sulfanilic acid, and the like, and polyisocyanate and polyol In the step of reacting, a tertiary nitrogen atom is introduced by adding N-methyl-diethanolamine or the like in advance, and the tertiary nitrogen atom is quaternized with dimethyl sulfate or the like. For example, as a method for introducing a hydrophilic group such as a hydrophilic polyether chain, after reacting a polyisocyanate and a polyol, a part of the terminal isocyanate group has a molecular weight of 350 to 3,000. Examples thereof include a method of reacting a compound having at least one active hydrogen and a hydrophilic polyether chain, such as functional polyethylene glycol monoalkyl ethers (for example, Brox 350, 550, and 750 (manufactured by BPC Chemicals)). The hydrophilic polyether chains of these compounds contain at least 80%, preferably 100%, alkylene oxide units such as ethylene oxide and / or propylene oxide.

  The organic polyisocyanates used for the aqueous urethane compound include an aromatic methylene bond structure, and examples thereof include methylene diphenyl polyisocyanate and polymethylene polyphenyl polyisocyanate. A polymethylene polyphenyl polyisocyanate having a molecular weight of 6,000 or less is preferable, and a polymethylene polyphenyl polyisocyanate having a molecular weight of 40,000 or less is more preferable. (JP 2001-98245 [0093])

  The aqueous urethane compound preferably contains a structure in which aromatics are methylene-bonded, for example, an aromatic-containing organic polyisocyanate such as diphenylmethane diisocyanate or polyphenylene polymethylene polyisocyanate and a blocking agent. The aqueous urethane compound is preferably a molecule in a relatively low to medium molecular weight region, preferably a molecular weight of 9,000 or less, more preferably 5,000 or less. As the compound containing a blocking agent for aromatic polyisocyanate, a blocked isocyanate compound containing a known isocyanate blocking agent is preferred.

  The aqueous urethane compound is a urethane prepolymer having a free isocyanate group obtained by reacting an organic polyisocyanate compound having 3 to 5 functional groups with a compound having a molecular weight of 5,000 or less and 2 to 4 active hydrogens. Obtained by treating a polymer with a thermally dissociable blocking agent that blocks isocyanate groups, and a compound having at least one active hydrogen and at least one anionic, cationic or nonionic hydrophilic group, It is preferably an aqueous resin having two or more thermally dissociable blocked isocyanate groups and hydrophilic groups in one molecule.

  More preferably, the aqueous urethane compound has an organic polyisocyanate compound (α) having a molecular weight of 2,000 or less and a functional group number of 3 to 5, and 2 to 4 molecules having a molecular weight of 5,000 or less. 5 to 35% by mass of a compound (β) having active hydrogen, 5 to 35% by mass of a thermally dissociable isocyanate group blocking agent (γ), at least one active hydrogen and at least one anionic, cationic or non-active A water-soluble resin based on a reaction product of 5 to 35% by mass of a compound (δ) having an ionic hydrophilic group and 0 to 50% by mass of a compound (ε) containing active hydrogen other than these, The sum of the weight percentages of (α) to (ε) is 100 based on the weight of (α) to (ε), and the amount of these components is a thermally dissociable blocked isocyanate group (NCO, molecular weight = 42 and It is preferable Te calculation) is water-dispersible or water-soluble aqueous resin is selected to be from 0.5 to 11 mass%.

（式中、Ａは官能基数３〜５の有機ポリイソシアネート化合物のイソシアネート残基を示し、Ｙは熱処理によりイソシアネート基を遊離するブロック化剤化合物の活性水素残基を示し、Ｚは分子中、少なくとも１個の活性水素原子および少なくとも１個の塩を生成しうる基もしくは親水性ポリエーテル鎖を有する化合物の活性水素残基を示し、Ｘは２〜４個の水酸基を有し平均分子量が５，０００以下のポリオール化合物の活性水素残基であり、ｎは２〜４の整数であり、ｐ＋ｍは２〜４の整数（ｍ≧０．２５）である）で示される熱反応型水溶性ポリウレタン化合物であることが好ましい。 More preferably, the aqueous urethane compound has the following general formula:

(In the formula, A represents an isocyanate residue of an organic polyisocyanate compound having 3 to 5 functional groups, Y represents an active hydrogen residue of a blocking agent compound that liberates an isocyanate group by heat treatment, and Z represents at least in the molecule. 1 represents an active hydrogen residue of a compound having one active hydrogen atom and a group capable of forming at least one salt or a hydrophilic polyether chain, and X represents 2 to 4 hydroxyl groups and an average molecular weight of 5, Thermally reactive water-soluble polyurethane compound represented by an active hydrogen residue of a polyol compound of 000 or less, n is an integer of 2 to 4, and p + m is an integer of 2 to 4 (m ≧ 0.25) It is preferable that

Examples of the compound having an average molecular weight of 5,000 or less and 2 to 4 active hydrogens include compounds selected from the group consisting of the following (i) to (vii).
(I) polyhydric alcohols having 2 to 4 hydroxyl groups,
(Ii) polyvalent amines having 2 to 4 primary and / or secondary amino groups,
(Iii) amino alcohols having 2 to 4 primary and / or secondary amino groups and hydroxyl groups,
(Iv) polyester polyols having 2 to 4 hydroxyl groups,
(V) polybutadiene polyols having 2 to 4 hydroxyl groups and copolymers thereof with other vinyl monomers,
(Vi) polychloroprene polyols having 2 to 4 hydroxyl groups and copolymers thereof with other vinyl monomers,
(Vii) Polyether polyols having 2 to 4 hydroxyl groups, C2 to C4 alkylene oxide polyadducts of polyhydric amines, polyhydric phenols and amino alcohols, C2 of polyhydric alcohols of C3 or higher -C4 alkylene oxide polyadduct, C2-C4 alkylene oxide copolymer, or C3-C4 alkylene oxide polymer.
In the present invention, an active hydrogen residue of a polyol compound having 2 to 4 hydroxyl groups and an average molecular weight of 5,000 or less can be used, and particularly selected from the group consisting of the above (i) to (vii). The compound is not limited as long as it is a compound.

  Examples of the polyol compound having 2 to 4 hydroxyl groups and having an average molecular weight of 5,000 or less include the polyols described above for the thermoplastic polymer as long as the average molecular weight is 5,000 or less. It is done. Among these, if it is a polyol compound having a structure in which aromatics are methylene-bonded, such as an ethylene oxide adduct of bisphenol A, not only an organic isocyanate residue of an aqueous urethane compound but also an active hydrogen residue of a polyol A structure in which aromatics are bonded with methylene can be introduced. (JP 2001-98245 [0095])

  Furthermore, examples of the blocking agent compound that liberates isocyanate groups by the heat treatment include known isocyanate blocking agents.

  As a method for synthesizing the aqueous urethane compound, specifically, it can be produced by a known method such as the method described in JP-B 63-51474. In addition to the heat-reactive water-based urethane resin synthesized based on these methods, products such as Elastron BN27 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can also be used.

  (D) An aliphatic epoxide compound is included as a crosslinking agent of an adhesive composition. The aliphatic epoxide compound is a compound containing preferably 2 or more, more preferably 4 or more epoxy groups in one molecule. The reason for this is that as the epoxy group is more multifunctional, the effect of suppressing creep and flow due to stress in the high temperature region of the adhesive composition is higher, and the adhesive force at high temperature is higher.

  The compound containing two or more epoxy groups is preferably a reaction product of a polyhydric alcohol and epichlorohydrin. Examples of the aliphatic epoxide compound include glycidyl esters of fatty acids, glycidyl ethers of aliphatic polyhydric alcohols, and cyclic aliphatic epoxide compounds. As this epoxide compound, glycidyl ester of long chain fatty acid, glycidyl ether of polyhydric alcohol, etc., which are the above-mentioned flexible epoxy resins, are particularly preferably used.

  Specific examples of the aliphatic epoxide compound include diethylene glycol diglycidyl ether, polyethylene diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Reactive formation of polychloridyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether and epichlorohydrin Things.

  Of the reaction products of polyhydric alcohols and epichlorohydrin, polyglycerol / polyglycidyl ether and sorbitol / polyglycidyl ether are particularly preferable. The reason for this is that these compounds have a polyfunctional epoxy group, less flow due to stress in the adhesive layer at high temperatures, less decrease in high-temperature adhesion due to creep, and are flexible with a long-chain flexible main skeleton structure. Therefore, the occurrence of curing / shrinkage of the adhesive layer due to cross-linking is small, and the decrease in adhesive force due to internal strain stress is small. As these sorbitol / polyglycidyl ether, polyglycerol / polyglycidyl ether, and novolac type epoxy resin, commercially available chemicals can be used.

  Such aliphatic epoxide compounds can be used by dissolving in water or dispersing in water by emulsification. In order to obtain an emulsified liquid, for example, such a polyepoxide compound is dissolved in water as it is, or a solution obtained by dissolving it in a small amount of a solvent as necessary is used as a known emulsifier, for example, sodium alkylbenzenesulfonate, dioctylsulfosuccinate. It can be emulsified in water using sodium salt, nonylphenol ethylene oxide adduct and the like.

  The adhesive composition used in the present invention preferably further contains at least one selected from the group consisting of (E) a metal salt, (F) a metal oxide, and (G) a rubber latex. Among these, metal salts and metal oxides are included as fillers in the adhesive composition, so that the cost is good with an inexpensive filler and the ductility and toughness are imparted to the adhesive composition. Can be used.

  As (E) metal salt and (F) metal oxide, polyvalent metal salt and polyvalent metal oxide are preferable. The “metal” here includes boron and similar metals such as silicon. In addition to monovalent alkali such as sodium hydroxide, polyvalent metal salts and polyvalent metal oxides are preferable because they have a small deterioration effect such as alkali hydrolysis of a resin material serving as a base material such as polyester. The effect which bridge | crosslinks between the polymers containing the carboxyl group in an adhesive composition by an ion bond interaction can also be anticipated. Examples of polyvalent metal salts include sulfates, nitrates, acetates, carbonates, chlorides, hydroxides, silicates and the like that are divalent or higher, such as calcium, magnesium, zinc, barium, aluminum, iron, nickel, etc. Of the salt. As the polyvalent metal oxide, for example, magnesium, calcium, barium, zinc, aluminum, titanium, boron, silicon, bismuth, manganese, iron, nickel oxide, or these oxides are constituent elements. , Bentonite, silica, zeolite, clay, talc, satin white, smectite and the like. These fillers of metal salts and metal oxides are preferably added as fine particles to the adhesive composition, and the average particle diameter is preferably 20 μm or less, particularly preferably 1 μm or less. Further, the metal salt and the metal oxide can be used by being dispersed in water with a known surfactant or water-soluble polymer. In the present invention, a relatively stable aqueous dispersion is obtained by using a water-soluble polymer as its protective colloid, but the method is not particularly limited as long as it can be dispersed in water.

  (G) As rubber latex, well-known rubber latex can be used. For example, vinylpyridine-conjugated diene compound copolymer latex and modified latex thereof, styrene-butadiene copolymer latex and modified latex thereof, acrylonitrile-butadiene copolymer latex and modified latex thereof, natural rubber latex, etc. Can be contained in one kind or two or more kinds. As the modified latex, carboxylation modification or epoxy modification can be performed.

  As a compounding ratio of the adhesive composition used in the present invention, the content of the component (A) is 10 to 75 mass%, particularly 15 to 65 mass%, more preferably 20 to 55 mass% of the dry weight of the adhesive composition. %, The content of the component (B) is 5 to 75% by weight, particularly 15 to 60% by weight, more preferably 18 to 45% by weight of the dry weight of the adhesive composition, and the content of the component (C) is the adhesive. 15 to 77% by weight of the dry weight of the composition, in particular 15 to 55% by weight, more preferably 18 to 55% by weight, and the content of component (D) is 9 to 70% by weight of the dry weight of the adhesive composition; In particular, it is preferable to select 10 to 45% by mass, and further 15 to 30% by mass.

  Moreover, it is preferable that content of (E) component which is an arbitrary component is 50 mass% or less of the dry weight of an adhesive composition, More preferably, it is 3-40 mass%. Moreover, it is preferable that content of (F) component is 50 mass% or less of the dry weight of an adhesive composition, More preferably, it is 3-40 mass%. Furthermore, it is preferable that content of (G) component is 18 mass% or less of the dry weight of an adhesive composition, More preferably, it is 10 mass% or less.

  In the adhesive composition used in the present invention, in addition to the above components (A) to (G), solvents such as water and organic solvents, water-soluble and / or water-dispersible polyester resins, water-soluble and / or It may contain water-soluble resins such as water-dispersible nylon resins, water-based urethane resins having no crosslinking group, water-soluble cellulose copolymers, and water-dispersible resins. These water-soluble resins and water-dispersible resins are generally preferably contained at 30% by mass or less of the dry weight of the adhesive composition, but are not limited thereto.

  The adhesive composition includes a vulcanizing agent contained in any adherend such as an adhesive between an adherend of a synthetic resin material such as synthetic fiber and an adherend of a rubber composition containing sulfur. The effect is obtained in an adhesive method in which the adhesive composition is cross-linked with a vulcanizing agent by shifting to the composition.

  Examples of the vulcanizing agent include sulfur; thiuram polysulfide compounds such as tetramethylthiuram disulfide and dipentamethylenethiuram tetrasulfide, 4,4-dithiomorpholine, p-quinonedioxime, p, p′-dibenzoquinonedioxime, Organic vulcanizing agents such as cyclic sulfur imides can be mentioned.

  The adhesive treatment using the adhesive composition can be performed according to a conventional method, and is not particularly limited. Methods for coating the cord with the adhesive composition include dipping the cord in the adhesive composition, applying the adhesive composition with a brush, and spraying the adhesive composition. An appropriate method can be selected accordingly. The method for coating the cord surface with the adhesive composition is not particularly limited, but when the cord composition is coated on the cord surface, the adhesive composition is dissolved in various solvents to reduce the viscosity. Since application | coating becomes easy, it is preferable. Moreover, it is environmentally preferable that this solvent consists mainly of water.

  The cord after coating with the adhesive composition can be dried, for example, at a temperature of 100C to 210C. Thereafter, the subsequent heat treatment is performed at a temperature not lower than the glass transition temperature of the polymer of the resin material constituting the cord, preferably not lower than [melting temperature−70 ° C.] and not higher than [melting temperature−10 ° C.]. preferable. The reason for this is that the molecular mobility of the polymer is poor below the glass transition temperature of the polymer, and the adhesive composition and resin cannot be sufficiently interacted with the component that promotes adhesion in the adhesive composition. This is because the bonding strength with the material cannot be obtained. Such a resin material may be pretreated by an electron beam, microwave, corona discharge, plasma treatment or the like in advance. Further, the dry weight of the adhesive composition covering the cord is preferably 0.5 to 6.0 mass% with respect to the cord weight.

  In the present invention, it is preferable that the cord after the treatment with the epoxy adhesive composition is further subjected to an adhesive treatment with an RFL adhesive composition. After twisting, after the adhesive treatment with the epoxy adhesive composition described above, further treatment with an RFL adhesive can be performed, whereby more excellent dynamic adhesiveness can be expressed. Usually, when the number of times of the adhesive treatment process is increased, the cord physical properties are changed due to the influence of the heating process in the middle of the process, and it was considered unpreferable. A polyester cord excellent in dynamic adhesiveness to rubber can be obtained by combining an adhesive treatment with an epoxy adhesive composition and a cord treatment using an RFL adhesive with respect to a cord using a rubber.

  The adhesive treatment with the RFL adhesive can be carried out according to a conventional method and is not particularly limited. Examples of the RFL adhesive treatment liquid include resorcin / formalin initial condensate / rubber latex (for example, 30 to 60% emulsion of styrene butadiene latex, vinylpyridine / styrene / butadiene terpolymer latex, etc.) = 1: 2-1 : 20 (weight ratio) can be used. In addition to these components, if necessary, a blocked isocyanate aqueous dispersion containing a resorcin / formalin condensate obtained by a novolak reaction or methylenediphenyldipolyisocyanate, aroma An adhesion improver having a structure in which a methylene group is bonded to a family can be blended. When the cord is treated with the RFL adhesive treatment solution, the dry weight of the RFL adhesive composition covering the cord is 0.5 to 6.0 mass%, preferably 2 to 6 mass based on the cord weight. %. The cord after the treatment can be heat-treated at, for example, a temperature of 200 to 250 ° C. after drying at a temperature of 100 to 150 ° C., for example.

  As described above, the above-mentioned epoxy adhesive composition, and preferably a polyester cord obtained by subjecting the cord to an adhesive treatment with an RFL adhesive is embedded in unvulcanized rubber and added. A rubber-cord composite in which the cord and rubber are firmly bonded can be obtained by a method such as vulcanization.

  In the tire of the present invention, such a rubber-cord composite is excellent in heat-resistant adhesion with rubber, and therefore can be suitably used for a carcass ply cord, a reinforcing material for a belt reinforcing layer, an insert for a bead portion, and the like.

  Although the number of carcass plies 2 is one in the illustrated example, the number of carcass plies 2 is not limited to this in the present invention, and may be two or more. Further, the structure is not particularly limited. The locking structure of the carcass ply 2 in the bead portion is not limited to the structure in which the carcass ply 2 is wound and locked around the bead core 1 as shown in the figure, and may be a structure in which the end portion of the carcass ply is sandwiched between two layers of bead cores (see FIG. Not shown). When the reinforcing material made of the rubber-cord composite is applied to the carcass ply 2, the number of driving can be set to 35 to 65 pieces / 50 mm, for example. In a tire in which conventional PET is applied to a carcass ply, in a high-speed drum endurance test when a camber angle is imparted, the shoulder portion is rarely broken and the carcass ply is exposed, leading to cutting. By applying the reinforcing material made of polyester filament to the carcass ply, the breaking mode after the durability test is improved, and the tread portion is broken, and accordingly, high-speed durability can be improved.

  The belts 3a and 3b are made of, for example, a rubberized layer of a cord, preferably a steel corded rubberized layer that extends at an inclination of ± 15 to 40 ° with respect to the tire circumferential direction. In the illustrated example, two layers of belts 3a and 3b are laminated so that the cords constituting each belt intersect with each other across the tire equator plane, but in the present invention, It is sufficient that at least one layer of belt is disposed, and the present invention is not limited to the illustrated example.

  In the illustrated example, the belt reinforcing layer includes a single cap layer 4 disposed over the entire width of the belt 3 and a pair of layer layers 5 disposed in a region covering both ends of the belt 3. The cap layer 4 or the layer layer 5 alone or a combination of two or more cap layers 4 and / or two or more layer layers 5 may be used. Such a belt reinforcing layer can be formed, for example, by spirally winding a strip of a certain width formed by aligning a plurality of organic fiber cords and covering them with rubber in the tire circumferential direction. When a reinforcing material made of the rubber-cord composite is applied to the belt reinforcing layer, the number of driving operations can be set to 35 to 65/50 mm, for example. Conventionally, when PET is applied to the belt reinforcement layer, its adhesion is inferior to that of nylon, so it is inferior in high-speed durability performance. However, the reinforcement material comprising the polyester filament according to the present invention is used as the belt reinforcement layer. By applying it, high speed durability performance level equivalent to nylon can be achieved.

  Moreover, as shown in the drawing, the insert 6 can be disposed outside the carcass ply 2 in the bead portion 11 and is formed of a rubberized layer of a reinforcing cord. In the case where the reinforcing material made of the rubber-cord composite is applied to the insert, the number of driving can be set to 35 to 65 pieces / 50 mm, for example. When conventional PET is applied to the insert, since the adhesiveness is insufficient, the insert was destroyed in the bead portion durable drum test, but the reinforcing material made of the polyester filament according to the present invention was used for the insert. By applying, the fracture form is improved and the durability performance level in the bead portion durable drum test is improved.

  Further, although not shown in the drawings, in the present invention, an inner liner is usually disposed in the innermost layer of the tire, and a tread pattern is appropriately formed on the tread surface. Furthermore, in the tire of the present invention, as the gas filled in the tire, normal or air having a changed oxygen partial pressure, or an inert gas such as nitrogen can be used.

Hereinafter, the present invention will be described in detail with reference to examples.
<Example 1-1>
(Manufacture of polyester fiber)
Polyester fibers as shown below were prepared by using a polyethylene terephthalate chip having an intrinsic viscosity of 1.03 and having a high carboxy group end, performing high-speed spinning and multistage drawing by a melt spinning method, and performing epoxy treatment on the surface. The oil agent used for the epoxy treatment adhered to 0.2 parts by mass with respect to 100 parts by mass of the fiber, and the amount of polyglycerol polyglycidyl ether, which is an epoxy compound component, was 0.12% by mass. It was.

This polyester fiber has mechanical properties of an intrinsic viscosity of 0.91, a fineness of 1130 dtex, 384 filament, a strength of 6.9 cN / dtex, an elongation of 12%, and a dry heat shrinkage of 10.5%. The amount of carboxy groups is 22 equivalents / ton, the long period by X-ray small angle diffraction is 10 nm, the amount of terminal carboxy groups on the fiber surface is 7 equivalents / ton, the crystal size in the fiber horizontal axis direction is 45 nm ² , and the amount of terminal methyl groups is It was 0 equivalent / ton, the titanium oxide content was 0.05% by mass, and the surface epoxy group amount (epoxy index) was 0.1 × 10 ⁻³ equivalent / kg.

  Here, the intrinsic viscosity, strength and elongation of the polyester fiber, dry heat shrinkage rate, terminal carboxy group amount, long period by X-ray small angle diffraction and crystal size in the fiber transverse axis direction, terminal carboxy group amount on the fiber surface, terminal The methyl group content, titanium oxide content, and surface epoxy group content were measured according to the following. The same applies to the following.

(Intrinsic viscosity)
The diluted solution which melt | dissolved the polyester chip | tip and the polyester fiber in orthochlorophenol in 100 degreeC for 60 minutes was calculated | required from the value measured using the Ubbelohde viscometer at 35 degreeC.

(Terminal carboxy group content)
40.00 g of the polyester sample powdered using a pulverizer and 100 ml of benzyl alcohol were added to the flask, and the polyester sample was dissolved in benzyl alcohol under a nitrogen stream at 215 ± 1 ° C. for 4 minutes. After dissolution, the sample solution is allowed to cool to room temperature, and then an appropriate amount of 0.1% by mass phenol red benzyl alcohol is added and titrated quickly with N normal sodium hydroxide in benzyl alcohol until discoloration occurs. The amount of dripping was Aml. As a blank, add the same amount of 0.1% by weight of phenol red benzyl alcohol to 100 ml of benzyl alcohol, quickly titrate with N normal sodium hydroxide benzyl alcohol solution, and add the amount of dripping until discoloration occurs. Bml. From these values, the terminal COOH group content in the polyester sample was calculated by the following formula.
COOH end group content ^{(eq / 10 0 g) =} (A-B) × 10 3 × N × 10 6/40
The benzyl alcohol used here is a reagent-grade grade distilled and stored in a light-shielding bottle. As the N normal sodium hydroxide solution of benzyl alcohol, a solution obtained by titrating with a sulfuric acid solution having a known concentration in advance by a conventional method and obtaining the normality N accurately was used.

(Terminal methyl group content)
The polyester was hydrolyzed to acid component and glycol component, and then the methyl ester component was quantified by gas chromatography and calculated from this value.

(Titanium oxide content)
The content of each element was measured using a fluorescent X-ray apparatus (manufactured by Rigaku Corporation, Model 3270E), and quantitative analysis was performed. In the case of this fluorescent X-ray analysis, while a polyester fiber resin polymer sample was heated at 260 ° C. for 2 minutes with a compression press machine, a test molded body having a flat surface was produced under a pressure of 7 MPa, Measurements were performed.

(X-ray diffraction)
The X-ray diffraction of the polyester composition / fiber was performed using an X-ray diffractometer (manufactured by Rigaku Corporation, RINT-TTR3, Cu-Kα ray, tube voltage 50 kV, current 300 mA, parallel beam method). The long period interval is a diffraction line of meridian interference obtained by using a X-ray small angle scattering measurement device and irradiating at a right angle to the fiber axis using a Cu-Kα ray having a wavelength of 1.54 mm as a radiation source. From this, it was calculated using the Bragg equation. The crystal size was determined from the X-ray wide angle diffraction using the half-width of the (010) (100) intensity distribution curve of the equator scan using the shirare equation.

(Amount of terminal carboxy groups on the fiber surface)
According to JIS K0070-3.1 neutralization titration method, the amount of carboxy groups (acid value) on the fiber surface was determined. That is, 50 ml of diethyl ether / ethanol = 1/1 solution was added to about 5 g of a fiber sample, a few drops of a phenolphthalein solution was added as an indicator, and ultrasonically shaken at room temperature for 15 minutes. This solution was titrated with a 0.1 ml potassium hydroxide ethanol solution (factor value f = 1.030), and the indicator dripping amount was measured when the indicator continued to light red for 30 seconds. The value was calculated.
Acid value A (eq / ton) = (B × 1.030 × 100) / S
(Here, B represents 0.1 ml potassium hydroxide ethanol solution titration (ml), and S represents the sample amount (g))

(Fiber strength and elongation)
It measured according to JIS L-1013 using the tensile load measuring device (Shimadzu Corporation autograph).

(Dry heat shrinkage)
According to JIS-L1013, after being left for 24 hours in a room where the temperature and humidity are controlled at 20 ° C. and 65% RH, it was heat-treated in a dryer at 180 ° C. for 30 minutes, and calculated from the difference in test length before and after the heat treatment. .

(Epoxy index (EI))
About the polyester fiber after a heating process, the epoxy index | exponent (EI: epoxy equivalent number per kg of fiber) was measured according to JISK-7236.

(Preparation of adhesive composition)
An epoxy adhesive composition (1) was prepared with the formulation shown in the following table.
The following components were used for the epoxy adhesive composition. The following were used as the thermoplastic polymer (A).
(A-1) Epocross K1010E, manufactured by Nippon Shokubai Co., Ltd., solid concentration 40%, (acryl-styrene copolymer emulsion containing 2-oxazoline group), polymer Tg: -50 ° C., oxazoline group amount: 0.9 (mmol / g, solid) product (A-2) Epocross K1030E, manufactured by Nippon Shokubai Co., Ltd., solid content concentration 40%, (acryl-styrene copolymer emulsion containing 2-oxazoline group) , Polymer Tg: 50 ° C., oxazoline group content: 0.9 (mmol / g, solid) (A-3) polymer obtained by the following synthesis example, (urethane copolymer emulsion containing hydrazino group) )

(Synthesis Example) Adjustment Method of (A-3) A hydrazino group-containing aqueous urethane resin was produced according to the description of Synthesis Example 1 described in JP-A-10-139839. That is, in a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 80 parts by mass of polycaprolactone (manufactured by Daicel Chemical Industries, Ltd., molecular weight 2,000), 99.9 parts by mass of isophorone diisocyanate, dimethylolpropion 30 parts by weight of acid, 100 parts by weight of polyester polyol (manufactured by Unitika Ltd., Elitel 3320, molecular weight 2,000), 28.1 parts by weight of propylene glycol diglycidyl ether-acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd.) 30 parts by mass of N-methylpyrrolidone and 150 parts by mass of ethyl acetate were charged, the temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere, and urethanization reaction was performed at this temperature for 1 hour. Then, it cooled to 40 degreeC and obtained the prepolymer of the NCO terminal. Next, 20 parts by mass of triethylamine was added to the prepolymer for neutralization, and then 600 parts by mass of ion-exchanged water was added. Next, 12.0 parts by mass of adipic acid dihydrazide was added to the reaction system, and stirring was continued at 50 ° C. for 1 hour. Then, ethyl acetate was distilled off under reduced pressure, and then water was added so that the solid content concentration became 30%. Dilution was performed to obtain a hydrazine-terminated urethane copolymer emulsion. It was the weight average molecular weight Mw of polystyrene conversion measured by GPC = 35,000.

The following were used as water-soluble polymer (B).
(B-1) Isoban 10, Kuraray Co., Ltd., solid content concentration 100%, (copolymer of isobutylene and maleic anhydride), molecular weight: 160,000 to 170,000
(B-2) Isoban 04, Kuraray Co., Ltd., solid content concentration 100%, (copolymer of isobutylene and maleic anhydride), molecular weight: 55,000-65,000
(B-3) Isoban 110, Kuraray Co., Ltd., solid content concentration 100%, (maleic anhydride unit of a copolymer of isobutylene and maleic anhydride was reacted with ammonia to obtain a monoamide unit of maleic acid Thereafter, the ring is closed by heating to obtain a maleimide unit), molecular weight: 190,000 to 200,000

The following were used as the compound (C).
(C-1) DELION PAS-037, manufactured by Takemoto Yushi Co., Ltd. (diphenylmethanebis (4,4′-carbamoyl-ε-caprolactam): including molecular structure of diphenylmethane diisocyanate and blocking agent), solid content concentration 27 .5%
(C-2) Penacolite R-50, Indspec Chem. Co. Manufactured, (resorcinol and formaldehyde condensate by novolak reaction), solid content concentration 50%
(C-3) Elastolon BN77, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (a heat-reactive aqueous urethane resin containing a molecular structure of methylenediphenyl), solid content concentration 31%

The following were used as the aliphatic epoxide compound (D).
(D-1) Denacol EX614B, manufactured by Nagase Kasei Kogyo Co., Ltd. (sorbitol polyglycidyl ether)

  The polyester filament made of the polyester fiber obtained above is twisted into a cord in accordance with the conditions shown in the table below, and then the cord is subjected to an adhesive treatment using the epoxy adhesive composition (1). did. Next, this cord was further subjected to an adhesive treatment with an RFL adhesive composition to obtain a tire reinforcing polyester cord.

  The obtained tire reinforcing polyester cord was covered with a rubber to produce a treat with a driving number of 50 pieces / 50 mm, which was applied to a cap layer and a layer layer of a tire having a tire size of 205 / 65R15. No. 1 test tire was produced. This test tire has a carcass made of a single layer of carcass ply (material: PET) extending in a toroidal shape between a pair of left and right bead cores, and the outer side in the tire radial direction of the carcass is ± It had two layers of belts (material: steel) arranged in an intersecting manner at an angle of 40 °, a cap layer arranged over the entire width of the belt, and layer layers arranged at both ends of the belt.

<Example 1-2>
A test tire of Example 1-2 was produced in the same manner as Example 1-1 except that the epoxy-based adhesive composition (2) shown in the above table was used as the adhesive composition.

<Example 1-3>
A test tire of Example 1-3 was produced in the same manner as Example 1-1 except that the epoxy adhesive composition (3) shown in the above table was used as the adhesive composition.

<Comparative Example 1-1>
Polyester similar to Example 1-1, except that a general-purpose tire cord polyethylene terephthalate chip having a low carboxy group end was used and the fiber surface was not subjected to epoxy treatment, and the stretching conditions were fine-tuned to make the physical properties uniform. Fiber was prepared.

This polyester fiber has an intrinsic viscosity of 0.91, fineness of 1130 dtex, 384 filament, strength of 6.9 cN / dtex, elongation of 12%, dry heat shrinkage of 10.5%, long period by X-ray small angle diffraction 10 nm, the crystal size in the fiber horizontal axis direction was 45 nm ² and had the same mechanical properties as the polyester fiber used in Example 1. However, the amount of terminal carboxy groups is 18 equivalents / ton, the amount of terminal carboxy groups on the fiber surface is 11 equivalents / ton, and the amount of surface epoxy groups (epoxy index) is 0.0 × 10 ⁻³ equivalents / kg. From the difference, the amount of terminal methyl groups was 5 equivalent / ton, and the titanium oxide content was 0.00 mass%. A test tire of Comparative Example 1-1 was produced in the same manner as in Example 1-1 except that the polyester filament made of this polyester fiber was used.

<Comparative Example 1-2>
An adhesive liquid (4) was prepared with the formulation shown in the following table, and this adhesive liquid was diluted and adjusted so as to be a 20 mass% adhesive aqueous solution at the above ratio. The blocked isocyanate compound was added immediately before use after blending an RFL adhesive solution and aging at 20 ° C. for 24 hours. The blocked isocyanate compounds used are Daiseki Kogyo Seiyaku Co., Ltd .: Elastron BN69 (blocking agent separation temperature 120 ° C.) and BN27 (blocking agent separation temperature 180 ° C.). The latex was made by emulsion polymerization.

  A polyester filament made of polyester fiber was twisted according to the conditions shown in the following table to form a cord, and then this cord was subjected to an adhesive treatment using an adhesive liquid (4) in the step shown in FIG. Except that, the test tire of Comparative Example 1-2 was manufactured in the same manner as Example 1-1. Specifically, the cord 102 delivered from the unwinding device 101 is passed through the adhesive solution 103, the cord 102 is impregnated with the adhesive solution 103 (impregnation step), and the impregnated cord 102 is sent to the drying zone 104. The cord 102 was dried (drying step), and the dried cord 102 was passed through the heat setting zone 105 and the normalizing zone 106 (heat treatment step), and then the cord 102 was cooled and wound by the winding device 107. The drying temperature of the drying zone 104 in the drying process was the temperature shown in the following table, and the drying time was 2 minutes. In the subsequent heat treatment step including the heat setting zone 105 and the normalizing zone 106, the treatment temperature was 250 ° C. and the treatment time was 1 minute. At this time, the cord tension was 1 kg / piece.

<Comparative Example 1-3>
A polyester fiber similar to Example 1-1 was prepared except that a general-purpose tire cord polyethylene terephthalate chip having a low carboxy group terminal was used and the stretching conditions were finely adjusted to make the physical properties uniform.

This polyester fiber has an intrinsic viscosity of 0.91, fineness of 1130 dtex, 384 filament, strength of 6.9 cN / dtex, elongation of 12%, dry heat shrinkage of 10.5%, long period by X-ray small angle diffraction 10 nm, the crystal size in the fiber horizontal axis direction was 45 nm ² and had the same mechanical properties as the polyester fiber used in Example 1. The surface epoxy group amount (epoxy index) was also the same as 0.1 × 10 ⁻³ equivalent / kg. However, the amount of terminal carboxy groups was 18 equivalents / ton, the amount of terminal carboxy groups on the fiber surface was 9 equivalents / ton, and from the difference in the polymers used, the amount of terminal methyl groups was 5 equivalents / ton, and the titanium oxide content was 0.00. It was 00 mass%. A test tire of Comparative Example 1-3 was produced in the same manner as in Example 1-1 except that the polyester filament made of this polyester fiber was used.

  About each obtained test tire, dynamic adhesiveness and high-speed drum durability were evaluated according to the following. The obtained results are shown in the following table.

<Dynamic adhesiveness>
FIG. 3 is a perspective view showing the rubber test piece 1 used in the dynamic adhesion test. As shown in the drawing, the tire reinforcing polyester cords 2 of the examples and comparative examples were embedded in a rubber matrix so that the cord layers were parallel to each other, and the width W was 50 mm, the length L was 500 mm, and the height. Each rubber test piece 1 was produced at H: 5.5 mm. The number of cords to be driven was 50/50 mm, the distance h ₁ between cords was 2.5 mm, and the distance h ₂ from the cord center to the surface was 1.5 mm. As shown in FIG. 4, each rubber test piece 1 obtained was hung on a pulley 3, a load of 50 kg / inch was applied in the cord axis direction, and tension and compressive force were cyclically applied 300,000 times at 100 rpm. . The pulling speed during the adhesion test was 300 mm / min. After the test, the tensile strength of the cord on the tension side was measured and the dynamic adhesive strength was determined. The results were displayed as an index with the distance of Comparative Example 1-1 as 100. The larger the value, the better and better the dynamic adhesiveness.

<High-speed drum durability>
Each test tire was loaded with 200% of the maximum load condition of JATMA, traveled on the drum, and the distance to failure was indicated as an index with the distance of Comparative Example 1-1 as 100. The higher the number, the better the result. In addition, the form of destruction at the time of failure was observed.

  As shown in the above table, in the tires of the examples, it was confirmed that the occurrence of a failure starting from the cap layer or the layer layer was effectively suppressed and the high-speed drum durability was improved.

<Example 2-1>
The polyester filament obtained in the same manner as in Example 1-1 was twisted into a cord according to the conditions shown in the following table, and then the same epoxy-based adhesive as used in Example 1-1 was attached to this cord. An adhesive treatment was performed using the agent composition (1). Next, this cord was further subjected to an adhesive treatment with an RFL adhesive composition to obtain a tire reinforcing polyester cord.

  The obtained tire reinforcing polyester cord is covered with rubber to prepare a treat with a driving number of 50 pieces / 50 mm, which is applied to a carcass ply of a tire having a tire size of 225 / 55R16. A test tire was produced. This test tire has a carcass made up of two layers of carcass plies extending in a toroidal shape between a pair of left and right bead cores, and the carcass has a radius of ± 40 ° with respect to the tire circumferential direction on the tire radial direction outer side. It had two layers of belts (material: steel) that were interlaced with each other.

<Example 2-2>
A test tire of Example 2-2 was produced in the same manner as in Example 2-1, except that the epoxy-based adhesive composition (2) shown in the above table was used as the adhesive composition.

<Example 2-3>
A test tire of Example 2-3 was produced in the same manner as in Example 2-1, except that the epoxy-based adhesive composition (3) shown in the above table was used as the adhesive composition.

<Comparative Example 2-1>
A test tire of Comparative Example 2-1 was produced in the same manner as in Example 2-1, except that the same polyester filament as in Comparative Example 1-1 was used.

<Comparative Example 2-2>
A test tire of Comparative Example 2-2 was produced in the same manner as in Example 2-1, except that the same adhesive composition as in Comparative Example 1-2 was used.

<Comparative Example 2-3>
A test tire of Comparative Example 2-3 was produced in the same manner as in Example 2-1, except that the same polyester filament as in Comparative Example 1-3 was used.

  Each of the obtained test tires was evaluated for dynamic adhesiveness in the same manner as described above (the reference was Comparative Example 2-1) and evaluated for high-speed drum durability when camber angles were applied according to the following. did. The obtained results are shown in the following table.

<High-speed drum durability (when camber angle is applied)>
Each test tire was loaded with a 200% load of JATMA's maximum load condition, traveled on a drum with a camber angle of 4.0 °, and the distance until failure was determined as Comparative Example 2-1. The distance was expressed as an index with 100 as the distance. The higher the number, the better the result. In addition, the form of destruction at the time of failure was observed.

  As shown in the above table, in the tires of the examples, it was confirmed that the shoulder portion was prevented from being broken and the high-speed drum durability was improved.

<Example 3-1>
The polyester filament obtained in the same manner as in Example 1-1 was twisted into a cord according to the conditions shown in the following table, and then the same epoxy-based adhesive as used in Example 1-1 was attached to this cord. An adhesive treatment was performed using the agent composition (1). Next, this cord was further subjected to an adhesive treatment with an RFL adhesive composition to obtain a tire reinforcing polyester cord.

  The obtained polyester cord for reinforcing a tire is covered with rubber to prepare a treat with a driving number of 50 pieces / 50 mm, which is applied to an insert of a tire having a tire size of 245 / 45R19. A tire was produced. This test tire has a carcass made of a two-layer carcass ply (material: PET) extending in a toroidal shape between a pair of left and right bead cores, and the outer side in the tire radial direction of the carcass is ± It had two layers of belts (material: steel) that were interlaced with each other at an angle of 40 °. Moreover, the insert was arrange | positioned on the outer side of the carcass ply in a bead part.

<Example 3-2>
A test tire of Example 3-2 was produced in the same manner as in Example 3-1, except that the epoxy-based adhesive composition (2) shown in the above table was used as the adhesive composition.

<Example 2-3>
A test tire of Example 3-3 was produced in the same manner as in Example 3-1, except that the epoxy adhesive composition (3) shown in the above table was used as the adhesive composition.

<Comparative Example 3-1>
A test tire of Comparative Example 3-1 was produced in the same manner as in Example 3-1, except that the same polyester filament as in Comparative Example 1-1 was used.

<Comparative Example 3-2>
A test tire of Comparative Example 3-2 was produced in the same manner as in Example 3-1, except that the same adhesive composition as in Comparative Example 1-2 was used.

<Comparative Example 3-3>
A test tire of Comparative Example 3-3 was produced in the same manner as in Example 3-1, except that the same polyester filament as in Comparative Example 1-3 was used.

  Each test tire obtained was evaluated for dynamic adhesiveness in the same manner as described above (the reference was Comparative Example 3-1), and a bead portion durable drum test was performed according to the following. The obtained results are shown in the following table.

<Bead Durability Drum Test>
Each test tire was run on a drum under high internal pressure and high load conditions of an internal pressure of 400 kPa and a load of 5.0 kN, and durability was evaluated based on a running distance until a bead portion failure occurred. The results are shown as an index with the distance of Comparative Example 3-1 as 100. The higher the number, the better the result. In addition, the form of destruction at the time of failure was observed. When the adhesive force of the insert material is low, the drum travel distance is reduced due to the occurrence of peeling of the adhesive portion in advance. On the other hand, when the adhesive force of the insert material is high, the fracture nucleus changes to the folded portion of the carcass ply, and the drum travel distance is improved.

  As shown in the above table, in the tires of the examples, it was confirmed that the occurrence of failure starting from the peeling of the insert was effectively suppressed and the drum durability was improved.

  From the above results, it was confirmed that the polyester cord according to the present invention is superior in heat-resistant adhesiveness to rubber as compared with the conventional polyester cord, and that it is possible to realize a tire having improved durability.

DESCRIPTION OF SYMBOLS 1 Bead core 2 Carcass ply 3a, 3b Belt 4, 5 Belt reinforcement layer 6 Insert 11 Bead part 12 Side wall part 13 Tread part 21 Rubber test piece 22 Tire reinforcement polyester cord 23 Pulley 101 Unwinding device 102 Cord 103 Adhesive liquid 104 Drying zone 105 Heat setting zone 106 Normalizing zone 107 Winding device

Claims (9)

A tire in which a rubber-cord composite made of polyester cord and rubber is used as a reinforcing material,
The polyester cord is subjected to an adhesive treatment with an adhesive composition after twisting polyester filaments,
The polyester filament is a fiber made of polyester having an intrinsic viscosity of 0.85 or more, the main repeating unit of which is ethylene terephthalate, and the amount of terminal carboxy groups in the fiber is 20 equivalents / ton or more, and X-ray small angle diffraction A long period of 9 to 12 nm, a polyester fiber formed by attaching a surface treatment agent having an epoxy group to the fiber surface, and
The adhesive composition comprises (A) an ethylenic addition polymer containing a 2-oxazoline group or a (blocked) isocyanate group, or a thermoplastic polymer polymer comprising a urethane polymer containing a hydrazino group. (B) a reaction product of (B) a water-soluble polymer comprising a copolymer comprising maleic anhydride units and isobutylene units or a derivative thereof; and (C) diphenylmethane diisocyanate and a thermally dissociable blocking agent for isocyanate groups. , A condensate of resorcin and formaldehyde obtained by a novolak reaction, a condensate of chlorophenol, resorcin and formaldehyde, a compound comprising an epoxy cresol novolac resin, or an organic polyisocyanate having a structure in which aromatics are bonded with methylene Multiple active hydrogens Tire compound and an aqueous urethane compound obtained by reacting a thermally dissociative blocking agent to the isocyanate groups with, characterized in that it comprises, and (D) an aliphatic epoxide compound.   The tire according to claim 1, wherein the polyester cord is further treated with an adhesive with a resorcin / formaldehyde / latex adhesive composition.   The tire according to claim 1 or 2, wherein the adhesive composition further includes at least one selected from the group consisting of (E) a metal salt, (F) a metal oxide, and (G) a rubber latex. .   The tire according to any one of claims 1 to 3, wherein the amount of terminal carboxy groups on the fiber surface of the polyester fiber is 10 equivalents / ton or less. The tire of any one of claims 1 to 4 crystal size of the fiber transverse axis direction of the polyester fiber is 35~80nm ^2.   The tire according to any one of claims 1 to 5, wherein the amount of terminal methyl groups in the fibers of the polyester fiber is 2 equivalents / ton or less.   The tire according to any one of claims 1 to 6, wherein a content of titanium oxide in the fiber of the polyester fiber is 0.05 to 3.0 mass%. The tire according to any one of claims 1 to 7, wherein an epoxy index of a fiber surface of the polyester fiber is 1.0 x ^10-3 equivalent / kg or less.   A carcass ply extending in a toroidal shape between a pair of left and right bead portions is used as a skeleton, and at least one layer of a belt disposed on the outer side in the tire radial direction of the carcass, and disposed on the outer side in the tire radial direction of the belt, At least one cap layer that covers the entire width of the belt, and at least a pair of layer layers that cover both ends of the belt in the width direction, wherein the reinforcing material is either the cap layer or the layer layer. The tire according to any one of claims 1 to 8, which is used on one or both sides.

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