Adhesive agent composition, organic fibrous material, rubber article, organic fiber-rubber composite, and tire

Abstract

To provide an adhesive agent composition that can ensure desired adhesiveness without using resorcin and that does not compromise the workability during use.SOLUTION: This adhesive agent composition comprises (A) a rubber latex having an unsaturated diene and (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and further comprises (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) an aqueous component having a plurality of amino groups in the molecule, and (F) at least one compound selected from the group consisting of compounds including an amide bond structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an adhesive composition, an organic fiber material, a rubber article, an organic fiber-rubber composite, and a tire.

Background Art

[0002] Conventionally, for the purpose of reinforcing rubber articles such as tires, an organic fiber such as a tire cord made of nylon fiber, polyester fiber, etc. and a rubber composition such as a rubber composition for tires are adhered to form an organic fiber-rubber composite. And for the said adhesion, the method of coat | covering an organic fiber with an adhesive composition, embedding it in a rubber composition, and co-vulcanizing with a rubber composition is widely used.

[0003] Also, in the step of coating the organic fiber with the adhesive composition, a solvent is generally used for the purpose of adjusting the viscosity of the adhesive composition. However, since the solvent volatilizes in this step, it is preferable to use water with a low environmental load as the solvent. Further, when the organic fiber is coated with the adhesive composition by dipping, it is necessary to make the viscosity of the adhesive composition low enough to be applied by dipping.

[0004] Generally, components contained in an aqueous, i.e., water-soluble or dispersible, aqueous adhesive composition need to have a polar molecular structure. However, on the other hand, polymer materials such as rubber and organic fibers as adherends have low polarity, and when the difference between the polarity of the surface of rubber and organic fibers and the polarity of the components contained in the adhesive composition becomes large, it becomes difficult to adhere. Therefore, in order to use the aqueous adhesive composition as an adhesive composition for rubber articles, the components contained in the aqueous adhesive composition need to have polarity because they are aqueous, but on the other hand, polarity control is required so that the difference from the polarity of the adherend does not cause a decrease in adhesiveness. Therefore, an aqueous adhesive composition having a function capable of satisfying these conflicting requirements is preferably used.

[0005] Here, regarding the step of coating the organic fiber with the adhesive composition, an example of the step when an organic fiber cord such as a tire cord is immersed in the adhesive composition will be described with reference to FIG. 1.

[0006] The organic fiber cord 1 is unwound from the unwinding roll, conveyed by a roll, and immersed in the adhesive composition 2 in a dipping bath (dipping tank) 3 containing the adhesive composition 2. The organic fiber cord 4 coated with the adhesive composition 2 is pulled out from the dipping bath 3, and the excess adhesive composition 2 is removed by a squeezing roll 5. Next, the organic fiber cord 4 coated with the adhesive composition 2 is further conveyed by a roll, dried in a drying zone 6, undergoes heat curing of the resin while being stretched by applying tension in a hot zone 7, and in a normalization zone 8, the tension is accurately adjusted so as to achieve the target strength and elongation physical properties and is normalized (normalizing) while undergoing heat curing of the resin. After being air-cooled outside the zone, it is wound around a winding roll. In this way, the organic fiber is coated with the adhesive composition.

[0007] Conventionally, a composition containing a rubber latex component such as rubber paste has been used as the adhesive composition. In particular, an RFL (resorcin - formaldehyde - latex) adhesive composition obtained by aging a mixed solution containing resorcin, formaldehyde, and rubber latex has been found, and thereafter, an adhesive composition obtained by mixing a specific adhesion promoter with the RFL adhesive composition has been used (see Patent Documents 1 to 4).

[0008] As is well known, in the rubber industry, an adhesive composition (Patent Document 1) consisting of an aqueous rubber latex component, and an aqueous phenolic resin obtained by mixing and aging water-soluble resorcinol and formaldehyde, has been found to have the function of achieving both adhesion to rubber as an adherend and adhesion to the surface of a substrate with low polarity such as organic fibers, and is widely used worldwide. In the adhesion by the RFL adhesive composition, first, by containing a rubber latex component, it adheres by co-vulcanization with the adherend rubber side, and on the other hand, a phenolic resin component composed of a condensate of resorcinol and formaldehyde contained as a component for improving the adhesion to an organic fiber substrate firmly adheres to the adherend substrate side.

[0009] Here, the reason why resorcinol is preferably used is that it can provide a phenolic condensation resin, which is a resin type with high adhesiveness to a resin adherend with high fracture strength, and the polar functional group introduced into the phenol ring to obtain water solubility is a hydroxyl group with relatively low polarity and difficult to cause steric hindrance, and can provide a resin component with high adhesiveness to the organic fiber substrate side.

[0010] Further, the RFL adhesive composition is obtained by mixing and aging resorcinol, formaldehyde, and a rubber latex using rosin acid or the like as an emulsifier during polymerization in the presence of a basic composition. Thereby, water-soluble resorcinol and formaldehyde condense by a resole-type condensation reaction under a base (see Patent Document 2), and it is presumed that rosin acid on the latex surface undergoes addition condensation with the methylol group at the end of the resole-type phenol-formaldehyde addition condensate (see Non-Patent Document 1).

[0011] By this aging, the latex crosslinks with the resole-type resorcinol-formaldehyde condensate via rosin acid, the adhesion is strengthened, the latex is combined with the aqueous resin to become a protective colloid encapsulated, and when the adhesive composition is processed in the apparatus as shown in FIG. 1, the rubber tackiness of the latex is suppressed, so that the stain due to the adhesion of the adhesive composition to the apparatus is reduced.

[0012] As an adhesion promoter added to the RFL adhesive composition, in order to improve the adhesion of an aqueous adhesive composition to a substrate surface with low polarity such as an organic fiber cord, an adhesion promoter having an aqueous property, that is, a property of being soluble or dispersible in water has been used.

[0013] As the water-dispersible adhesion promoter, (blocked) isocyanates such as methylene diphenyl diisocyanate having a particle size of 0.01 to 0.50 μm (see Patent Document 3), and water-dispersed particles of phenolic or novolak-type resins that are water-insoluble such as cresol novolak-type polyfunctional epoxy resins (see Patent Document 4) are used.

[0014] In addition, as an adhesion promoter containing a water-soluble group, a sodium hydroxide solution of a novolak-type condensate obtained by subjecting resorcinol and formaldehyde to a novolakization reaction (see Patent Document 5), phenolic resins that dissolve in water in the presence of a basic substance such as an ammonium solution of a novolak-type condensate of chlorophenols and formaldehyde, and aqueous urethane compounds having a (thermally dissociable blocked) isocyanate group and a self-water-soluble group (see Patent Document 6) have been proposed.

[0015] However, in recent years, regarding resorcinol that has been used as a water-soluble component in the RFL adhesive composition, reduction of the usage amount has been demanded from the viewpoint of reducing environmental load.

[0016] In order to cope with this, adhesive compositions based on water as a solvent have been variously studied and proposed by using polyphenols that do not contain resorcinol.

[0017] For example, an adhesive composition composed of rubber latex and lignin resin (see Patent Document 7), an aqueous adhesive composition based on rubber latex and polyphenols such as flavonoids and aromatic polyaldehydes (see Patent Documents 8 and 9), etc. are known as adhesive compositions that do not contain resorcinol and formaldehyde.

[0018] In addition, Patent Document 10 below discloses a dienic copolymer latex containing an aliphatic polyaminoamide compound, a coating liquid composition for offset printing paper using the same, and the like. However, the coating liquid composition disclosed in Patent Document 10 is a coating composition for coating only one side of the resin surface, not both rubber and resin, and there is little knowledge of an adhesive composition containing polyacrylamide as an adhesive composition between adherent rubber and adherent resin that does not contain resorcinol and formaldehyde.

[0019] In addition, Patent Document 11 below discloses a resin composition for printing ink containing a polyvalent acrylate monomer obtained by reacting polyglycerin with an alkylene oxide. Further, Patent Document 12 below discloses an aqueous composition containing a polymerizable (meth)acrylate or (meth)acrylamide monomer having a hydrophilic group, characterized by the absence of a photoinitiator, a polymerization catalyst, and an organic solvent. However, there is almost no disclosure of knowledge of an aqueous adhesive composition of these polyvalent acrylates and a rubber latex.

Prior Art Documents

Patent Documents

[0020]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

[0021] [Non-Patent Document 1] Kouichi Hakata, Network Polymer, Vol. 31, No. 5, p. 252 (2010) [Summary of the Invention] [Problems to be Solved by the Invention]

[0022] However, when using an adhesive composition for organic fiber cords that does not contain resorcinol as described above, the adhesiveness of the rubber latex measured as the mechanical stability under shear strain of the adhesive liquid increases. As a result, for example, in the process of coating the organic fiber cord 1 with the adhesive composition 2 and drying and thermosetting it as shown in FIG. 1, the adhesion of the adhesive composition 2 to the squeezing roll 5 and the rolls in the drying zone 6 increases, and a new problem occurs that the workability of this process deteriorates.

[0023] In addition, such an adhesive composition that does not contain resorcinol and formaldehyde (referred to as so-called rubber paste) has the problem that the adhesiveness of the rubber latex cannot be suppressed without coating with a condensate of resorcinol and formaldehyde. Therefore, especially due to the adhesion to the device, the surface of the adhesive coating becomes rough and the adhesiveness is likely to decrease. Furthermore, since crosslinking between the latex component and the resorcinol-formaldehyde condensate cannot be obtained, there is also the problem that the adhesiveness between the organic fiber and the coated rubber composition is lower than that of the conventional RFL adhesive composition in the first place.

[0024] Furthermore, when producing an aqueous adhesive composition by mixing an aromatic dialdehyde such as terephthalaldehyde or 2,5-furandicarboxaldehyde, which has low solubility in water, with polyphenol mixed with rubber latex as in Patent Document 7, the aromatic dialdehyde is hardly soluble in water during production, which is insufficient in terms of workability. Also, compared with the condensate of resorcinol and formaldehyde that is water-soluble even without adding an alkali, in the step of preparing the adhesive composition liquid, when it generally becomes a condensate of aromatics and aromatic dialdehydes with low water solubility, it will be made water-soluble by adding an alkali to the phenolic group. For this reason, in the subsequent vulcanization adhesion with the rubber to be adhered, the amount of base contained in the adhesive composition increases, and since the vulcanization reaction of the contained rubber latex is generally promoted, there is also a problem that the adhesion decreases due to over-vulcanization under heat over time.

[0025] Furthermore, the adhesive composition not containing resorcinol as described above also had a problem of causing a decrease in the cord strength of the organic fiber cord coated with the adhesive composition.

[0026] Therefore, an object of the present invention is to provide an adhesive composition that can ensure desired adhesiveness without using resorcinol and does not impair workability during use, and an organic fiber material, a rubber article, an organic fiber-rubber composite, and a tire using the same.

Means for Solving the Problems

[0027] In order to solve the above problems, the present inventors have conducted intensive research on the composition of the adhesive composition. As a result, together with a predetermined rubber latex, an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule is blended. Furthermore, by blending one or more of an aqueous component having a plurality of phenolic hydroxy groups in the molecule, an aqueous component having a plurality of amino groups in the molecule, and a compound containing an amide bond structure, adhesiveness can be improved without using resorcinol, and an adhesive composition that does not impair the workability during use can be obtained. Based on these findings, the present invention has been completed. That is, the gist configurations of the adhesive composition, organic fiber material, rubber article, organic fiber-rubber composite, and tire of the present invention are as follows.

[0028] [1] (A) A rubber latex having an unsaturated diene, and (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, and furthermore, the following (D) to (F): (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) an aqueous component having a plurality of amino groups in the molecule, (F) a compound containing an amide bond structure An adhesive composition, characterized by containing one or more compounds selected from the group consisting of. The adhesive composition of the present invention described in the above [1] can ensure adhesiveness without using resorcinol, and does not impair the workability during use.

[0029] [2] Furthermore, the adhesive composition according to [1], which contains (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group. The adhesive composition described in the above [2] can achieve further excellent adhesiveness and mechanical stability even when it does not contain formaldehyde and resorcinol.

[0030] [3] The rubber latex having the (A) unsaturated diene includes at least one selected from the group consisting of natural rubber (NR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), and vinyl pyridine-styrene-butadiene copolymer rubber (Vp), and the adhesive composition according to [1] or [2]. When the adhesive composition according to the above [3] is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0031] [4] The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is an aqueous compound containing a polyether structure in the molecule, and the adhesive composition according to any one of [1] to [3]. In the adhesive composition according to the above [4], the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) can be mixed with the adhesive composition containing the (A) rubber latex, which is an aqueous solvent, without being separated from the aqueous phase.

[0032] [5] The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is a compound (B-1) containing two or more polymerizable (meth)acrylate structures and a polyglycerol structure in the molecule, a compound (B-2) containing two or more polymerizable (meth)acrylamide structures and a main-chain linked ether structure in the molecule, or a compound (B-3) containing two or more polymerizable (meth)acrylamide structures and a main-chain linked amine structure in the molecule, or a compound (B-4) containing two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the molecule, and the adhesive composition according to any one of [1] to [4]. When the adhesive composition described in [5] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0033] [6] The adhesive composition according to any one of [1] to [5], wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is a plant-derived component having a plurality of phenolic hydroxy groups in the molecule. When the adhesive composition described in [6] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0034] [7] The adhesive composition according to [6], wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is lignin, tannin, tannic acid, flavonoid, or a derivative thereof. When the adhesive composition described in [7] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0035] [8] The adhesive composition according to [7], wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is a derivative of lignin sulfonic acid. When the adhesive composition described in [8] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes particularly good.

[0036] [9] The adhesive composition according to any one of [1] to [8], wherein the aqueous component having a plurality of amino groups in the molecule (E) is (E-1) a polypeptide having an amino group, (E-2) a polyetheramine, (E-3) a polyethyleneimine, or (E-4) a polyamidoamine. When the adhesive composition described in [9] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0037]

[10] The adhesive composition according to [9], wherein the aqueous component having a plurality of amino groups in the molecule (E) is polylysine. When the adhesive composition described in

[10] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0038]

[11] The adhesive composition according to any one of [1] to

[10] , wherein the compound containing the (F) amide bond structure is a polymer composed of (meth)acrylamide or a copolymer containing (meth)acrylamide and other polymerizable monomers. When the adhesive composition described in

[11] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0039]

[12] The adhesive composition according to any one of [2] to

[11] , wherein the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is a water-dispersible (thermally dissociable blocked) isocyanate compound composed of an addition product of a polyisocyanate having an aromatic ring (C-1) and a blocking agent having one or more active hydrogen groups. When the adhesive composition described in

[12] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0040]

[13] The adhesive composition according to

[12] , wherein the water-dispersible (thermally dissociable blocked) isocyanate compound composed of an addition product of a polyisocyanate having an aromatic ring (C-1) and a blocking agent having one or more active hydrogen groups is a blocked body of methylene diphenyl diisocyanate. When the adhesive composition described in

[13] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0041]

[14] The adhesive composition according to any one of [2] to

[11] , wherein the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is an aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group. When the adhesive composition described in the above

[14] is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0042]

[15] The aqueous urethane compound having the (C-2) (thermally dissociable blocked) isocyanate group is (α) An organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, (β) A compound having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less, (γ) A thermally dissociable blocking agent, and (δ) A compound having at least one active hydrogen group and at least one hydrophilic group that is anionic, cationic or nonionic, wherein the mixing ratios of (α), (β), (γ) and (δ) with respect to the total amount of (α), (β), (γ) and (δ) are (α) is 40% by mass or more and 85% by mass or less, (β) is 5% by mass or more and 35% by mass or less, (γ) is 5% by mass or more and 35% by mass or less, and (δ) is 5% by mass or more and 35% by mass or less, and the reaction product after mixing and reacting them, and The constituent ratio of the (thermally dissociable blocked) isocyanate group in the reaction product, when the molecular weight of the isocyanate group (-NCO) is 42, is 0.5% by mass or more and 11% by mass or less, the adhesive composition described in

[14] . When the adhesive composition described in the above

[15] is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0043]

[16] The aqueous urethane compound having the (C-2) (thermally dissociable blocked) isocyanate group is represented by the following general formula (1):

Chemical formula

[14] or

[15] , the adhesive composition according to

[14] or

[15] . When the adhesive composition according to

[16] above is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0044]

[17] The adhesive composition according to any one of [1] to

[16] , which does not contain resorcinol. The adhesive composition according to

[17] above can reduce the environmental load.

[0045]

[18] The adhesive composition according to any one of [1] to

[17] , which does not contain a photoinitiator. The adhesive composition according to

[18] above can obtain adhesiveness with organic fibers by heating instead of light.

[0046]

[19] The adhesive composition according to any one of [1] to

[18] , which is for adhesion to rubber. The adhesive composition according to any one of [1] to

[18] above is preferable for adhesion to rubber because of its high adhesiveness to rubber.

[0047]

[20] The adhesive composition according to any one of [1] to

[19] , which is for adhesion to organic fibers. The adhesive composition according to any one of [1] to

[19] above is preferable for adhesion to organic fibers because of its high adhesiveness to organic fibers.

[0048]

[21] The adhesive composition according to any one of [1] to

[20] , which is for bonding rubber and organic fibers. Since the adhesive composition according to any one of [1] to

[20] has high adhesiveness to both rubber and organic fibers, it is preferable for bonding rubber and organic fibers.

[0049]

[22] An organic fiber material comprising an organic fiber and an adhesive layer covering the surface of the organic fiber, The organic fiber material, wherein the adhesive layer is composed of the adhesive composition according to any one of [1] to

[21] . The organic fiber material of the present invention described in

[22] above is excellent in durability while ensuring environmental properties and workability.

[0050]

[23] The organic fiber material according to

[22] , wherein the organic fiber is an organic fiber cord formed by twisting a plurality of filaments. The organic fiber material described in

[23] above is suitable for reinforcing rubber articles such as tires and conveyor belts.

[0051]

[24] The organic fiber cord is formed by applying a right twist and a left twist, the fiber thickness of the twisted cord is 100 dtex to 5000 dtex, and the number of twists for twisting is 10 to 50 turns / 10 cm for the right twist and 10 to 50 turns / 10 cm for the left twist. The organic fiber material according to

[23] . The organic fiber material described in

[24] above is more suitable for reinforcing rubber articles such as tires and conveyor belts.

[0052]

[25] The organic fiber material according to

[23] or

[24] , wherein the adhesive layer is 0.5 to 6.0% by mass of the mass of the organic fiber cord in terms of dry mass. The organic fiber material described in

[25] above can ensure appropriate adhesiveness.

[0053]

[26] The organic fiber material according to any one of

[22] to

[25] , wherein the organic fiber is made of a polyester resin. The organic fiber material described in the above

[26] has further improved adhesiveness.

[0054]

[27] A rubber article, characterized in that it is reinforced with the organic fiber material described in any one of

[22] to

[26] . The rubber article of the present invention described in the above

[27] is excellent in durability while ensuring environmental properties and workability.

[0055]

[28] An organic fiber-rubber composite, characterized in that the organic fiber is coated with the adhesive composition described in any one of [1] to

[21] . The organic fiber-rubber composite (particularly, the organic fiber cord-rubber composite) of the present invention described in the above

[28] can obtain good adhesiveness and has good environmental properties and workability.

[0056]

[29] A tire, characterized in that the organic fiber-rubber composite described in

[28] is used. The tire of the present invention described in the above

[29] is excellent in environmental properties and productivity. [Advantages of the Invention]

[0057] According to the present invention, it is possible to provide an adhesive composition that can ensure desired adhesiveness without using resorcinol and does not impair workability during use, and an organic fiber material, a rubber article, an organic fiber-rubber composite, and a tire using the same. [Brief Description of the Drawings]

[0058]

Figure 1

Figure 2

[0059] Hereinafter, the adhesive composition, organic fiber material, rubber article, organic fiber-rubber composite, and tire of the present invention will be exemplified and described in detail based on their embodiments. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.

[0060] [Definitions] The compounds described in this specification may be partially or entirely derived from fossil resources, may be derived from biological resources such as plant resources, or may be derived from recycled resources such as used tires. Further, it may be derived from a mixture of any two or more of fossil resources, biological resources, and recycled resources.

[0061] In this specification, when representing a range, unless otherwise specified, the ends of the range are also included within the range.

[0062] [Adhesive Composition] The adhesive composition of the present invention comprises (A) a rubber latex having an unsaturated diene, and (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and further comprises one or more compounds selected from the group consisting of (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) an aqueous component having a plurality of amino groups in the molecule, and (F) a compound containing an amide bond structure.

[0063] According to the adhesive composition of the present invention, with the above configuration, good adhesiveness can be obtained without using resorcinol. In particular, good adhesiveness between the organic fiber and the coating rubber composition can be ensured. In the adhesive composition of the present invention, (A) a rubber latex having an unsaturated diene can improve the adhesiveness between the adhesive composition and the adherend rubber and contribute to the improvement of adhesiveness. Further, by using in combination (A) a rubber latex having an unsaturated diene and components (D) to (F) which are (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) an aqueous component having a plurality of amino groups in the molecule, and (F) a compound containing an amide bond structure, by suppressing the tackiness of the rubber latex measured as the mechanical stability under shear strain of the adhesive liquid, in the step of coating the organic fiber with the adhesive composition and drying and thermosetting it, the adhesion of the adhesive composition to a roll or the like can be suppressed, and the workability is good.

[0064] Furthermore, the adhesive composition of the present invention, when combined with (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, coats the organic fiber with the adhesive composition and dries and heat-cures it, due to the Michael addition reaction with the components (D) to (F), or the formation of an interpenetrating network by cross-linking of the moistened (B) component within the component (F), resulting in an increase in the interaction between the components, the dispersion state of the rubber latex (A) having an unsaturated diene is further stabilized. Therefore, particularly in the step of thermosetting the organic fiber with the adhesive composition, the adhesion of the adhesive composition to a roll or the like is suppressed, and the workability is further improved. Also, the adhesive strength at high temperatures is improved and excellent. Therefore, according to the adhesive composition of the present invention, the desired adhesiveness can be obtained without using resorcinol, and the workability during use can also be ensured well.

[0065] Also, according to the adhesive composition of the present invention, since there is no need to use resorcinol, the environmental load can be reduced. Therefore, the adhesive composition of the present invention can be made free of resorcinol. Furthermore, the adhesive composition of the present invention preferably does not contain formaldehyde. In this case, the environmental load can be further reduced.

[0066] Moreover, although the adhesive composition of the present invention is not particularly limited, it preferably further contains an aqueous compound having a (C) (thermally dissociable blocked) isocyanate group. In this case, excellent adhesiveness and mechanical stability can be achieved even when formaldehyde and resorcinol are not contained.

[0067] Since the adhesive composition of the present invention has high adhesiveness to rubber, it is preferable as an adhesive composition for bonding to rubber. Further, since the adhesive composition of the present invention has high adhesiveness to organic fibers, it is preferable as an adhesive composition for bonding to organic fibers. Furthermore, since the adhesive composition of the present invention has high adhesiveness to both rubber and organic fibers, it is more preferable as an adhesive composition for bonding rubber and organic fibers. In particular, the adhesive composition of the present invention is useful when applied to an organic fiber cord described later.

[0068] <(A) Rubber latex having an unsaturated diene> In the adhesive composition of the present invention, examples of the (A) rubber latex having an unsaturated diene include a synthetic rubber latex having an unsaturated diene and a natural rubber latex.

[0069] The synthetic rubber latex having an unsaturated diene in the adhesive composition of the present invention means a synthetic rubber latex containing an unsaturated diene having vulcanizability by sulfur.

[0070] In one embodiment of the present invention, the rubber latex having an (A) unsaturated diene contained in the adhesive composition is a component for adhering the adhesive layer formed by the adhesive composition and the coated rubber composition which is the adherend, similar to the above-described rubber paste. The rubber latex having an (A) unsaturated diene is compatible with the rubber polymer contained in the coated rubber composition which is the adherend, and further forms a rubber co-vulcanization adhesion by co-vulcanization of the unsaturated diene moieties. As a result, according to the adhesive composition of the present invention containing the rubber latex having an (A) unsaturated diene, for example, the organic fiber cord and the coated rubber composition can be adhered well.

[0071] Examples of the rubber latex having an (A) unsaturated diene include, but are not limited to, natural rubber (NR) latex, or latexes of synthetic rubbers such as isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), and vinyl pyridine-styrene-butadiene copolymer rubber (Vp). These may be used alone or in combination of two or more.

[0072] Among these, the latex of vinyl pyridine-styrene-butadiene copolymer rubber is preferred. The vinyl pyridine-styrene-butadiene copolymer rubber latex is a rubber latex that has been widely used in conventional adhesive compositions and articles such as tires. In the adhesive composition of the present invention as well, it provides a good bond between the adhesive layer and the adherend rubber, and due to the advantages of being relatively flexible and having flexibility, the adhesive layer is imparted with strain relaxation due to rubber elasticity, resulting in high fracture resistance, and it also enables deformation of the organic fiber cord.

[0073] In addition, the content (solid content ratio) of the rubber latex having the (A) unsaturated diene in the total solid content of the adhesive composition of the present invention is not particularly limited, but is preferably 25% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Further, the content of the rubber latex having the (A) unsaturated diene is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. When the content of the rubber latex having the (A) unsaturated diene is 50% by mass or more, the compatibility between the rubber polymers of the adherend rubber composition and the rubber latex contained in the adhesive composition becomes more appropriate, and the adhesion state of the coating rubber in the organic fiber-rubber composite becomes more excellent. On the other hand, when the content of the rubber latex having the (A) unsaturated diene is 95% by mass or less, compared with the rubber paste, the amount of the coating component that suppresses the adhesion of the latex contained as other components in the adhesive composition can be ensured to be relatively constant or more, the mechanical stability of the adhesive liquid under shear strain can be obtained, and in the step of coating the fiber material to be adhered with the adhesive composition, the adhesive composition can be prevented from adhering to the apparatus as shown in FIG. 1. Furthermore, the problem that the surface of the coated adhesive composition becomes rough and the adhesiveness to the coating rubber composition decreases hardly occurs, so that the adhesiveness can be improved.

[0074] The rubber latex having the (A) unsaturated diene can be obtained, for example, by dissolving an emulsifier such as potassium rosinate in water, adding a monomer mixture thereto, further adding an electrolyte such as sodium phosphate and a peroxide as a polymerization initiator to carry out polymerization, then adding a charge transfer agent after reaching a predetermined conversion rate to stop the polymerization, and further removing the remaining monomer. In addition, it is also preferable to use a chain transfer agent during the polymerization.

[0075] As the emulsifier, it is used for emulsifying a monomer mixture in an aqueous system, and one or more of anionic surfactants such as alkali metal salts of fatty acids, alkali metal salts of rosin acids, sodium formaldehyde condensate naphthalenesulfonate, sulfuric acid esters of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, or nonionic surfactants such as alkyl ester type, alkyl ether type, and alkyl phenyl ether type of polyethylene glycol are used. Among these emulsifiers, it is preferable to contain a metal salt of rosin acid, particularly an alkali metal salt of rosin acid. This can be used alone, that is, only one type, or in combination with two or more other emulsifiers. Rosin acid is a mixture of resin acids with a similar chemical structure, mainly composed of tricyclic diterpenoids obtained from pine resin and the like. These resin acids have three ring structures, two double bonds, and one carboxyl group, and the double bond part has a functional group rich in reactivity such as esterification with an unsaturated carboxylic acid or the methylol end of a resol type phenolic resin at the carboxyl group part. The usage amount of such an emulsifier is usually 0.1 to 8 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of all monomers used in latex polymerization.

[0076] As the polymerization initiator, for example, water-soluble initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, redox initiators, or oil-soluble initiators such as benzoyl peroxide can be used. Among these, it is preferable to use potassium persulfate.

[0077] Examples of the chain transfer agent include monofunctional alkyl mercaptans such as n-hexyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and t-hexyl mercaptan; difunctional mercaptans such as 1,10-decane dithiol and ethylene glycol dithiodiglycolate; trifunctional mercaptans such as 1,5,10-candtrithiol and trimethylolpropane tristithiodiglycolate; tetrafunctional mercaptans such as pentaerythritol tetrakisthiodiglycolate; disulfides; halogen compounds such as carbon tetrachloride, carbon tetrabromide, and ethylene bromide; α-methylstyrene dimer, terpinolene, α-terpinene, dipentene, allyl alcohol, etc. These can be used alone or in combination of two or more. Among these chain transfer agents, alkyl mercaptans are preferably used, and more preferably n-octyl mercaptan and t-dodecyl mercaptan. Among these, it is preferable to use t-dodecyl mercaptan. The amount of such a chain transfer agent used is usually 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of all the monomers used in the latex polymerization.

[0078] In addition to the above components, general additives such as antioxidants such as hindered phenols, silicone-based, higher alcohol-based, and mineral oil-based defoaming agents, reaction terminators, and antifreeze agents may be used in the latex as needed. In addition, the components (B) to (F) of the present invention can be added to the latex in advance, but in that case, it is included in the composition consisting of (A) to (F) in the adhesive composition of the present invention.

[0079] --Vinylpyridine-Styrene-Butadiene Copolymer Rubber Latex-- The vinylpyridine-styrene-butadiene copolymer rubber latex is obtained by terpolymerizing a vinylpyridine monomer, a styrene monomer, and a conjugated diene-based butadiene monomer, and may further contain other monomers copolymerizable with these monomers.

[0080] Here, the vinylpyridine monomer includes vinylpyridine and substituted vinylpyridine in which a hydrogen atom in the vinylpyridine is substituted with a substituent. Examples of such vinylpyridine monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. Among these, 2-vinylpyridine is preferred. These vinylpyridine monomers may be used alone or in combination of two or more.

[0081] The styrene monomer includes styrene and substituted styrene in which a hydrogen atom in the styrene is substituted with a substituent. Examples of the styrene monomer include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, hydroxymethylstyrene, etc. Among these, styrene is preferred. These styrene monomers may be used alone or in combination of two or more.

[0082] Examples of the conjugated diene-based butadiene monomer include aliphatic conjugated butadiene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene. Among these, 1,3-butadiene is preferred. These conjugated diene-based butadiene monomers may be used alone or in combination of two or more.

[0083] For the synthesis of the vinylpyridine-styrene-butadiene copolymer rubber latex, known methods can be used. Specifically, for example, the method described in Japanese Patent Application Laid-Open No. 9-78045 based on the studies by the inventors of the present invention can be used. And by using those methods, various compositions and internal particle structures such as copolymers having a uniform or different composition ratio within the same particles of the vinylpyridine-styrene-butadiene copolymer rubber latex can be obtained.

[0084] Regarding the vinylpyridine-styrene-butadiene copolymer rubber latex, commercially available products of copolymers having a monomer mixing ratio with a uniform composition within the same particles include Nipol 2518 manufactured by Nippon Zeon Co., Ltd., and Piratex manufactured by Nippon A & L Co., Ltd. Further, commercially available products of copolymers having a monomer mixing ratio with different compositions within the same particles include V0658 manufactured by JSR Corporation. All of these can be used as the rubber latex having an unsaturated diene (A) of the adhesive composition of the present invention.

[0085] In the vinylpyridine-styrene-butadiene copolymer rubber latex, the monomer ratio of vinylpyridine:styrene:butadiene is not particularly limited. However, among the copolymers constituting the vinylpyridine-styrene-butadiene copolymer particles, it is preferable to contain a copolymer obtained by polymerizing a monomer mixture consisting of 5 to 20% by mass of vinylpyridine, 10 to 40% by mass of styrene, and 45 to 75% by mass of butadiene. If the vinylpyridine is 5% by mass or more, an appropriate amount of pyridine sites having a vulcanization acceleration effect is present in the rubber component, and as the degree of crosslinking by sulfur increases, the adhesive strength of the entire adhesive layer is further improved. If it is 20% by mass or less, the degree of crosslinking of the rubber does not become over-vulcanized, and a hard adhesive can be obtained. Also, if the styrene is 10% by mass or more, the strength of the latex particles and the adhesive layer is sufficient, and the adhesive strength is further improved. If it is 40% by mass or less, while making the co-vulcanization property of the adhesive layer and the adherend rubber appropriate, it also leads to ensuring the adhesive strength. Furthermore, if the butadiene is 45% by mass or more, it becomes possible to form a more sufficient crosslink, and if it is 75% by mass or less, the crosslink is made appropriate, and the durability due to changes in volume and modulus can be ensured well. The composition ratio of the monomer mixture of vinylpyridine:styrene:butadiene can preferably be, for example, 15:15:70.

[0086] In the present invention, as the rubber latex having the (A) unsaturated diene, in addition to the synthetic rubber latex having an unsaturated diene, natural rubber latex can also be used. The natural rubber latex is not particularly limited, and for example, field latex, ammonia-treated latex, centrifugally concentrated latex, deproteinized latex treated with a surfactant or an enzyme, and combinations thereof can be used. Among these, it is preferable to use field latex.

[0087] <(B) An aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule> The adhesive composition of the present invention contains (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule. Since the deterioration due to hydrolysis of functional groups by moisture is small, for example, compared with a water-soluble epoxide compound, the storage stability (pot life) of the adhesive composition is excellent. Further, since the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) has low reactivity in radical polymerization at normal temperature, an increase in liquid viscosity due to crosslinking of the adhesive composition does not occur in an aqueous solution. Therefore, the stability during the operation of the coating process applied to the organic fiber cord is also excellent, and a radical reaction can be caused by heating in the subsequent drying and curing processes of the adhesion treatment process. For this reason, the adhesive composition of the present invention containing the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) has an effect of reducing the adhesion to the roll in the furnace in the curing process of the adhesion treatment process, and also has an effect of improving the adhesive strength at a high temperature of 100 °C or higher of the adhesive composition.

[0088] Examples of the polymerizable (meth)acrylate structure include (meth)acryloyloxy groups (CH2=CH-CO-O-, CH2=C(CH3)-CO-O-), etc. Examples of the polymerizable (meth)acrylamide structure include (meth)acryloylamino groups (CH2=CH-CO-NH-, CH2=C(CH3)-CO-NH-), etc. Examples of the polymerizable (meth)allyl structure include (meth)allyl groups (CH2=CH-CH2-, CH2=C(CH3)-CH2-), etc.

[0089] The aqueous compound (B) having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule has a structure that imparts hydrophilicity in the molecule. Specific structures are not particularly limited, but examples include a structure containing a main-chain linking ether bond, a structure containing a main-chain linking amine bond, a structure obtained by urethanizing a polyol compound and a hydroxyl group-containing acrylic monomer with an isocyanate compound, a structure in which a reactive group of an acrylic monomer is introduced into an acrylic polymer, and the like.

[0090] As the aqueous compound (B) having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, an aqueous compound containing a polyether structure in the molecule is one of the preferred structures because water solubility is imparted by the hydrophilicity of the ether group. Furthermore, the aqueous compound containing a polyether structure in the molecule is nonionic and has miscibility with an aromatic hydrocarbon-based solvent system, so it is likely to adhere to an organic fiber tire cord having an aromatic hydrocarbon in its molecular skeleton. In addition, the polyether structure in the molecule can include, for example, acidic groups such as carbonates, sulfates, sulfonates, sulfinates, phosphates, phosphonates, phosphinates, and other functional groups such as hydroxyl groups, amino groups, amine groups, and thiol groups.

[0091] Thus, since the aqueous compound (B) having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule contains a structure that imparts hydrophilicity in the molecule, a uniform adhesive composition liquid using water as a solvent can be prepared. In addition, it can form a combination with the other components of the adhesive composition described above, namely, the aqueous component (D) having a plurality of phenolic hydroxyl groups in the molecule, the aqueous component (E) having a plurality of amino groups in the molecule, the compound (F) containing an amide bond structure, which are wetted in water and the networks in water penetrate each other.

[0092] The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B) can be obtained, for example, by reacting an α,β-unsaturated acid with a compound serving as a main chain skeleton structure. Further, when two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures (i.e., polymerizable functional groups) are introduced, a compound capable of crosslinking by an addition reaction is obtained if there are two or more per molecule. For example, as the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B), polyfunctional monomers such as difunctional, trifunctional, tetrafunctional, pentafunctional, hexafunctional, heptafunctional, octafunctional, nonafunctional or decafunctional monomers can be used. However, when a large number of hydrophobic (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures (functional groups) are introduced, the solubility in an aqueous solution also decreases. Therefore, the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B) is not particularly limited, but preferably has 2 to 5 polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures per molecule.

[0093] The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B) preferably contains, in the molecule, a skeleton structure including a unit in which a main chain ether derived from a compound serving as a main chain skeleton structure such as trimethylolpropane, pentaerythritol, xylitol, diglycerol, triglycerol, dipentaerythritol, sorbitol, (poly)glycerin, diethylene glycol, aliphatic polyether, polyethylene glycol or polypropylene glycol and an aliphatic spacer (such as CH2CH2) are linked, or a skeleton structure including a unit in which a main chain-linked amine and an aliphatic spacer (such as CH2CH2) are linked, two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures. Alternatively, the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B) is preferably a compound containing a skeleton structure in which diallyldimethylammonium chloride or a copolymerizable monomer such as diallyldimethylammonium chloride and acrylamide, allylamine, dimethylamine, epichlorohydrin, maleic acid, SO2, etc. are linked, and two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule.

[0094] The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule (B) is particularly preferably a compound containing (B-1) two or more polymerizable (meth)acrylate structures and a polyglycerin structure in the molecule, (B-2) two or more polymerizable (meth)acrylamide structures and a main chain-linked ether structure in the molecule, (B-3) two or more polymerizable (meth)acrylamide structures and a main chain-linked amine structure in the molecule, (B-4) two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the molecule.

[0095] In the compound containing two or more polymerizable (meth)acrylate structures and a polyglycerin structure in the molecule (B-1), the polyglycerin to be constituted preferably has an average degree of polymerization of 2 to 20, more preferably 4 to 20. Although there is no particular limitation on the production method, it can be obtained by adding an alkylene oxide (such as ethylene oxide or propylene oxide) to the hydroxyl group of polyglycerin and reacting the terminal hydroxyl group with acrylic acid or methacrylic acid. Specifically, SA-TE60 etc., which are polyglycerin-based (meth)acrylates manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., can be used.

[0096] As the compound containing two or more polymerizable (meth)acrylamide structures and a main chain-linked ether structure in the molecule (B-2), the following structural formula: [Chemical formula] N,N’-{[(2-acrylamido-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide represented by The following structural formula: [Chemical formula] Examples of the polyfunctional (meth)acrylamide compound such as N,N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine represented by

[0097] Examples of the compound containing two or more polymerizable (meth)acrylamide structures and a main chain-linked amine structure in the (B-3) molecule include the following structural formula: [Chemical formula] N,N',N''-triacryloyl diethylenetriamine represented by The following structural formula: [Chemical formula] Examples of the polyfunctional (meth)acrylamide compound such as N,N',N'',N'''-tetraacryloyl triethylenetetramine include products commercially available such as FOM-03007 and FOM-03009 manufactured by Fujifilm Wako Pure Chemical Corporation.

[0098] Examples of the compound containing two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the (B-4) molecule include the following structural formula: [Chemical formula] Examples include aqueous solutions of diallyldimethylammonium chloride represented by , and commercially available products include DADMAC manufactured by Osaka Swords Co., Ltd., D2003 manufactured by Tokyo Chemical Industry Co., Ltd., etc. In addition, a poly(diallyldimethylammonium chloride) solution manufactured by Sigma-Aldrich Japan K.K., which is a polymer thereof, can be used.

[0099] The content (solid content ratio) of the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) in the total solid content of the adhesive composition is not particularly limited, but is preferably 0.3% by mass or more, and more preferably 0.7% by mass or more. Further, the content of the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is preferably 7% by mass or less, and more preferably 3% by mass or less. If the content of the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is 0.3% by mass or more, it can form a combination with the other components of the adhesive composition described above, namely, the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D), the aqueous component having a plurality of amino groups in the molecule (E), the compound containing an amide bond structure, which are wet in water and the networks in water penetrate each other. Also, if the content of the aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is 7% by mass or less, it becomes possible to ensure a certain amount or more of the other components such as the rubber latex (A) and components (D) to (F) blended in the adhesive composition. As a result, the adhesiveness to the adherend rubber becomes better.

[0100] <The aqueous component having a plurality of phenolic hydroxy groups in the molecule (D)> One embodiment of the adhesive composition of the present invention includes (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule.

[0101] The aqueous component (D) having a plurality of phenolic hydroxy groups in the molecule is preferably a plant-derived aqueous component having a plurality of phenolic hydroxy groups in the molecule. In this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0102] As the plant-derived aqueous component having a plurality of phenolic hydroxy groups in the molecule, a plant-derived polymer having a plurality of phenolic hydroxy groups in the molecule is preferable, and water-soluble polyphenols are preferably mentioned. Specifically, polyphenols such as lignin, tannin, tannic acid, flavonoid, and its derivatives are included. In this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0103] The aqueous component having a plurality of phenolic hydroxy groups in the molecule (also referred to as "polyphenols") can be chemically or physically adsorbed onto latex particles in the rubber latex having (A) an unsaturated diene, similar to the rosin salt of the latex emulsifier, and can function as a dispersant for disperse dyes due to the phenolic hydroxyl groups. By keeping each particle in a stable dispersed state, the effect of improving the storage stability (pot life) and mechanical stability of the adhesive composition is enhanced. Further, since the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) has a plurality of phenolic hydroxy groups in the molecule, it has the effect of a phenolic antioxidant and can suppress the oxidation degradation reaction at the unsaturated diene site of the rubber latex having (A) an unsaturated diene contained in the adhesive composition, thereby preventing the reduction in the amount of unsaturated diene on the surface of the adhesive composition over time due to radical oxidation reaction by heat or light. Therefore, when the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is used in the adhesive composition, there is little adhesive degradation over time between the organic fiber and the coated rubber composition, and the adhesiveness is good.

[0104] Research on separating polyphenols such as lignin and tannin, which are components in wood and bark, and reacting them with formaldehyde to produce adhesives (see, for example, Japanese Patent Laid-Open No. 07-53858) has been conducted for a long time, but there is little knowledge on producing a water-based adhesive composition that does not contain resorcinol, particularly on producing a water-based adhesive composition containing a rubber latex having an unsaturated diene.

[0105] The aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is preferably lignin or a derivative thereof. Lignin is a main component constituting the plant cell wall together with polysaccharides such as cellulose. Lignin contains functional groups such as, for example, hydroxyl groups, methoxy groups, carbonyl groups, and carboxyl groups. In particular, since phenolic hydroxy groups are highly reactive, an addition by an electron-withdrawing group such as a (meth)acrylate structure, a (meth)acrylamide structure, or a (meth)allyl structure having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B), or an interaction with an aqueous compound having a cationic substance such as an aqueous component having a plurality of amino groups in the molecule (E) can be achieved.

[0106] Lignin is a polymer having a structure based on phenylpropane. However, since the molecular structure of lignin is various and it is a giant biopolymer forming a three-dimensional network structure, its molecular structure has not yet been fully elucidated.

[0107] Since natural lignin forms a strong composite material with polysaccharides such as cellulose in the plant cell wall, the isolation of natural lignin without chemical structure modification is considered very difficult. Various industrial separation methods are used to extract lignin from materials such as wood. Lignins obtained after separation include sulfonated lignin, kraft lignin, soda lignin, steam explosion lignin, and the like. Among these industrially handled lignins, from the viewpoints of availability and economy, lignin obtained on a large scale from the pulp waste liquid of the chemical pulping process in the paper pulp manufacturing process, that is, lignosulfonate or kraft lignin is a well-known material.

[0108] Examples of other lignins include lignin modified by hydroxymethylation, epoxidation, deamination, acylation or hydroxylation, diethanolamine-modified lignin, enzyme-modified lignin, laccase-modified lignin, urea-modified lignin, lignosulfonate, sulfite lignin, alkali-granite lignin, polyethylene glycol-added lignin, and the like.

[0109] The kraft lignin is derived from a chemical pulping method (high-temperature and high-pressure reaction) called the kraft cooking method, which is a high-temperature and high-pressure reaction in which wood chips such as hardwood, softwood, miscellaneous wood, bamboo, kenaf, and bagasse as raw material wood are put into a digester together with a cooking liquor such as sodium hydroxide / sodium sulfide. It is obtained by adding an acid and / or carbon dioxide to the kraft waste liquor obtained after kraft cooking to precipitate the dissolved lignin denatured product, and dehydrating and washing the produced precipitate. Further, the precipitate after dehydration and washing can be dissolved by adding an organic solvent such as alcohol or acetone, the impurities which are insoluble substances can be separated, and purification by drying can be carried out, or modification can be carried out by introducing various functional groups as necessary. The kraft lignin can be obtained and used as a commercially available product. Among them, the reagent named "Lignin,alkali,kraft" (CAS Number: 8068-05-1) manufactured by Sigma-Aldrich Co. LLC, BioPiva 100 (CAS Number: 8068-05-1) or BioPiva 395 (CAS Number: 8068-05-1) manufactured by UPM Biochemicals is preferable.

[0110] The sulfonic acid lignin is lignosulfonic acid and its salts obtained from waste liquid eluted from sulfite pulp, etc. as raw materials in a chemical pulping method by the sulfite cooking method in which wood chips are reacted at high temperature and high pressure with a cooking liquor using sulfurous acid and / or sulfite. Calcium lignosulfonate, sodium lignosulfonate, potassium lignosulfonate, and magnesium lignosulfonate salts are particularly preferred. Among them, sodium lignosulfonate, etc. are preferred. These sulfonic acid lignins are commercially available. For example, as lignosulfonate or modified lignosulfonate, products of the Sun Extract series manufactured by Nippon Paper Industries Co., Ltd. can be used.

[0111] Examples of high-added-value products of lignosulfonate include not only high-purity products but also partially desulfonated (low) sulfonated lignosulfonate with a reduced degree of sulfonation by heating lignosulfonate in an alkaline aqueous solution using sodium hydroxide or ammonia in the presence of an oxidizing agent such as oxygen (see, for example, JP-A-2016-135834, etc.). As high-purity lignosulfonate or modified lignosulfonate, products of the Pearllex series manufactured by Nippon Paper Industries Co., Ltd. can be used, and as partially desulfonated lignosulfonic acid, products of the Vanilex series manufactured by Nippon Paper Industries Co., Ltd. can be used. Among them, "Lignin (Alkali)" (CAS Number: 8061-51-6, solid powder), manufactured by Tokyo Chemical Industry Co., Ltd., which is a partially desulfonated (low) sulfonated lignosulfonate with a reduced degree of sulfonation, is preferred. In this specification, "derivatives of lignosulfonic acid" include lignosulfonate, modified lignosulfonate, partially desulfonated lignosulfonic acid, partially desulfonated (low) sulfonated lignosulfonate, etc.

[0112] In addition, when the lignosulfonic acid is partially desulfonated lignosulfonic acid, it can be preferably used because it has good dispersibility on the surface of organic fibers during the fixing of the adhered organic fibers (see JP-A-2002-146028).

[0113] The tannin is a group of polyphenols present in a wide range of plants, such as not only woody trees but also fruits, leaves and seeds, such as grapes, oysters, berries, cloves, beans, herbs, tea leaves and cocoa beans. Tannin molecules generally contain a number of hydroxyl groups and often also carboxyl groups, and tend to form strong complexes and composites with a variety of polymers in a wide range.

[0114] The tannin includes tannic acid, proanthocyanidin, flavonoid, gallic acid ester, catechin, etc., and also includes derivatives such as salts and modified forms thereof. The flavonoid is ubiquitous in the leaves, trunks and barks of plants and is generally a substance called tannin, and consists of hydrolyzable tannin and condensed tannin. The identification of these tannins is that when boiled with dilute hydrochloric acid, the condensed tannin produces an insoluble precipitate, and the tannin belonging to the hydrolyzable type is hydrolyzed to produce a water-soluble substance.

[0115] Both hydrolyzable tannin and condensed tannin are water-soluble, and can be obtained by extraction from plant materials such as xylem, bark, leaves, fruits, pods, galls, etc. by methods such as hot water extraction. Hydrolyzable tannin can be obtained, for example, from chestnuts, the xylem of nuts, the bark of oak, tea leaves, galls of Chinese gallnuts or gallnuts, and condensed tannin can be obtained from the xylem of quebracho, the bark of mimosa, the fruits of persimmons and buckwheat, etc. In particular, the condensed tannin obtained from the bark of mimosa, manufactured by Kawamura Tsusho Co., Ltd., trade name "Mimosa" (solid powder), etc. is preferable.

[0116] The content (solid content ratio) of the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) in the total solid content in the adhesive composition is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. Further, the content of the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is preferably 60% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. When the content of the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is 1% by mass or more, the adhesiveness between the organic fiber and the coating rubber composition becomes better. Also, when the content of the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is 60% by mass or less, it becomes possible to ensure a certain amount or more of other components such as rubber latex blended in the adhesive composition, and as a result, the adhesiveness to the adherend rubber becomes better.

[0117] <(aqueous component having a plurality of amino groups in the molecule (E))> One preferred embodiment of the adhesive composition of the present invention includes (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, and (E) an aqueous component having a plurality of amino groups in the molecule. In addition, the aqueous component having a plurality of amino groups in the molecule (E) of the present invention is not particularly limited as long as the number of amino groups in one molecule is plural, and may be two or three or more.

[0118] As the aqueous component having a plurality of amino groups in the molecule (E), a polyfunctional amine compound having two or more primary to tertiary amino groups is preferably used. When the aqueous component having a plurality of amino groups in the molecule (E) is a polyfunctional amine compound having two or more primary to tertiary amino groups, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition can be made better. Examples of the aqueous component having a plurality of amino groups in the (E) molecule include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, phenylenediamine, metaxylylenediamine, diethylenetriamine, triethylenetetramine, triaminopropane, or amino group-containing resins having amino groups such as polyvinylamine, polyethyleneimine, polyallylamine, polyetheramine, and polylysine.

[0119] The number average molecular weight of the amino group-containing resin is, for example, from 100 to 1,000,000, preferably from 200 to 10,000, more preferably from 300 to 5,000. The number average molecular weight of the amino group-containing resin is determined, for example, by a known viscosity method. When the molecular weight of the amino group-containing resin is too large, the viscosity may become too high due to gel crosslinking in the liquid of the adhesive composition, which may cause problems in workability.

[0120] The aqueous component having a plurality of amino groups in the (E) molecule coats the surface of the rubber latex having the (A) unsaturated diene in the adhesive composition to suppress tackiness. By the function of surface adsorption of the (E) component, the surface of the rubber latex having the (A) unsaturated diene is coated to form a complex with the rubber latex having the (A) unsaturated diene. And by this coating, the effect of suppressing the tackiness of the rubber latex having the (A) unsaturated diene can be obtained, which has the effect of improving the storage stability (pot life) and mechanical stability of the adhesive composition. Also, by coating the adhesive composition on an organic fiber cord, it also has the effect of improving the heat-resistant adhesive strength between the rubber and the organic fiber cord.

[0121] It is preferable that the aqueous component having a plurality of amino groups in the (E) molecule is (E-1) a polypeptide having an amino group, (E-2) a polyetheramine, (E-3) a polyethyleneimine, or (E-4) a polyamidoamine.

[0122] In the adhesive composition of the present invention, the content of the aqueous component having a plurality of amino groups in the molecule (E) is not particularly limited, but is preferably 0.05% by mass or more, and preferably 20% by mass or less. The content of the aqueous component having a plurality of amino groups in the molecule (E) is more preferably 0.2% by mass or more and 15% by mass or less, and particularly preferably 0.5% by mass or more and 12% by mass or less. If the content of the aqueous component having a plurality of amino groups in the molecule (E) is 0.05% by mass or more, the adhesiveness between the organic fiber and the coating rubber composition will be better. Further, if the content of the aqueous component having a plurality of amino groups in the molecule (E) is 20% by mass or less, it becomes possible to ensure a certain amount or more of other components such as rubber latex blended in the adhesive composition. As a result, the adhesiveness to the adherend rubber becomes better.

[0123] --(E-1) Polypeptide having an amino group-- Specific examples of the polypeptide (E-1) having an amino group include proteins derived from animals such as polylysine, wool, milk, silk (silk fibroin), fish scales, and skin (such as pig skin), proteins derived from plants such as beans (soybeans, almonds, etc.), denatured proteins such as acid casein, or hydrolyzed polypeptides obtained by hydrolyzing these proteins. In the present invention, the polypeptide having a plurality of amino groups in the molecule (E-1) is not particularly limited, but in the examples described later, polylysine was used.

[0124] The polylysine is a polyamino acid in which L-lysine, an essential amino acid, is polymerized linearly, and includes α-polylysine produced by chemical synthesis and ε-polylysine produced by a fermentation method. ε-Poly-L-lysine is a water-soluble polyamino acid in which the amino group at the ε-position of L-lysine is peptide-bonded to a carboxyl group and connected linearly. It is an excellent biodegradable cationic polymer produced by fermentation by bacteria and is used as a natural preservative for foods. As polylysine, the following structural formula (2): [Chemical formula] Compounds represented by the following formula are included. In the formula above, n represents the degree of polymerization of lysine.

[0125] The degree of polymerization n of the polylysine is preferably 25 to 35. Also, the weight average molecular weight of the polylysine is preferably 3,000 or more, more preferably 4,000 or more, and preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, and particularly preferably 5,000 or less.

[0126] --(E-2) Polyetheramine-- The (E-2) polyetheramine is a polyetheramine containing at least one primary and / or secondary amine functional group bonded to the main chain composed of the polyether, or a modified form of these compounds. Useful polyetheramines include polyetheramines in which an amine functional group is introduced at the end of a polyether polymer or the like. Examples of the (E-2) polyetheramine include polyether monoamine, polyether diamine, polyether triamine, and polyether polyamine.

[0127] The (E-2) polyetheramine is preferably a compound containing a skeletal structure composed of a polyether and an amine functional group. Here, the "skeletal structure composed of a polyether" means a hydrocarbon chain in which an oxygen atom of an ether bond is incorporated. Generally, as long as the effects of the present invention are not significantly impaired, it can include a polyether polymer obtained by ring-opening polymerization of a cyclic monomer such as a polyalkylene oxide or a polyalkyleneimine, or a polyether such as a naturally-derived molecule. For example, examples of the polyether obtained by ring-opening polymerization of the above cyclic monomer include polyether-based polymers such as polyethylene oxide obtained by ring-opening polymerization of ethylene oxide, polypropylene oxide obtained by ring-opening polymerization of propylene oxide, or polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran. A polyether polymer obtained by ring-opening polymerization of a cyclic polyalkylene oxide has an oxyalkylene unit -R 1 -O-(R 1 which is a linear or branched alkylene group having 1 to 14 carbon atoms). For example, as the repeating oxyalkylene unit, -CH2O-, -CH2CH2O- (i.e., oxyethylene unit), -CH2CH(CH3)O- (i.e., oxypropylene unit), -CH2CH(C2H5)O-, -CH2C(CH3)2O-, -CH2CH2CH2CH2O- and the like can be mentioned. The repeating oxyalkylene unit of this polyether polymer may consist of only one kind of repeating unit or may consist of two or more kinds of units.

[0128] When the (E-2) polyetheramine has a skeletal structure composed of the polyether which is a "polyether polymer obtained by polymerizing a polyalkylene oxide", the (E-2) polyetheramine is liable to dissolve or disperse in water. Therefore, the molecular chain of the polymer composed of polyether preferably contains an alkylene oxide unit showing hydrophilicity. Specifically, a structure containing an oxyethylene unit, an oxypropylene unit, or a combination of an oxyethylene unit and an oxypropylene unit is preferable. When such a molecular chain composed of polyether has an HLB value in the range of 8 to 20 by the Griffin method, the (E-2) polyetheramine is particularly preferable because it easily dissolves in water.

[0129] In the present invention, the polyether polymer obtained by ring-opening polymerization of the above cyclic monomer includes dimers, trimers and oligomers in the polymer, but it is preferable that the weight average molecular weight Mw measured by GPC and converted by the calibration curve of polystyrene is 200 to 200,000. The lower limit value of the weight average molecular weight Mw is more preferably 300, still more preferably 500. The upper limit value of the weight average molecular weight Mw is more preferably 100,000, still more preferably 10,000, and particularly preferably 3,000.

[0130] In one embodiment, the (E-2) polyetheramine is preferably a polyetheramine selected from the group consisting of polyether monoamines, polyether diamines, polyether triamines, polyfunctionalized polyetheramines, and mixtures thereof.

[0131] Commercially available polyether monoamines are not particularly limited. However, when it is a polyether monoamine, examples include JEFFAMINE® M-600, M-1000, M-2005, M-2070, M-2095, M-3085 manufactured by Huntsman Petrochemical LLC, and Genamin® M41 / 2000 manufactured by CLARIANT AG.

[0132] When it is a polyether diamine, examples include JEFFAMINE® D-230, D-400, D-2000, D-2010, D-4000, ED-600, ED-900, ED-2003, EDR-148, THR-100, THR-170, and the secondary diamine SD-2001 manufactured by Huntsman Petrochemical LLC; Baxxodur® EC-130, EC-280, EC-301, EC-302, EC-303 manufactured by BASF SE; Genamin® D01 / 2000 manufactured by CLARIANT AG; D-230, D-400, D-2000, ED-600, ED-900, ED-2003 manufactured by Yangzhou Chehua New Materials Co., Ltd.; D-400, D-2000 manufactured by Yantai Dasteck Chemicals Co., Ltd.; MA-223, MA-240, MA-2200 manufactured by WUXI ACRYL TECHNOLOGY CO., LTD.; AMD-230, AMD-400, AMD-1000, AMD-2000 manufactured by Yantai Minsheng Chemicals Co., Ltd.; D-230, D-400, D-2000 manufactured by IRO COATING ADDITIVE CO., LTD.

[0133] In the case of polyether triamine, examples include JEFFAMINE® T-403, T-3000, and T-5000 manufactured by Huntsman Petrochemical LLC, Baxxodur® EC-311, EC-5000 manufactured by BASF SE, Genamin® T01 / 5000 manufactured by CLARIANT AG, T-403 and T-3000 manufactured by Yangzhou Chehua New Materials Co., Ltd., T-403 manufactured by Yantai Dasteck Chemicals Co., Ltd., MA-340 and MA-3500 manufactured by WUXI ACRYL TECHNOLOGY CO., LTD., AMT-403 and AMT-5000 manufactured by Yantai Minsheng Chemicals Co., Ltd., T-403, T-3000, and T-5000 manufactured by IRO COATING ADDITIVE CO., LTD., and the like. In the following examples, as the (E-2) polyetheramine, Baxxodur EC301, which is polyoxypropylene diamine manufactured by BASF SE, was used.

[0134] --(E-3) Polyethyleneimine-- In the present invention, as the (E) aqueous component having a plurality of amino groups in the molecule, the above (E-3) polyethyleneimine can be preferably used. Polyethyleneimine is a water-soluble polymer obtained by polymerizing ethyleneimine, and is a polymer composed of repeating units of amine and ethylene (CH2CH2). Polyethyleneimine generally contains primary, secondary, and tertiary amino groups. For example, a commercially available reagent polyethyleneimine having a branched structure instead of a complete linear molecule and an average molecular weight of about 600 can be used. The above (E-3) polyethyleneimine is available in liquid form, but is preferably used as an aqueous solution in the use in the adhesive composition of the present invention.

[0135] --(E-4) Polyamidoamine-- Examples of the (E-4) polyamideamine include reaction products of polyamines and long-chain carboxylic acids (polycarboxylic acids). Here, examples of the polyamine include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyether diamine, diethylaminopropylamine, 1,4-cyclohexanediamine, isophoronediamine, bis(aminomethyl)norbornane, bis(4-aminocyclohexyl)methane, N-aminoethylpiperazine, diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, norbornenediamine, and the like. Examples of the long-chain carboxylic acid (polycarboxylic acid) include dimer acid (a polymer of unsaturated fatty acids).

[0136] <Compound containing (F) amide bond structure> One preferred embodiment of the adhesive composition of the present invention includes (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and (F) a compound containing an amide bond structure.

[0137] By using a compound containing an (F) amide bond structure together with the (A) rubber latex having an unsaturated diene in the adhesive composition, the compound containing the (F) amide bond structure covers the surface of the rubber latex particles and suppresses the aggregation of the rubber latex particles. As a result, the dispersibility of the rubber latex when subjected to a mechanical load is enhanced, and excellent mechanical stability can be achieved. As a result, in the step of coating an organic fiber cord with the adhesive composition containing a compound having an (F) amide bond structure and drying and thermosetting the coated cord, it becomes possible to suppress the adhesion of the adhesive composition to a roll or the like, and the workability becomes good. Furthermore, when a compound having an (F) amide bond structure is fixed on the surface of a rubber latex having an (A) unsaturated diene, the adhesiveness between the adhesive composition and the adherend rubber composition becomes good.

[0138] Furthermore, as described above, by containing an aqueous compound having two or more polymerizable (meth) acrylate structures, (meth) acrylamide structures, or (meth) allyl structures in the molecule (B), the compound having an (F) amide bond structure and the aqueous compound having two or more polymerizable (meth) acrylate structures, (meth) acrylamide structures, or (meth) allyl structures in the molecule (B) are affinity due to some structures being similar, and when the (B) component wetted with the compound having an (F) amide bond structure crosslinks, a mutual wetting network is formed, increasing the interaction between the components and making the adhesiveness between the adhesive composition and the adherend rubber composition good.

[0139] The compound having an (F) amide bond structure is preferably a polymer composed of (meth) acrylamide, or a copolymer containing (meth) acrylamide and other polymerizable monomers. For example, it can include a structure composed of a copolymer composed of (a) (meth) acrylamide and / or (b) a vinyl monomer having a cationic group, and / or (c) a vinyl monomer having an anionic group, and / or (d) other copolymerizable polymerizable monomers.

[0140] Here, the (meth)acrylamide in (a) refers to acrylamide and methacrylamide. In the following, (meth)acryl is similarly abbreviated on the assumption that it is synonymous with acrylic and / or methacrylic. The "amide bond structure" can be mainly obtained from the structure formed by polymerizing the (meth)acrylamide in (a). The (meth)acrylamide can be used alone or in combination of two types. Preferably, from the perspective of economy, it is better to use acrylamide alone.

[0141] The content ratio of the (meth)acrylamide in (a) is, for example, 50 mol% or more, preferably 60 mol% or more, and preferably 100 mol% or less, based on all the monomers constituting the acrylamide-based polymer. When the content of component (a) is less than 50 mol%, the adhesive force due to cohesive forces such as hydrogen bonding by the amide moiety decreases.

[0142] Examples of the vinyl monomer having a (b) cationic group include vinyl monomers having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium salt.

[0143] Examples of the vinyl monomer having a primary amino group include 2-propenylamine, 2-methyl-2-propenylamine; or inorganic acid salts such as hydrochlorides and sulfates of the above primary amino-based monomers; or organic acid salts such as formates and acetates of the above primary amino-based monomers.

[0144] Examples of the vinyl monomer having a secondary amino group include di(2-propenyl)amine (diallylamine), di(2-methyl-2-propenyl)amine; or inorganic acid salts such as hydrochlorides and sulfates of the above secondary amino-based monomers; or organic acid salts such as formates and acetates of the above secondary amino-based monomers.

[0145] Examples of the vinyl monomer having a tertiary amino group include dialkylaminoalkyl (meth) acrylates such as N,N-dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate, and N,N-dimethylaminopropyl (meth) acrylate; dialkylaminoalkyl (meth) acrylamides such as N,N-dimethylaminoethyl (meth) acrylamide, N,N-diethylaminoethyl (meth) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide, and N,N-diethylaminopropyl (meth) acrylamide; tertiary amine-based monomers such as allylamine, diallylamine, and vinylpyridine; or inorganic acid salts such as hydrochlorides and sulfates of the above tertiary amine-based monomers; or organic acid salts such as formates and acetates of the above tertiary amine-based monomers. Among these, N,N-dimethylaminoethyl (meth) acrylate is preferred in terms of polymerizability and price.

[0146] The vinyl monomer having a quaternary ammonium salt is a cationic copolymerizable monomer having a quaternary ammonium group and an ethylenic double bond. For example, a vinyl monomer of a quaternary ammonium salt obtained by reacting the above vinyl monomer having a tertiary amino group with an alkylating agent (a quaternized product of a tertiary amine-based monomer), or, for example, a quaternized product obtained by quaternizing the tertiary amino group of a diallylamine derivative monomer, etc. These quaternary ammonium-based monomers can be used alone or in combination of two or more.

[0147] Examples of the quaternized product of the tertiary amine-based monomer include quaternized products using alkyl halides such as methyl chloride (methyl chloride) and methyl bromide as the alkylating agent for quaternizing the tertiary amino group of the above polymerizable monomer having a tertiary amino group; aralkyl halides such as benzyl chloride (benzyl chloride); dimethyl sulfate, diethyl sulfate, epichlorohydrin, glycidyl trialkylammonium chloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride. Among the quaternized products of these tertiary amino group-containing monomers, preferably, the quaternized products of dialkylaminoalkyl (meth)acrylamides can be mentioned. Further, as a preferable alkylating agent for quaternization, quaternized products with methyl chloride or benzyl chloride can be mentioned.

[0148] Examples of the quaternized products of the diallylamine derivative monomers include diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride, diallyldibutylammonium chloride, diallylmethylethylammonium chloride and the like. Among these quaternized products of the diallylamine derivative monomers, preferably, diallyldimethylammonium chloride can be mentioned.

[0149] In the present invention, these vinyl monomers having a primary amino group, a secondary amino group, a tertiary amino group or a quaternary ammonium salt can be used alone or in combination of two or more. Note that the dissociation of the primary to tertiary amino groups is suppressed at pH 7 or higher, whereas when a quaternary ammonium base is contained, it can dissociate even at pH 9 or higher. Therefore, when generally mixed with a latex having a pH of 10 or higher, the function as a cation can be maintained in a wide pH range. However, since the primary amine group has a high hydrogen bonding force with respect to the tertiary and quaternary amines, the interaction with other components of the adhesive composition can be increased.

[0150] The content ratio of the vinyl monomer having the (b) cationic group is not particularly limited. However, when it is included, it is, for example, 0.01 mol% or more, preferably 0.5 mol% or more, and, for example, 20 mol% or less, preferably 10 mol% or less, based on all the monomers constituting the acrylamide-based polymer. When the content ratio of the vinyl monomer having a cation group is 0.01 mol% or more, when it is adsorbed on the surface of latex particles dispersed in water with an anionic surfactant by coacervation and surface-coated, the adhesiveness of the latex can be suppressed. Preferably it is 0.5 mol% or more. Also, if it is 20 mol% or less, the cohesiveness between particles becomes high, which is not preferable. Further, if the content ratio of the vinyl monomer having a cation group is 10 mol% or less, the degree of polymerization in production tends to be short, which is preferable.

[0151] The vinyl monomer having the (c) anionic group is not particularly limited as long as it is a vinyl monomer having an anionic group in the molecule, and examples include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, unsaturated tetracarboxylic acids, and their salts. Specifically, unsaturated monocarboxylic acids such as (meth)acrylic acid, angelic acid, tiglic acid, crotonic acid, isocrotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, muconic acid, citraconic acid; unsaturated tricarboxylic acids such as 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid, aconitic acid; or alkali metal salts such as sodium salts and potassium salts of these various organic acids or ammonium salts; sulfonic acid-based monomers having a vinyl group such as vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (meth)allylsulfonic acid, diacryloylimide; or salts such as alkali metal salts such as sodium salts and potassium salts of these various organic acids or ammonium salts, etc. are mentioned. In the present invention, these vinyl monomers having an anionic carboxyl group and their salts can be used alone or in combination of two or more. Among these, from the viewpoints of polymerizability and price, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids, specifically, acrylic acid, 2-acrylamido-N-glycolic acid, itaconic acid and their salts are preferable, and particularly, acrylic acid or its sodium salt is preferable.

[0152] The content ratio of the vinyl monomer having the (c) anionic group is not particularly limited. When included, it is, for example, 0.01 mol% or more, preferably 0.5 mol% or more, based on all the monomers constituting the acrylamide polymer, and is, for example, 20 mol% or less, preferably 10 mol% or less. When the polymerization component contains 0.01 mol% or more of an anionic polymerizable monomer, the polyamide adsorbed on the latex has a high effect of suppressing the adhesiveness due to the anionic group. On the other hand, when the carboxyl group increases, the acidity becomes strong in rubber vulcanization. Here, the sulfur crosslinking reaction of the rubber latex becomes low when the acidity is strong, so the crosslinking of the adhesive layer tends to decrease.

[0153] Further, from the viewpoint of processability, the compound containing the (F) amide bond structure may be a copolymer containing (d) other copolymerizable polymerizable monomers.

[0154] Specific examples of other polymerizable monomers include N-substituted lower alkyl acrylamides other than (meth)acrylamide such as N-ethylacrylamide, N,N-dimethylacrylamide, and N-isopropylacrylamide; N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N,N-diisopropyl (meth)acrylamide; alkylene bis(meth)acrylamides such as methylene bis(meth)acrylamide and ethylene bis(meth)acrylamide; allyl (meth)acrylamide; N-substituted acrylamide-based monomers such as N,N'-dimethylacrylamide, diacetone acrylamide, and isopropylacrylamide. Further, examples of other polymerizable monomers containing an imide group include diacryloyl imide. Preferably, alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate are mentioned.

[0155] In addition, examples of other copolymerizable polymerizable monomers that do not contain an amide group or an imide group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl meth) acrylate, cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and (meth) acrylates having a hydroxyl group such as glycerol mono (meth) acrylate; polyalkylene glycol mono (meth) acrylates such as diethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate; polyalkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate; polyalkylene glycol monoether mono (meth) acrylates such as acrylate of diethylene glycol monoethyl ether compound; epoxy acrylate; urethane acrylate; nitrile compound-based monomers such as acryloyl morpholine, (meth) acrylonitrile; olefins such as vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene; substituted vinyl acetates such as isopropenyl acetate, 1-methoxyvinyl acetate; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylpyrrolidone, vinyloxazoline, and the like.

[0156] These other polymerizable monomers may be used alone or in combination of two or more. Among them, when a branched structure is introduced by an elongation reaction during polymerization, the cured film after heat treatment of the adhesive composition has high hardness and excellent adhesion to the substrate. Therefore, crosslinkable monomers containing an amide group such as N-substituted acrylamide-based monomers such as methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, allyl (meth)acrylamide, N,N'-dimethylacrylamide, diacetone acrylamide, isopropylacrylamide; crosslinkable monomers containing an imide group such as diacryloylimide; difunctional crosslinkable monomers that do not contain nitrogen such as divinylbenzene, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, allyl (meth)acrylate, and polyfunctional crosslinkable monomers that do not contain nitrogen such as pentaerythritol triacrylate, trimethylolpropane acrylate, tetraallyloxyethane are preferably used. Among these, N,N-dialkyl(meth)acrylamide and alkylene bis(meth)acrylamide are preferred, and N,N-dimethylacrylamide and methylene bis(meth)acrylamide are more preferred.

[0157] (d) These monomers, which are provided to a copolymer containing other copolymerizable polymerizable monomers, are not limited to the exemplified monomers. They are optional components, and their usage amount is not particularly limited, but generally 0.01 mol% or more, preferably 0.1 mol% to 40 mol%. For example, 0.01 mol% or more, preferably 0.1 mol% or more, and for example, 30 mol% or less, preferably 20 mol% or less.

[0158] The compound containing the (F) amide bond structure may be further modified, including modified products cross-linked by adding hydrazide compounds such as hydrazine, or modified products obtained by Mannich modification of polyacrylamide, in which a part of the acrylamide structure derived from (a) (meth)acrylamide is modified into a cationic group, and modified products obtained by modifying cationic polyacrylamide such as glyoxalated polyacrylamide with formaldehyde-based cross-linking agents such as glyoxal.

[0159] Specifically, the compound containing the above (F) amide bond structure, the polymer composed of (a) (meth)acrylamide is also called nonionic polyacrylamide, the copolymer composed of (a) (meth)acrylamide and (b) vinyl monomer having a cationic group is also called cationic polyacrylamide, the compound composed of a copolymer of (a) (meth)acrylamide and (c) vinyl monomer having an anionic group is also called anionic polyacrylamide, and the copolymer of the polymer composed of (a) (meth)acrylamide and (b) vinyl monomer having a cationic group and (c) vinyl monomer having an anionic group is also called amphoteric polyacrylamide.

[0160] These compounds containing (F) amide bond structures can be obtained by reacting them with known methods of nonionic polyacrylamide, cationic polyacrylamide, anionic polyacrylamide containing a carboxyl group, and amphoteric polyacrylamide. For example, the production method is not particularly limited. However, a copolymer can be obtained by copolymerizing a mixture of (meth)acrylamide and a cationic vinyl monomer and / or an ionic vinyl monomer by aqueous solution polymerization, emulsion polymerization using water and an organic solvent, suspension polymerization, etc. The production can be carried out by various conventionally known methods such as simultaneous polymerization and continuous dropping polymerization. For example, a mixture of the above monomers and water is charged, a persulfate such as potassium persulfate or ammonium persulfate, or a known radical polymerization initiator such as a redox polymerization initiator is added, and a chain transfer agent can be further added as appropriate. Under stirring, a copolymer can be produced by polymerizing at about 15°C to 100°C for 0.1 to several hours. The polymerization reaction is stopped by adding a known polymerization terminator such as sodium thiosulfate or sodium sulfite.

[0161] Examples of the chain transfer agent include isopropyl alcohol, mercaptans (e.g., mercaptoethanol, thiourea, thioglycolic acid, mercaptopropionic acid, thiosalicylic acid, thiolactic acid, aminoethanethiol, thioglycerol, thiomalic acid, etc.). The amount of such a chain transfer agent used is usually 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total monomers of the compound containing an acrylamide structure having a cationic group and / or a carboxyl group.

[0162] The compound containing (F) amide bond structure thus obtained can be obtained in the form of an aqueous solution or an aqueous dispersion. Note that polyacrylamide obtained in gel form may be mechanically pulverized and then redispersed in water for use. In the use in the adhesive composition of the present invention, it is preferably used as an aqueous solution.

[0163] The weight average molecular weight of the copolymerized polyacrylamide thus obtained is, for example, 1,000,000 or more, preferably 2,000,000 or more, more preferably 2,000,000 or more, and for example, 15,000,000 or less, preferably 10,000,000 or less, more preferably 8,000,000 or less. When the weight average molecular weight of the acrylamide-containing compound is 1,000,000 or more, the aggregation of the rubber latex particles can be more reliably suppressed. When the weight average molecular weight of the acrylamide-containing compound is 15,000,000 or less, problems such as crosslinking and gelation of the acrylamide-containing compound do not occur.

[0164] Also, when the pH is usually about 3 to 9 and the viscosity is about 100 to 10,000 mPa·s in a 10% by mass aqueous solution, it becomes easier to use in a liquid state for storage in a liquid state, liquid transfer, etc.

[0165] As the compound containing the (F) amide bond structure, commercially available nonionic, anionic, cationic or amphoteric polyacrylamide products can be used. In particular, papermaking chemicals exemplified by a yield improver, a drainage improver, a paper strength enhancer, etc., which are internal additives for paper, can be used.

[0166] The copolymerized polyacrylamide for papermaking chemicals can obtain a function of imparting strength to the paper of the product by fixing (adsorbing) to the pulp. By adding a paper strength enhancer, the adhesive strength between cellulose fibers constituting the paper in papermaking is improved (Yasushi Takahata, Utilization of Synthetic Polymers in the Papermaking Industry (First Report), Journal of the Paper and Pulp Technical Association of Japan, 1973, Vol. 27, No. 12, p. 607). The amide group of the polyacrylamide resin is highly reactive and has strong affinity with fillers due to hydrogen bonds, van der Waals forces, etc., and thus has excellent cohesive force. Therefore, the amide site is a site for improving paper strength. When it is a compound containing an amide bond structure composed of (a) (meth)acrylamide, etc., in the adhesive composition of the present invention, an effect of improving the cohesive failure resistance can be obtained in the adhesive layer between the adhered fiber filaments, which is preferable.

[0167] In addition, for nonionic polyacrylamide composed of (meth)acrylamide, since some amide bond structures are decomposed to have anionic groups and cationic groups, it is not actually completely nonionic but has a slight zwitterionic property. These nonionic polyacrylamides are inexpensive and have a certain fixing property due to slight zwitterionic property, which is preferable. Also, amphoteric polyacrylamide has a function of fixing to rubber latex and a function of fixing to a substrate. Moreover, even if it is thickened or the cationic groups become excessive, it has a self-fixing function, so it is not likely to thicken the liquid and can be used well.

[0168] The content (solid content ratio) of the compound containing the (F) amide bond structure in the total solid content of the adhesive composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.4% by mass or more. Also, the content of the compound containing the (F) amide bond structure is preferably 25% by mass or less, more preferably 15% by mass or less, and still more preferably 8% by mass or less. This is because if the content of the compound containing the (F) amide bond structure is 0.1% by mass or more, the adhesiveness between the organic fiber and the coating rubber composition becomes better. Also, if the content of the compound containing the (F) amide bond structure is 25% by mass or less, it becomes possible to ensure a certain amount or more of other components such as rubber latex blended in the adhesive composition. As a result, the adhesiveness to the adherend rubber becomes better.

[0169] <(C) Aqueous compound having a (thermally dissociable blocked) isocyanate group> One preferred embodiment of the adhesive composition of the present invention includes (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, and (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group. Furthermore, the following (D) to (F): (D) An aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) An aqueous component having a plurality of amino groups in the molecule, (F) A compound containing an amide bond structure, It contains one or more compounds selected from the group consisting of.

[0170] The adhesive composition of the preferred embodiment contains the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group, so that excellent adhesiveness and mechanical stability can be achieved even when formaldehyde and resorcin are not contained.

[0171] The (thermally dissociable blocked) isocyanate group of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group means a thermally dissociable blocked isocyanate group or an isocyanate group. Specifically, the (thermally dissociable blocked) isocyanate group means (i) a thermally dissociable blocked isocyanate group formed by the reaction of an isocyanate group with a thermally dissociable blocking agent for the isocyanate group, (ii) an isocyanate group in which the isocyanate group is unreacted with the thermally dissociable blocking agent for the isocyanate group, (iii) an isocyanate group formed by the dissociation of the thermally dissociable blocking agent from the thermally dissociable blocked isocyanate group, and (iv) an isocyanate group.

[0172] The aqueous property of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group indicates water solubility or water dispersibility. Also, the water solubility does not necessarily mean complete water solubility, but also means partial water solubility or no phase separation in the aqueous solution of the adhesive composition.

[0173] The aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is preferably a water-dispersible (thermally dissociable blocked) isocyanate compound (hereinafter, also simply referred to as the "(C-1) component") composed of an addition product of a polyisocyanate having an aromatic ring and a blocking agent having one or more active hydrogen groups. In this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better.

[0174] Here, regarding the (C-1) component, the active hydrogen group means a group containing hydrogen that becomes active hydrogen (atomic hydrogen (hydrogen radical) and hydride ion (hydride)) when placed under suitable conditions. Examples of the active hydrogen group include an amino group and a hydroxyl group.

[0175] The thermally dissociable blocking agent is not particularly limited as long as it is a blocking agent compound that can protect the isocyanate group from any chemical reaction and dissociate the blocking agent by heat treatment as necessary to restore the isocyanate group. Specifically, in the process shown in FIG. 1, at the temperature of the heat treatment for thermosetting after the adhesion treatment liquid is adhered and dried, it is preferably a thermal dissociation temperature at which the crosslinking reactivity of the isocyanate group blocked by the thermally dissociable blocking agent and suppressed in reactivity can be restored.

[0176] Examples of the blocking agent include, but are not particularly limited to, alcohol, phenol, active methylene, oxime, lactam, amine, etc. Specifically, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; phenols such as phenol, cresol, ethylphenol, butylphenol, octylphenol, nonylphenol, dinonylphenol, thiophenol, chlorophenol, amylphenol; oximes such as methyl ethyl ketoxime, acetoxime, acetophenone oxime, benzophenone oxime, cyclohexanone oxime; alcohols such as methanol, ethanol, butanol, isopropyl alcohol, butyl alcohol, cyclohexanol; dialkyl malonates such as dimethyl malonate, diethyl malonate; active methylenes such as methyl acetoacetate, ethyl acetoacetate, acetylacetone; mercaptans such as butyl mercaptan, dodecyl mercaptan; amides such as acetanilide, acetic amide; imides such as succinimide, phthalimide, maleimide; sulfites such as sodium bisulfite; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; pyrazoles such as pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, diphenylamine, xylidine, N,N-diethylhydroxyamine, N,N'-diphenylformamidine, 2-hydroxypyridine, 3-hydroxypyridine and 2-mercaptopyridine; and triazoles such as 1,2,4-triazole. Mixtures of two or more of these may also be used. Among these blocking agents, phenol, ε-caprolactam and ketooxime, which can easily and stably obtain the thermosetting of the adhesive composition by thermal dissociation upon heating, can be preferably used.

[0177] In addition, specifically, the component (C-1) includes aromatic polyisocyanates or araliphatic polyisocyanates. Examples of the aromatic isocyanates include phenylenediisocyanates such as m-phenylenediisocyanate and p-phenylenediisocyanate; tolylenediisocyanates such as 2,4-tolylenediisocyanate and 2,6-tolylenediisocyanate (TDI); diphenylmethane diisocyanates such as 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), dialkyldiphenylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate; polymethylene polyphenyl polyisocyanate (polymeric MDI); m- or p-isocyanatophenylsulfonyl isocyanates; diisocyanatobiphenyls such as 4,4'-diisocyanatobiphenyl and 3,3'-dimethyl-4,4'-diisocyanatobiphenyl; naphthalenediisocyanates such as 1,5-naphthalenediisocyanate; and the like. Examples of the araliphatic polyisocyanates include xylylene diisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate; diethylbenzene diisocyanate; and α,α,α,α-tetramethylxylylene diisocyanate (TMXDI); and the like. Further, modified products such as carbodiimide, polyol, and allophanate of the above polyisocyanate are also included. Among these polyisocyanates containing an aromatic ring in the molecule, from the viewpoint of the code focusing property of the adhesive composition, aromatic isocyanates are preferred, more preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or polymethylene polyphenyl polyisocyanate (polymeric MDI), and particularly preferably diphenylmethane diisocyanate (MDI) type. By using a blocked body of methylene diphenyl isocyanates, especially a blocked body of methylene diphenyl diisocyanate (also called "diphenylmethane diisocyanate"), when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better.

[0178] Further, it is more preferable that the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is an aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group (hereinafter, also simply referred to as "(C-2) component"). Also in this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes better. Details of the above (C-2) component will be described later for convenience of explanation.

[0179] The content (solid content ratio) of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group in the total solid content of the adhesive composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 18% by mass or more. Also, the content of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 45% by mass or less. This is because when the content of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is 5% by mass or more, the adhesiveness between the organic fibers and the coating rubber composition becomes better. Also, when the content of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is 70% by mass or less, it becomes possible to ensure a certain amount or more of other components such as rubber latex blended in the adhesive composition. As a result, the adhesiveness with the adherend rubber becomes better.

[0180] Here, in a conventional adhesive composition containing resorcin and formaldehyde, a sea-island structure in which rubber latex particles (exemplified as islands) are dispersed in a phenolic resin (exemplified as the sea) in which these resorcin and formaldehyde are co-condensed is formed. Thereby, good adhesiveness between the phenolic resin covering the organic fiber surface and the organic fiber is obtained.

[0181] On the one hand, in a preferred embodiment of the adhesive composition of the present invention, instead of the phenolic resin obtained by the co - condensation of the resorcinol and formaldehyde, the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group acts as an adhesion promoter with the following two functional effects (x) and (y). As a result, in the adhesive composition, the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group contributes to the characteristic of good adhesion between the organic fiber and the coating rubber composition.

[0182] (x) A functional effect in which the aqueous compound is distributed near the interface between the organic fiber and the adhesive layer formed by the adhesive composition, promoting the adhesion between the organic fiber and the adhesive layer. (y) A functional effect in which a three - dimensional network structure is formed by cross - linking with isocyanate groups by the compound having the (thermally dissociable blocked) isocyanate group within the adhesive layer formed by the adhesive composition, reinforcing the adhesive layer.

[0183] In one embodiment of the adhesive composition of the present invention, an example of the principle of the two functional effects (x) and (y) of the aqueous compound having the (C) (thermally dissociable blocked) isocyanate group as the adhesion promoter will be described in detail below.

[0184] --Regarding the functional effect as the adhesion promoter of (x)-- Synthetic resin materials such as 6,6 - nylon and polyethylene terephthalate, which are widely used as organic fibers, are composed of flat linear polymer chains. And the surface of the polymer chain or the gap between the polymer chains has a π - electron atmosphere derived from aromatics and the like contained in the polymer chain. Therefore, conventionally, in order to obtain sufficient adhesive strength, an adhesive composition used for organic fibers made of polyester or the like aims to disperse the adhesive composition into the gaps between the polymer chains of the organic fiber and to make the adhesive layer formed by the adhesive composition adhere closely to the surface of the polymer chains of the organic fiber, and contains molecules with a planar structure having an aromatic ring with aromatic π - electrons on the side (a part that is easy to diffuse into the organic fiber) as an adhesion promoter. In the present invention, in an adhesive composition that does not contain resorcinol which is an aromatic compound, even in an adhesive composition for 6,6-nylon, it is preferable to add an adhesion promoter for molecules having a planar structure (a portion that easily diffuses into organic fibers) having an aromatic ring with aromatic π electrons on the side to promote adhesion.

[0185] --Regarding the functional effects of the adhesion promoter of (y)-- When the adhesive composition contains an aqueous component having a plurality of phenolic hydroxy groups in the molecule (D), in the adhesive layer containing the component (C), by forming a covalent bond by isocyanate crosslinking between the phenolic hydroxy groups of the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) and the isocyanate from which the blocking agent has dissociated by heat treatment, the adhesion by the adhesive composition can be strengthened.

[0186] As described above, the particle size of the component (C-1) is preferably 0.01 to 0.50 μm. When the particle size of the component (C-1) is 0.50 μm or less, the smaller the particle size, the more difficult it is for the component (C-1) to settle in the liquid, and the less likely it is for the dispersion in the adhesive layer to become non-uniform. On the other hand, when it is an aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group, since the water solubility is high, sedimentation of components in the adhesive composition liquid hardly occurs, and there are few component non-uniformities even during standing storage. Therefore, adhesion over time is stable, which is preferable.

[0187] --Thermally dissociable blocking agent, aqueous urethane compound-- The thermal dissociation blocking agent of the component (C-2) is not particularly limited as long as it is a blocking agent compound capable of protecting isocyanate groups from any chemical reaction and dissociating the blocking agent by heat treatment as necessary to restore the isocyanate groups. As specific examples of the thermal dissociation blocking agent, the same compounds as the blocking agents described above for the component (C-1) can be used. Preferably, phenols such as phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol, tert-butyl alcohol; aromatic secondary amines such as diphenylamine, xylylidene; phthalimides; lactams such as δ-valerolactam; caprolactams such as ε-caprolactam; dialkyl malonates such as diethyl malonate, dimethyl malonate; active methylene compounds such as acetylacetone, alkyl acetoacetate; oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime; basic nitrogen compounds such as 3-hydroxypyridine, 1,2-pyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole, diisopropylamine, N,N'-diphenylformamidine; and sodium acid sulfite, etc. may be mentioned.

[0188] Among these blocking agents, phenol, ε-caprolactam and ketooxime, which can easily and stably obtain the thermosetting of the adhesive composition by thermal dissociation upon heating, can be preferably used.

[0189] Here, the water-solubility of the aqueous urethane compound means water-soluble or water-dispersible. Also, the water-solubility does not necessarily mean complete water-solubility, but also means partially water-soluble or not phase-separating in the aqueous solution of the adhesive composition.

[0190] The urethane compound of the aqueous urethane compound is a compound having a covalent bond formed between the nitrogen of the amine and the carbon of the carbonyl group, and means a compound represented by the following general formula (3). [Chemical formula] In the above formula (3), R and R' represent hydrocarbon groups.

[0191] The molecular weight of the aqueous urethane compound having the (C-2) (thermally dissociable blocked) isocyanate group is not particularly limited as long as it can maintain its aqueous nature, preferably the number average molecular weight is 1,500 to 100,000, and particularly preferably the number average molecular weight is 9,000 or less.

[0192] The method for synthesizing the (C-2) component is not particularly limited as described above, and known methods such as the method described in JP-A-63-51474 can be used.

[0193] --Preferred embodiments of the aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group-- A preferred embodiment of the component (C-2) is a reaction product obtained by mixing and reacting (α) an organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, (β) a compound having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less, (γ) a thermally dissociable blocking agent, and (δ) a compound having at least one active hydrogen group and at least one hydrophilic group that is anionic, cationic or nonionic, in a predetermined mixing ratio, and the constituent ratio of the (thermally dissociable blocked) isocyanate group in the reaction product, when the molecular weight of the isocyanate group (-NCO) is 42, is 0.5% by mass or more and 11% by mass or less. Here, the mixing ratio of each of (α), (β), (γ) and (δ) with respect to the total amount is 40% by mass or more and 85% by mass or less for (α), 5% by mass or more and 35% by mass or less for (β), 5% by mass or more and 35% by mass or less for (γ), and 5% by mass or more and 35% by mass or less for (δ). In this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coated rubber composition becomes even better. Such a component (C-2) has the advantage of increasing the self-water solubility of the urethane compound because it has both a site composed of (thermally dissociable blocked) isocyanate groups and a hydrophilic site having a hydrophilic group.

[0194] The organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less in (α) is not particularly limited, but is preferably an aromatic polyisocyanate compound and its oligomer, and other aliphatic, alicyclic, heterocyclic polyisocyanate compounds and their oligomers may also be used. The component (C-2), which is a reaction product obtained by reacting such an organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, is more easily dispersed in the gaps between the polymer chains of the organic fibers.

[0195] As specific examples, aliphatic polyisocyanate compounds include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, etc.; alicyclic polyisocyanate compounds include cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-(isocyanatomethyl)cyclohexane, etc.; heterocyclic polyisocyanate compounds include tolylene diisocyanate adduct of 1,3,5-tris(2'-hydroxyethyl)isocyanuric acid, etc.; aromatic polyisocyanate compounds include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, methine tris(4-phenyl isocyanate), tris(4-isocyanatophenyl)methane, thiophosphoric acid tris(4-isocyanatophenyl ester), 3-isopropenyl-α',α'-dimethylbenzyl isocyanate and oligomer mixtures thereof, or modified products such as carbodiimide, polyol, and allophanate of these polyisocyanate compounds, etc.

[0196] Among these, aromatic polyisocyanate compounds are preferred, and particularly preferred are methylene diphenyl polyisocyanate, polyphenylene polymethylene polyisocyanate, and the like. In particular, polyphenylene polymethylene polyisocyanate having a number average molecular weight of 2,000 or less is preferred, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 1,000 or less is particularly preferred. This is because the component (C-2), which is a reaction product after reacting such an organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, is more likely to be dispersed in the gaps between the polymer chains of the organic fiber.

[0197] The compound having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less in the above (β) is not particularly limited, but specifically, compounds selected from the group consisting of the following (i) to (vii) and the like can be mentioned. (i) Polyhydric alcohols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, (ii) Polyvalent amines having 2 or more and 4 or less primary and / or secondary amino groups and a number average molecular weight of 5,000 or less, (iii) Amino alcohols having 2 or more and 4 or less primary and / or secondary amino groups and hydroxyl groups and a number average molecular weight of 5,000 or less, (iv) Polyester polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, (v) Polybutadiene polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less and copolymers thereof with other vinyl monomers, (vi) Polychloroprene polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less and copolymers thereof with other vinyl monomers, (vii) Polyether polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less. C2-C4 alkylene oxide polyadducts of polyvalent amines, polyvalent phenols and amino alcohols, C2-C4 alkylene oxide polyadducts of polyhydric alcohols having 3 or more carbon atoms, C2-C4 alkylene oxide copolymers, or C3-C4 alkylene oxide polymers.

[0198] Here, with respect to the (C-2) component, the active hydrogen group means a group containing hydrogen that becomes active hydrogen (atomic hydrogen (hydrogen radical) and hydride ion (hydride)) when placed under suitable conditions. Examples of the active hydrogen group include an amino group and a hydroxyl group.

[0199] Examples of the compound having at least one active hydrogen group and at least one hydrophilic group that is anionic, cationic or nonionic, and having at least one active hydrogen group and at least one anionic hydrophilic group are not particularly limited, but include aminosulfonic acids such as taurine, N-methyltaurine, N-butyltaurine, sulfanilic acid, and aminocarboxylic acids such as glycine and alanine.

[0200] The method for synthesizing the (C-2) component by mixing and reacting the (α), (β), (γ) and (δ) is not particularly limited, but can be a known method such as the method described in JP-A-63-51474.

[0201] --Another preferred embodiment of the aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group-- Another preferred embodiment of the component (C-2) is a reaction product obtained by mixing and reacting (α) an organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, (β) a compound having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less, (γ) a thermally dissociable blocking agent, (δ) a compound having at least one active hydrogen group and at least one hydrophilic group selected from anionic, cationic or nonionic groups, and (ε) a compound containing an active hydrogen group and other than (α), (β), (γ) and (δ) so as to have a predetermined mixing ratio, and the constituent ratio of the (thermally dissociable blocked) isocyanate group in the reaction product, when the molecular weight of the isocyanate group (-NCO) is 42, is 0.5% by mass or more and 11% by mass or less. Here, the respective mixing ratios with respect to the total amount of (α), (β), (γ), (δ) and (ε) are, for (α), 40% by mass or more and less than 85% by mass, for (β), 5% by mass or more and 35% by mass or less, for (γ), 5% by mass or more and 35% by mass or less, for (δ), 5% by mass or more and 35% by mass or less, and for (ε), more than 0% by mass and 45% by mass or less. Such a component (C-2) has the advantage of increasing the self-water solubility of the urethane compound because it has a site composed of a (thermally dissociable blocked) isocyanate group and a hydrophilic site having a hydrophilic group.

[0202] Here, the organic polyisocyanate compound (α) having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, the compound (β) having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less, the thermally dissociable blocking agent (γ), and the compound (δ) having at least one active hydrogen group and at least one hydrophilic group selected from anionic, cationic or nonionic groups are as described in the above-mentioned "Preferred Embodiment of an Aqueous Urethane Compound Having a (C-2) (Thermally Dissociable Blocked) Isocyanate Group" except for the mixing ratio.

[0203] The method for synthesizing the component (C-2) by mixing and reacting the above (α), (β), (γ), (δ) and (ε) is not particularly limited, but known methods such as the method described in JP-A-63-51474 can be used.

[0204] --Another preferred embodiment of the aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group-- Another preferred embodiment of the component (C-2) is represented by the following general formula (1): [Chemical formula] [In formula (1), A is a residue obtained by eliminating an active hydrogen group from an organic polyisocyanate compound, X is a residue obtained by eliminating an active hydrogen group from a polyol compound having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, Y is a residue obtained by eliminating an active hydrogen group from a thermal dissociation blocking agent, Z is a residue obtained by eliminating an active hydrogen group from a compound having at least one active hydrogen group and at least one group capable of forming a salt or a hydrophilic polyether chain, n is an integer of 2 or more and 4 or less, p + m is an integer of 2 or more and 4 or less (m ≧ 0.25) [represented by]. Also in this case, when the adhesive composition is used for organic fibers, the adhesiveness between the organic fibers and the coating rubber composition becomes even better. This is because the component (C-2) has both a site composed of a (thermally dissociable blocked) isocyanate group and a hydrophilic site having a hydrophilic group, and thus has the advantage of increasing the self-water solubility of the urethane compound.

[0205] Here, the organic polyisocyanate compound, which is a residue obtained by eliminating an active hydrogen group from the organic polyisocyanate compound and is A in the general formula (1), preferably contains an aromatic ring. This is because the component (C-2) becomes more easily dispersed in the gaps between the polymer chains of the organic fibers.

[0206] Although not particularly limited, specifically, for example, methylene diphenyl polyisocyanate, polyphenylene polymethylene polyisocyanate, etc. may be mentioned. Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 6,000 or less is preferred, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 4,000 or less is particularly preferred.

[0207] The residue obtained by eliminating the active hydrogen groups of a polyol compound having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, which is X in the general formula (1), as a polyol compound having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less is not particularly limited, and specifically, compounds selected from the group consisting of the following (i) to (vi) may be mentioned. (i) Polyhydric alcohols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, (ii) Amino alcohols having 2 or more and 4 or less primary and / or secondary amino groups and hydroxyl groups and a number average molecular weight of 5,000 or less, (iii) Polyester polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, (iv) Polybutadiene polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less and copolymers thereof with other vinyl monomers, (v) Polychloroprene polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less and copolymers thereof with other vinyl monomers, (vi) Polyether polyols having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less. Polyvalent amines, polyvalent phenols, and alkylene oxide polyadducts of C2-C4 of amino alcohols, alkylene oxide polyadducts of C3 or higher polyhydric alcohols, C2-C4 alkylene oxide copolymers, or C3-C4 alkylene oxide polymers.

[0208] The (C-2) component is not particularly limited, but commercially available products such as Elastron BN27, BN77, BN11, and F-2955-D manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can also be used. Among them, Elastron BN77 is preferable.

[0209] In the adhesive composition of the present invention, when an aqueous compound having a (C) (thermally dissociable blocked) isocyanate group is included, the mixing mass ratio [(A):(C)] (in terms of solid content) is not particularly limited, but it is preferably in the range of 100:0 to 100:80, more preferably in the range of 100:10 to 100:70, and even more preferably in the range of 100:20 to 100:60. If the mixing mass ratio is 100:70 or less (if the ratio value is 0.7 or less), the curing of the adhesive composition due to excessive cross-linking is less, and the adhesiveness of the adhesive composition layer can be maintained under the strain input during tire running, and the deterioration of the adhesive layer of the organic fiber coated with the adhesive composition or the strength of the organic fiber cord under strain can be suppressed, which is good.

[0210] <Others> In the adhesive composition of the present invention, as other additives, polyvinyl alcohol, gum arabic, carrageenan, CM Cs, water-soluble epoxy compounds, organic salts, or metal salts such as aluminum, iron, chromium, copper, tin, nickel, and titanium can be used. Further, a water-soluble liquid substance in which the film-forming material therein dissolves less than water, for example, alcohols such as ethanol and propanol, polyethylene glycol, glycerol, or water-soluble polymers such as isobutylene-maleic anhydride ring-opening copolymer salts can also be used.

[0211] <Method for producing adhesive composition> The adhesive composition of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and the following (D) to (F): (D) An aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E) An aqueous component having a plurality of amino groups in the molecule, (F) A compound containing an amide bond structure, characterized by containing one or more compounds selected from the group consisting of, Preferably, further, it contains (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group.

[0212] In producing the adhesive composition, these (A) a rubber latex having an unsaturated diene, (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, and one or more compounds selected from the group consisting of (D) to (F), preferably, further, (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group can be mixed in any order.

[0213] Although not particularly limited, a preferred addition order is that the components to be included in the adhesive composition are (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group, (E) an aqueous component having a plurality of amino groups in the molecule, (F) a compound containing an amide bond structure, (A) a rubber latex having an unsaturated diene, and (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule in this order.

[0214] In the adhesive composition of the present invention, the mixing mass ratio [(A):(B)] (in terms of solid content) of (A) a rubber latex having an unsaturated diene and (B) an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule is not particularly limited, but is preferably in the range of 100:0.1 to 100:40, and more preferably in the range of 100:0.3 to 100:20. If the above-mentioned mixing mass ratio is 100:0.1 or more (if the ratio value is 0.001 or more), a rubber latex having an unsaturated diene (A) can be used as a core, and a film for protecting latex particles with an aqueous compound (B) can be formed around it, and an adhesive layer with sufficient strength can also be obtained. Further, if the above-mentioned mixing mass ratio is 100:40 or less (if the ratio value is 0.4 or less), a rubber latex having an unsaturated diene (A) is used as a core, and the film of the protective layer of the matrix of the aqueous compound (B) formed around it does not become too thick. When co-vulcanizing and adhering a coated rubber composition, which is an adherend of an organic fiber, and an adhesive composition, the coated rubber composition, which is the adherend, and the rubber latex having an unsaturated diene (A) are favorably compatible. As a result, the initial process of adhesion between the coated rubber composition, which is the adherend, and the adhesive composition proceeds favorably.

[0215] Moreover, the components (A) to (F) of the adhesive composition of the present invention are preferably aqueous. This is because water, which causes less environmental pollution, can be used as a solvent.

[0216] [Organic fiber material] By coating the adhesive composition configured as described above on the surface of an organic fiber, for example, an organic fiber made of nylon resin, polyester resin, aromatic polyamide resin, acrylic resin, etc., and subjecting it to appropriate heat treatment, an adhesive layer made of the adhesive composition can be coated on the surface of the organic fiber (resin base material), and an organic fiber material subjected to an adhesion treatment can be produced.

[0217] The organic fiber material of the present invention includes an organic fiber and an adhesive layer that coats the surface of the organic fiber, and the adhesive layer is characterized by being made of the above-mentioned adhesive composition. Thereby, an organic fiber material excellent in durability can be obtained while ensuring environmental friendliness and workability. Particularly preferably, the material of the organic fiber is nylon resin, polyester resin, aromatic polyamide resin, or acrylic resin. Among them, it is preferable that the material of the organic fiber is nylon resin or polyester resin. In the examples described later, polyester resin was used.

[0218] As methods for coating the surface of the organic fiber with the adhesive composition, there are methods such as immersing the organic fiber (especially an organic fiber cord) in the adhesive composition, applying the adhesive composition with a brush or the like, spraying the adhesive composition, etc., and an appropriate method can be selected as needed. The method for coating the surface of the organic fiber with the adhesive composition is not particularly limited. However, when coating the surface of the organic fiber with the adhesive composition, it is preferable to dissolve the adhesive composition in various solvents to lower the viscosity, as this facilitates coating (immersion, application, spraying, etc.). Also, it is environmentally preferable that the solvent for lowering the viscosity of the adhesive composition mainly consists of water.

[0219] Also, the solution concentration of the adhesive composition impregnated in the organic fiber is not particularly limited, but it is preferably 5.0% by mass or more and 25.0% by mass or less, more preferably 7.5% by mass or more and 20.0% by mass or less, in terms of the solid content conversion value with respect to the mass of the organic fiber.

[0220] Here, the thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but it is preferably 50 μm or less, more preferably 0.5 μm or more and 30 μm or less.

[0221] In particular, when applying the organic fiber-rubber composite of the present invention to a tire, if the adhesion amount of the adhesive composition due to the adhesion treatment becomes thick, the adhesion durability under tire rolling tends to decrease. The reason for this is that the adhesive composition at the interface of the fiber material to be adhered bears the stress due to strain and has relatively little deformation because the fiber material has high rigidity. However, as it moves away from the interface, the deformation due to strain increases. Compared with the adhered rubber material, the adhesive composition contains a large amount of thermosetting condensates and is hard and brittle, so the adhesion fatigue under repeated strain tends to increase. From the above, the average thickness of the adhesive composition layer is preferably 50 μm or less, more preferably 0.5 μm or more and 30 μm or less.

[0222] The organic fiber is preferably an organic fiber cord formed by twisting a plurality of filaments. When the organic fiber is an organic fiber cord formed by twisting a plurality of filaments, it is suitable for reinforcing rubber articles such as tires and conveyor belts. Further, when the organic fiber is an organic fiber cord, in the organic fiber material, it is preferable that the adhesive layer is 0.5 to 6.0% by mass of the mass of the organic fiber cord in terms of dry mass. By setting the dry mass of the adhesive layer within this range, appropriate adhesiveness can be ensured. The organic fiber cord will be described in detail below.

[0223] The organic fiber coated with the adhesive composition can be dried, heat-treated, etc. in the same manner as in the case of the organic fiber material described above.

[0224] The organic fiber material coated with the adhesive composition on the surface of the organic fiber is preferably dried at a temperature of, for example, 100°C to 210°C and then heat-treated. This heat treatment is preferably performed at a temperature equal to or higher than the glass transition temperature of the polymer of the organic fiber (resin base material), preferably at a temperature of [melting temperature - 70°C] or higher and [melting temperature - 10°C] or lower. The reason for this is that when the temperature is lower than the glass transition temperature of the polymer, the molecular mobility of the polymer is poor, and the components in the adhesive composition that promote adhesion and the polymer cannot interact sufficiently, so the bonding strength between the adhesive composition and the organic fiber cannot be obtained. Such organic fibers may be those pre-treated by electron beam, microwave, corona discharge, plasma treatment, etc.

[0225] [Rubber article] The adhesive composition of the present invention described above can be suitably used for reinforcing various rubber articles. The rubber article of the present invention is characterized by being reinforced with the above organic fiber material. Thereby, a rubber article excellent in durability can be obtained while ensuring environmental properties and workability. Examples of such rubber articles of the present invention include tires, conveyor belts, belts, hoses, air springs, etc.

[0226] [Organic fiber-rubber composite] The organic fiber-rubber composite of the present invention is a composite of an organic fiber and a rubber, characterized in that the organic fiber is coated with the above-mentioned adhesive composition. Thereby, good adhesiveness can be obtained without using resorcinol, and an organic fiber-rubber composite with good environmental properties and workability can be obtained. The adhesive composition of the present invention is particularly excellent in the adhesiveness between an organic fiber such as an organic fiber cord and a coating rubber composition.

[0227] Next, the organic fiber-rubber composite of the present invention will be described in detail with reference to FIG. 2. FIG. 2 is a schematic cross-sectional view showing an organic fiber cord-rubber composite as an example of the organic fiber-rubber composite of the present invention. In the organic fiber-rubber composite 31 shown in FIG. 2, the outer surface of the organic fiber cord 1 in the outer diameter direction is coated with an adhesive layer 32 made of the adhesive composition 2 of the present invention. Then, the organic fiber cord 1 is adhered to a coating rubber composition 33 further outside in the outer diameter direction thereof through the adhesive 32 made of the adhesive composition 2, and the organic fiber-rubber composite 31 of the present invention is formed.

[0228] In addition, as the form of the reinforcing material of the rubber article using the adhesive composition of the present invention, in addition to the organic fiber cord-rubber composite, it can also be in the form of short fibers, non-woven fabrics, etc.

[0229] <Organic fiber cord> The organic fiber cord as an example of the organic fiber is used to supplement the strength of rubber articles such as tires. When using the organic fiber cord as a reinforcing material, first, the raw yarn of the spun organic fiber is twisted to form an organic fiber cord. Then, the organic fiber cord is embedded in a rubber that coats the organic fiber cord using an adhesive composition and vulcanized to be adhered to produce an organic fiber-rubber composite, and this organic fiber-rubber composite can be used as a reinforcing member for rubber articles such as tires.

[0230] The material of the organic fiber is not particularly limited, and examples thereof include fibers of nylon resins such as polyester fiber, 6-nylon, 6,6-nylon, 4,6-nylon (aliphatic polyamide fiber), protein fibers such as artificial fibroin fiber, polyketone fiber, poly(nonamethylene terephthalamide), fibers of aromatic polyamides typified by para-phenylene terephthalamide, acrylic fiber, carbon fiber, and fiber materials typified by cellulose fibers such as rayon and lyocell. Among these, polyester, 6-nylon, and 6,6-nylon are preferable, and polyester is particularly preferable.

[0231] The polyester material is a polymer having an ester bond in the main chain. Specifically, 80% or more of the bonding modes of the repeating units in the main chain are in the ester bond mode. This polyester is obtained by condensation through an esterification reaction or a transesterification reaction of glycols such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyethylene glycol, and pentaerythritol, and dicarboxylic acids such as terephthalic acid, isophthalic acid, and their dimethyl esters. The most typical polyester is polyethylene terephthalate.

[0232] The organic fiber cord is preferably an organic fiber cord formed by twisting a plurality of single fiber filaments, particularly for the purpose of reinforcing rubber articles such as tires and conveyor belts. Further, the organic fiber cord is preferably an organic fiber cord formed by twisting an upper-twisted single fiber filament and a lower-twisted single fiber filament. In this case, the fiber thickness of the organic fiber cord preferably ranges from 100 dtex to 5000 dtex. Also, the number of twists (turns / 10 cm) is preferably such that the lower number of twists is 10 to 50 turns / 10 cm in the tire of the present invention. Further, in the tire of the present invention, the upper number of twists is preferably 10 to 50 turns / 10 cm.

[0233] In the present invention, it is preferable that the organic fiber is a tire cord of polyethylene terephthalate having a twist structure of 1670 dtex / 2, a number of twists in the S direction of 39 turns / 10 cm, and a number of twists in the Z direction of 39 turns / 10 cm, and the organic fiber - rubber composite is formed by attaching the adhesive composition to the tire cord.

[0234] <Coating Rubber Composition of Organic Fiber - Rubber Composite> The coating rubber composition constituting the organic fiber - rubber composite of the present invention is preferably a composition in which various compounding agents usually used in the rubber industry are compounded with a rubber component. Here, the rubber component is not particularly limited. For example, in addition to natural rubber, conjugated diene - based synthetic rubbers such as polyisoprene rubber (IR), polybutadiene rubber (BR), styrene - butadiene copolymer rubber (SBR), acrylonitrile - butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR), and furthermore, ethylene - propylene copolymer rubber (EPM), ethylene - propylene - diene copolymer rubber (EPDM), polysiloxane rubber, etc. may be mentioned. Among these, natural rubber and conjugated diene - based synthetic rubbers are preferable. These rubber components may be used alone or in combination of two or more.

[0235] <Manufacturing Method of Organic Fiber - Rubber Composite> The organic fiber - rubber composite of the present invention is manufactured by coating an organic fiber such as an organic fiber cord with the adhesive composition of the present invention to form an adhesive layer, and co - vulcanizing and adhering (A) a rubber latex having an unsaturated diene in the adhesive composition and the rubber component in the coating rubber composition which is the adherend of the organic fiber.

[0236] Finally, the organic fiber coated with the adhesive composition is co - vulcanized and adhered with (A) a rubber latex having an unsaturated diene in the adhesive composition and the rubber component in the coating rubber composition which is the adherend of the organic fiber.

[0237] For the co-vulcanization of the rubber component in the coating rubber composition, for example, sulfur, tellurium polysulfide compounds such as tetramethylthiuram disulfide and dipentamethylene thiuram tetrasulfide, and organic vulcanizing agents such as 4,4-dithiomorpholine, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, and cyclic sulfur imide can be used. Among them, it is preferable to use sulfur. In addition, various compounding agents such as fillers such as carbon black, silica, and aluminum hydroxide, vulcanization accelerators, anti-aging agents, and softening agents commonly used in the rubber industry can be appropriately compounded into the rubber component in the coating rubber composition.

[0238] In addition, in the adhesive method in which the vulcanizing agent contained in the adherend of the synthetic organic fiber material such as organic fiber and / or the adherend of the coating rubber composition of the adhesive composition of the present invention migrates into the adhesive composition and the adhesive composition is crosslinked by the migrated vulcanizing agent, it goes without saying that the effect of adhesion can be obtained.

[0239] [Tire] The tire of the present invention uses the above-mentioned organic fiber-rubber composite. Thereby, good adhesiveness can be obtained without using resorcinol, and a tire with good environmental performance and productivity can be obtained.

[0240] Here, in the tire of the present invention, the above-mentioned organic fiber-rubber composite can be used, for example, as a reinforcing layer around the belt such as a carcass, a belt, a belt reinforcing layer, and a flipper.

[0241] The tire of the present invention may be obtained by molding with an unvulcanized rubber composition and then vulcanizing according to the type of tire to be applied, or by molding with a semi-vulcanized rubber that has undergone a pre-vulcanization process or the like and then further fully vulcanizing. In addition, in the tire of the present invention, an organic fiber cord or the like treated with the above-mentioned adhesive composition is used at any location of the tire, but other members are not particularly limited, and known members can be used. Further, the tire of the present invention is preferably a pneumatic tire, and as the gas filled in this pneumatic tire, in addition to normal air or air with adjusted oxygen partial pressure, inert gases such as nitrogen, argon, and helium can be used.

[0242] In addition to the tire, the above-mentioned adhesive composition, organic fiber material, and organic fiber-rubber composite of the present invention can also be applied to any rubber articles such as conveyor belts, belts, hoses, and air springs.

Examples

[0243] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples.

[0244] <(A) Rubber latex having an unsaturated diene> In the following Comparative Examples 1 to 23 and Examples 1 to 21, as the (A) rubber latex having an unsaturated diene, a vinyl pyridine-styrene-butadiene copolymer latex was prepared and used as follows in accordance with Comparative Example 1 described in JP-A-9-78045.

[0245] Into a 5-liter autoclave purged with nitrogen, 130 parts by mass of deionized water and 4.0 parts by mass of potassium rosinate as an emulsifier were charged and dissolved. To this, 15 parts by mass of a vinyl pyridine monomer, 15 parts by mass of styrene, and a monomer mixture having a composition of 70 parts by mass of butadiene, and 0.60 parts by mass of t-dodecyl mercaptan as a chain transfer agent were charged and emulsified. Then, the temperature was raised to 50 °C, and 0.5 parts by mass of potassium persulfate as a polymerization initiator was added to initiate polymerization. After the reaction rate of the monomer mixture reached 90%, 0.1 parts by mass of hydroquinone was added to stop the polymerization. Next, under reduced pressure, unreacted monomers were removed to obtain a vinyl pyridine-styrene-butadiene copolymer latex having a solid content concentration of 41% by mass.

[0246] <(B) An aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule> In the following Comparative Examples 2 to 5, Comparative Examples 19 to 21, Examples 1 to 14, and Examples 15 to 21, as the aqueous compound component having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule, a compound (B-1) containing two or more polymerizable (meth)acrylate structures and a polyglycerol structure in the molecule, a compound (B-2) containing two or more polymerizable (meth)acrylamide structures and a main chain linking ether structure in the molecule, a compound (B-3) containing two or more polymerizable (meth)acrylamide structures and a main chain linking amine structure in the molecule, and a compound (B-4) containing two or more polymerizable (meth)acrylate monomers and a diallyldimethylammonium chloride structure in the molecule were used.

[0247] Here, as (B-1), “SA-TE60” (liquid) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used. As (B-2), “FOM-03006” (liquid) manufactured by Fujifilm Wako Pure Chemical Corporation was used. As (B-3), “FOM-03007” (liquid) manufactured by Fujifilm Wako Pure Chemical Corporation was used. As (B-4), an aqueous solution of DADMAC manufactured by Osaka Soda Co., Ltd. (B-4-1) and an aqueous solution of poly(diallyldimethylammonium chloride) (B-4-2) manufactured by Sigma-Aldrich Japan K.K. were used. While stirring these, they were diluted with deionized water to produce an aqueous solution having a solid content concentration of 5% by mass, and this aqueous solution was used for the preparation of the adhesive composition.

[0248] <(C) An aqueous compound having a (thermally dissociable blocked) isocyanate group> In the following Examples 11 to 14 and Examples 20 to 21, as the aqueous compound having a (thermally dissociable blocked) isocyanate group, “DM-6400” (blocking agent thermal dissociation temperature: about 130°C, solid content concentration 40% by mass) manufactured by Myojo Chemical Industry Co., Ltd., which is a methyl ethyl ketoxime-blocked diphenylmethane diisocyanate compound (C-1), and “Elastron BN77 (F-2955D-1)” (blocking agent thermal dissociation temperature: about 160°C, pH 8.0, solid content concentration 31% by mass), which is an aqueous compound having a (thermally dissociable blocked) isocyanate group and is manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C-2), were used as they were.

[0249] <(D) An aqueous component having a plurality of phenolic hydroxy groups in the molecule> In Comparative Examples 6 to 7, Comparative Examples 15 to 18, Comparative Example 22, Examples 1 to 2, Examples 8 to 9, Examples 11 to 15, Example 18, Examples 20 to 21, as the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D), (D-1) partially desulfonated lignin sulfonate with reduced sulfonation degree, product name "Lignin (Alkali)" manufactured by Tokyo Chemical Industry Co., Ltd., and (D-2) condensed tannin, product name "Mimosa" manufactured by Kawamura Tsusho Co., Ltd. were used. These solid powder polyphenols were dissolved in deionized water adjusted to 80°C to produce an aqueous solution with a solid content concentration of 10% by mass, and this aqueous solution was used for the preparation of the adhesive composition. In addition, as the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D), (D-3) kraft lignin, product name "BioPiva 100" manufactured by UPM Biochemicals, was used and dissolved in an aqueous sodium hydroxide solution with a concentration of 1×10 -4 mol / L adjusted to 80°C to produce an aqueous solution with a solid content concentration of 10% by mass, and this aqueous solution was used for the preparation of the adhesive composition. The pH value after dissolution was 9.3.

[0250] <(Aqueous component having a plurality of amino groups in the molecule (E))> In Comparative Examples 8 to 11, Comparative Example 15, Comparative Example 18, Comparative Example 23, Examples 3 to 5, Examples 10 to 11, Example 14, Example 16, Examples 19 to 20, as the aqueous component having a plurality of amino groups in the molecule (E), (E-1) a polypeptide having an amino group, product name "Polylysine 10" manufactured by Ichimaru Pharcos Co., Ltd., (E-2) a polyetheramine, product name "Baxxodur EC301" manufactured by BASF SE, and (E-3) polyethyleneimine, reagent "Polyethyleneimine average molecular weight 600" manufactured by Wako Pure Chemical Industries, Ltd. were stirred and dissolved in deionized water to a solid content concentration of 0.5% by mass, and this aqueous solution was used for the preparation of the adhesive composition.

[0251] <(Compound containing an amide bond structure (F))> In Comparative Examples 12 to 14, Comparative Examples 16 to 17, Comparative Example 23, Examples 6 to 7, Examples 12 to 13, Example 17, Example 19, and Example 21, as the compound containing an (F) amide bond structure, (F-1) a nonionic polyacrylamide, "Haricot 1057" manufactured by Harima Chemicals, Inc., and as the compound containing an amide bond structure having a (F-2) cationic group and a carboxyl group, an amphoteric polyacrylamide, "DS4441" manufactured by Seiko PMC Co., Ltd., were dissolved in deionized water with stirring to a solid content concentration of 1% by mass, and the aqueous solution was used for the preparation of the adhesive composition.

[0252] <Preparation of latex adhesive composition (Comparative Example 1)> The above (A) rubber latex and water were blended (Wet blend) as shown in Table 2, the amounts were adjusted so that the solid content concentration became 21% by mass, and after mixing, stirring was carried out sufficiently to obtain a latex adhesive composition (Comparative Example 1).

[0253] <Preparation of adhesive compositions (Comparative Examples 2 to 23, Examples 1 to 21)> As shown in the formulations (Wet blends) of Tables 2 to 8, each predetermined diluting water, (D) an aqueous component having a plurality of phenolic hydroxy groups in the molecule, (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group, (E) an aqueous component having a plurality of amino groups in the molecule, (F) a compound containing an amide bond structure, (A) a rubber latex having an unsaturated diene, and (B) an aqueous compound having two or more polymerizable (meth) acrylate structures, (meth) acrylamide structures or (meth) allyl structures in the molecule were blended in this order, and after mixing so that the solid content concentration of the adhesive composition became 21% by mass, stirring was carried out sufficiently to obtain an adhesive composition which is one embodiment of the present invention.

[0254] <Coating of tire cord with each adhesive composition> As the organic fiber cord, a tire cord made of polyethylene terephthalate having a twist structure of 1670 dtex / 2, an upper twist number of 39 turns / 10 cm, and a lower twist number of 39 turns / 10 cm was used.

[0255] The above tire cord was immersed in each of the adhesive compositions of Comparative Examples 1 to 23 and Examples 1 to 21 so that the concentration of the adhesive composition impregnated in the tire cord was 3.5% by mass based on the mass of the organic fiber cord. Subsequently, it was sequentially subjected to drying in the drying zone (135 °C, 80 seconds), thermosetting of the resin while applying tension in the hot zone (33 N per strand) (238 °C, 60 seconds), and thermosetting while relaxing the above tension in the normalization zone (238 °C, 60 seconds) to obtain tire cords coated with each of the adhesive compositions of the respective comparative examples and examples.

[0256] <Preparation of tire cord-rubber composite> The tire cords coated with each of the adhesive compositions of Comparative Examples 1 to 23 and Examples 1 to 21 were embedded in an unvulcanized rubber composition and co-vulcanized at 160 °C for 20 minutes. As the unvulcanized rubber composition for coating, a rubber composition containing natural rubber, styrene-butadiene rubber, carbon black, vulcanizing chemicals, etc. was used.

[0257] <Evaluation of workability of adhesive composition> Regarding the workability of the adhesive compositions of the respective comparative examples and examples, the following evaluations were conducted.

[0258] (1) Evaluation of mechanical stability (coagulation rate) The mechanical stability (coagulation rate) of each adhesive composition was measured according to the method using a Maron type mechanical stability tester (manufactured by Kumagai Riki Kogyo Co., Ltd., Maron stability tester No. 2312-II) for copolymer latex compositions shown in JIS K6392-1995.

[0259] Briefly, after applying a shear strain for 10 minutes at a compression load of 10 kg and a rotation speed of 1000 r / min to each adhesive composition using the rotor of the above Maron type mechanical stability tester, the coagulation rate (%) was evaluated from the amount of coagulated matter generated by the following formula and rounded to a numerical value up to three decimal places. A smaller numerical value indicates better mechanical stability. Coagulation rate (%) = [(dry mass of the generated coagulated matter) / (solid content mass of the test adhesive liquid)] × 100

[0260] (2) Evaluation of Adhesion to the Diaphragm Roll Regarding the above-mentioned polyethylene terephthalate tire cord, which is an organic fiber cord, each adhesive composition was subjected to continuous treatment of 2000 m in an immersion treatment machine for storing each adhesive composition, and the amount of each adhesive composition adhering to the roll in the resin thermosetting (238 °C, 60 seconds) zone while applying the tension (33 N / strand) in the above-mentioned hot zone was visually observed and evaluated in the following 5 grades. Extra-large: Particularly large amount. Large: Large amount. Medium: Medium degree. Small: Small amount. Very small: Very small amount.

[0261] <Adhesion Evaluation of Adhesive Compositions> Regarding the adhesiveness of the adhesive compositions of each comparative example and example, the following evaluations were carried out.

[0262] (3) Evaluation of Adhesive Strength By pulling the tire cord-rubber composite obtained using each adhesive composition at a speed of 300 mm / min, the tire cord was peeled from the above-mentioned tire cord-rubber composite, and the peeling resistance per tire cord was determined and used as the normal temperature adhesive strength (N / strand). Also, a similar test for the cord peeling resistance was carried out after leaving it in an oven at 100 °C for 5 minutes, and peeling was performed at the same temperature, and the peeling resistance per tire cord was determined and used as the high temperature adhesive strength (N / strand).

[0263] (4) Evaluation of the Adhesion State of the Coated Rubber Regarding the tire cord peeled from the above-mentioned tire cord-rubber composite, the adhesion state of the coated rubber was visually observed and scored according to Table 1 below.

[0264]

Table 1

[0265] <Results of Workability Evaluation and Adhesion Evaluation of Adhesive Compositions> The formulations of the adhesive compositions of each comparative example and each example are shown in Tables 2 to 8 below, and the results of the workability evaluation and the adhesion evaluation are also shown in Tables 2 to 8 below, respectively.

[0266]

Table 2

[0267]

Table 3

[0268]

Table 4

[0269]

Table 5

[0270]

Table 6

[0271]

Table 7

[0272]

Table 8

[0273] (A-1): Rubber latex having an unsaturated diene, vinyl pyridine-styrene-butadiene copolymer latex synthesized by the above method, solid content concentration 41% by mass

[0274] (B-1): A compound containing two or more polymerizable (meth)acrylate structures and a polyglycerin structure in the molecule, polyglycerin-based (meth)acrylate, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name "SA-TE60", soluble in water, liquid (B-2): A compound containing two or more polymerizable (meth)acrylamide structures and a main-chain linking ether structure in the molecule, N,N’-{[(2-acrylamido-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide, manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "FOM-03006", soluble in water, liquid (B-3): A compound containing two or more polymerizable (meth)acrylamide structures and a main-chain linking amine structure in the molecule, N,N',N''-triacryloyl diethylenetriamine, manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "FOM-03007", soluble in water, liquid (B-4-1): A compound containing two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the molecule, diallyldimethylammonium chloride, manufactured by Osaka Soda Co., Ltd., trade name "DADMAC", 60 wt% aqueous solution (B-4-2): A compound containing two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the molecule, poly(diallyldimethylammonium chloride), reagent manufactured by Sigma-Aldrich Japan LLC, CAS number: 26062-79-3, average molecular weight Mw = 200,000 - 350,000, 20 wt% aqueous solution

[0275] (C-1): An aqueous compound having a (thermally dissociable blocked) isocyanate group, manufactured by Meisei Chemical Industry Co., Ltd., trade name "DM-6400" (blocking agent thermal dissociation temperature: about 130 °C, solid content concentration 40 mass%), methyl ethyl ketoxime-blocked diphenylmethane diisocyanate compound, aqueous dispersion (C-2): An aqueous compound having a (thermally dissociable blocked) isocyanate group, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Elastron BN77 (F-2955D-1)" (blocking agent thermal dissociation temperature: about 160 °C, pH 8.0, solid content concentration 31 mass%), aqueous dispersion

[0276] (D-1): Polyphenol (lignin sulfonate), manufactured by Tokyo Chemical Industry Co., Ltd., product name "Lignin (deaikalized)" (CAS Number: 8061-51-6), partially desulfonated lignin sulfonate with reduced sulfonation degree, solid powder (D-2): Polyphenol (condensed tannin), manufactured by Kawamura Tsusho Co., Ltd., product name "Mimosa", solid powder (D-3): Kraft lignin, manufactured by UPM Biochemicals, product name "BioPiva 100" (CAS Number: 8068-5-01), kraft lignin sulfonate, solid powder

[0277] (E-1): Polypeptide having an amino group, polylysine, manufactured by Ichimaru Pharcos Co., Ltd., product name "Polylysine 10" (solid content concentration 10%, aqueous solution), weight average molecular weight 5000 (E-2): Polyetheramine, product name "Baxxodur EC301" manufactured by BASF SE (CAS number: 9046-10-0, nominal molecular weight Mw: 230, nominal amine hydrogen equivalent: 61 g / Eq, specific gravity: 0.95), colorless liquid (E-3): Polyethyleneimine, reagent manufactured by Wako Pure Chemical Industries, Ltd., "Polyethyleneimine average molecular weight 600", solid content 100%, liquid

[0278] (F-1): Nonionic polyacrylamide, product name "Halicoat 1057" manufactured by Harima Chemicals, Inc. (solid content concentration 20% aqueous solution) (F-2): Amphoteric polyacrylamide, product name "DS4441" manufactured by Starlight PMC Co., Ltd. (solid content concentration 20% aqueous solution)

[0279] It can be seen from Tables 5 to 8 that in each example, an adhesive composition with good workability and good adhesion between the organic fiber and the coating rubber composition is obtained. In particular, it has been found that when an aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures or (meth)allyl structures in the molecule is included, roll scale in a high-temperature furnace is reduced and a further improvement in high-temperature adhesive strength is obtained.

Industrial Applicability

[0280] According to the present invention, it is possible to secure a desired adhesiveness without using resorcinol, and to provide an adhesive composition that does not impair workability during use, as well as an organic fiber material, a rubber article, an organic fiber-rubber composite, and a tire using the same. Therefore, the present invention can be used in the industrial field of manufacturing rubber articles such as tires.

[0281] [Contribution to the Sustainable Development Goals (SDGs) led by the United Nations] SDGs have been proposed towards the realization of a sustainable society. One embodiment of the present invention can be a technology that contributes to "No. 12 - The responsibility to produce, the responsibility to use" and "No. 13 - Specific measures against climate change".

Explanation of Symbols

[0282] 1: Organic fiber cord 2: Adhesive composition 3: Dipping bath 4: Organic fiber cord coated with the adhesive composition 5: Squeezing roll 6: Drying zone 7: Hot zone 8: Normalizing zone 31: Organic fiber-rubber composite 32: Adhesive layer by the adhesive composition 33: Coating rubber composition

Claims

1. (A)A rubber latex having an unsaturated diene, and (B)An aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule, and comprising: Furthermore, the following (D) to (F): (D)An aqueous component having a plurality of phenolic hydroxy groups in the molecule, (E)An aqueous component having a plurality of amino groups in the molecule, (F)A compound containing an amide bond structure An adhesive composition, characterized by containing at least one compound selected from the group consisting of.

2. Furthermore, the adhesive composition according to claim 1, further comprising (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group.

3. The rubber latex having an unsaturated diene (A) is at least one selected from the group consisting of natural rubber (NR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR), and vinyl pyridine-styrene-butadiene copolymer rubber (Vp). The adhesive composition according to claim 1 or 2.

4. The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is an aqueous compound containing a polyether structure in the molecule. The adhesive composition according to claim 1 or 2.

5. The aqueous compound having two or more polymerizable (meth)acrylate structures, (meth)acrylamide structures, or (meth)allyl structures in the molecule (B) is (B-1) a compound containing two or more polymerizable (meth)acrylate structures and a polyglycerol structure in the molecule, (B-2) a compound containing two or more polymerizable (meth)acrylamide structures and a main chain-linked ether structure in the molecule, (B-3) a compound containing two or more polymerizable (meth)acrylamide structures and a main chain-linked amine structure in the molecule, or (B-4) a compound containing two or more polymerizable (meth)allyl structures and a dimethylammonium chloride structure in the molecule. The adhesive composition according to claim 1 or 2.

6. The adhesive composition according to claim 1 or 2, wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is a plant-derived component having a plurality of phenolic hydroxy groups in the molecule.

7. The adhesive composition according to claim 6, wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is lignin, tannin, tannic acid, flavonoid, or a derivative thereof.

8. The adhesive composition according to claim 7, wherein the aqueous component having a plurality of phenolic hydroxy groups in the molecule (D) is a derivative of lignin sulfonic acid.

9. The adhesive composition according to claim 1 or 2, wherein the aqueous component having a plurality of amino groups in the molecule (E) is (E-1) a polypeptide having an amino group, (E-2) a polyetheramine, (E-3) polyethyleneimine, or (E-4) a polyamidoamine.

10. The adhesive composition according to claim 9, wherein the aqueous component having a plurality of amino groups in the molecule (E) is polylysine.

11. The adhesive composition according to claim 1 or 2, wherein the compound containing the (F) amide bond structure is a polymer composed of (meth)acrylamide or a copolymer containing (meth)acrylamide and other polymerizable monomers.

12. The adhesive composition according to claim 2, wherein the aqueous compound having a (C) (thermally dissociable blocked) isocyanate group is a water-dispersible (thermally dissociable blocked) isocyanate compound composed of an addition product of a polyisocyanate having an aromatic ring (C-1) and a blocking agent having one or more active hydrogen groups.

13. The adhesive composition according to claim 12, wherein the water-dispersible (thermally dissociable blocked) isocyanate compound composed of an addition product of a polyisocyanate having an aromatic ring (C-1) and a blocking agent having one or more active hydrogen groups is a blocked form of methylene diphenyl diisocyanate.

14. The adhesive composition according to claim 2, wherein the aqueous compound having a (C) (thermally dissociable blocked) isocyanate group is a water-based urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group.

15. The aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group is (α) an organic polyisocyanate compound having 3 or more and 5 or less functional groups and a number average molecular weight of 2,000 or less, (β) A compound having 2 or more and 4 or less active hydrogen groups and a number average molecular weight of 5,000 or less, (γ) A thermal dissociable blocking agent, and (δ) A compound having at least one active hydrogen group and at least one hydrophilic group that is anionic, cationic or nonionic, are mixed so that the respective mixing ratios with respect to the total amount of (α), (β), (γ) and (δ) are For (α), 40% by mass or more and 85% by mass or less, For (β), 5% by mass or more and 35% by mass or less, For (γ), 5% by mass or more and 35% by mass or less, and For (δ), 5% by mass or more and 35% by mass or less, and the reaction product after mixing and reacting, and The adhesive composition according to claim 14, wherein the constituent ratio of the (thermally dissociable blocked) isocyanate group in the reaction product is 0.5% by mass or more and 11% by mass or less when the molecular weight of the isocyanate group (—NCO) is 42.

16. The aqueous urethane compound having the (C-2) (thermally dissociable blocked) isocyanate group is represented by the following general formula (1): 【Chemical 1】 [In formula (1), A is the residue obtained by elimination of the active hydrogen group of an organic polyisocyanate compound, X is the residue obtained by elimination of the active hydrogen group of a polyol compound having 2 or more and 4 or less hydroxyl groups and a number average molecular weight of 5,000 or less, Y is the residue obtained by elimination of the active hydrogen group of a thermal dissociable blocking agent, Z is the residue obtained by elimination of the active hydrogen group of a compound having at least one active hydrogen group and at least one group that forms a salt or a hydrophilic polyether chain, n is an integer of 2 or more and 4 or less, p + m is an integer of 2 or more and 4 or less (m ≧ 0.25) The adhesive composition according to claim 14 or 15, which is represented by].

17. The adhesive composition according to claim 1 or 2, which does not contain resorcinol.

18. The adhesive composition according to claim 1 or 2, which does not contain a photoinitiator.

19. The adhesive composition according to claim 1 or 2, which is for adhesion to rubber.

20. The adhesive composition according to claim 1 or 2, which is for adhesion to organic fibers.

21. The adhesive composition according to claim 1 or 2, which is for adhesion between rubber and organic fibers.

22. An organic fiber material comprising an organic fiber and an adhesive layer covering the surface of the organic fiber, The organic fiber material, wherein the adhesive layer is composed of the adhesive composition according to claim 1 or 2.

23. The organic fiber material according to claim 22, wherein the organic fiber is an organic fiber cord formed by twisting a plurality of filaments together.

24. The organic fiber material according to claim 23, wherein the organic fiber cord is formed by applying a Z-twist and an S-twist, the fiber thickness of the cord formed by twisting is 100 dtex to 5000 dtex, and the number of twists for twisting is such that the Z-twist number is 10 to 50 turns / 10 cm and the S-twist number is 10 to 50 turns / 10 cm.

25. The organic fiber material according to claim 23, wherein the adhesive layer is 0.5 to 6.0% by mass of the mass of the organic fiber cord in terms of dry mass.

26. The organic fiber material according to claim 22, wherein the organic fiber is made of a polyester resin.

27. A rubber article, characterized in that it is reinforced with the organic fiber material according to claim 22.

28. An organic fiber-rubber composite, wherein the organic fiber is coated with the adhesive composition according to claim 1 or 2.

29. A tire, characterized in that the organic fiber-rubber composite according to claim 28 is used.

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