JP2006169456A - Hot-melt adhesive for rubber bonding and adhesion method using the adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hot-melt adhesive for bonding rubber that does not use any organic solvent and can surely bond rubber to adherends (rubber, plastics, metals and the like) with high bond strength. <P>SOLUTION: In an adhesive comprising the hot-melt adhesive resins, the proportion of functional groups (amino group, carboxy group, epoxy groups or the like) per kilogram of the adhesive is set more than 10 mmol. Such adhesive is selected from hot-melt adhesive polyamide resins and hot-melt adhesive polyester resins and can be comprised of at least one of hot-melt adhesive resins. Further, in order to adjust the concentration of the functional groups, the polymer may include compounds bearing functional groups (for example, a compound bearing an epoxy groups) or compounds having the carbon-carbon double bond or the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hot-melt adhesive for bonding rubber (or its adhesive) useful for bonding rubber and an adherend to the rubber (same or different rubber, different material (metal, plastic, wood, etc.)). The present invention relates to a composition), a bonding method using this adhesive, and a composite of rubber and adherend (adhesive composite) obtained by this method.

  Conventionally, in bonding between rubbers (for example, vulcanized rubber) and bonding between rubber (for example, vulcanized rubber) and dissimilar materials (metal, plastic, wood, etc.), an adhesive (chloroprene rubber, two (Tolyl rubber, epoxy adhesive, etc.) are usually used, and various treatments on the rubber surface such as polishing treatment and chemical treatment are usually required to prevent adhesion of the rubber compounding agent to the surface due to bleeding. is there.

  For bonding between rubber and dissimilar materials, a two-part coating type bonding method using two types of adhesives, that is, an adhesive having affinity for dissimilar materials and an adhesive having affinity for rubber, is generally used. It is. For example, in the adhesion between rubber and metal, phenolic adhesives are blended with chlorinated rubber as an undercoat adhesive, and topcoat adhesives are often blended with chlorinated rubber or cyclized rubber with a crosslinking agent. in use.

  In the case of bonding at the same time as rubber vulcanization, the same type of rubber does not necessarily require an adhesive, but in bonding between different types of rubber or between rubber and different materials, the bonding of vulcanized rubber The same adhesive and surface treatment agent are used. For example, when bonding unvulcanized rubber and fabric, a rubber solution containing a vulcanizing agent (nitrile rubber solution, etc.) is applied to the fabric, and the fabric coated with this rubber solution is bonded to the unvulcanized rubber. Vulcanized.

  Especially when rubber reinforcements are required to have strong adhesion to rubber, such as tires and belts, rubber reinforcement materials (fibers such as tire cords such as polyamide, aramid, and polyester) It is necessary to firmly bond the rubber. In such a case, these rubber reinforcing materials (synthetic fiber cords and the like) are previously immersed in a rubber solution containing an adhesive (for example, a mixed solution of resorcinol resin and rubber latex) and dried. In addition, a method of performing adhesion between rubber (rubber sheet) and an adherend (synthetic fiber cord, etc.) simultaneously with vulcanization of rubber is known, and various improved methods using such a rubber solution are also known. ing.

  For example, in JP-A-7-118401 (Patent Document 1), (a) an aramid cord is treated with an aramid-polydiene copolymer having a specific structural formula, and (b) a composite of the treated cord and rubber. A method is disclosed for improving the adhesion between an aramid cord and a sulfur vulcanized rubber comprising a step of vulcanizing the material. This document describes that the solution of the aramid-polydiene copolymer can be applied to the cord by a method such as dipping to coat the cord.

  Japanese Patent Application Laid-Open No. 2002-309224 (Patent Document 2) discloses an adhesive composition for increasing the adhesion between rubber and a reinforcing material, in which the adhesive composition contains a carboxylic acid, a hydroxyl group, and a hydroxyl group. An adhesive composition containing a compound obtained by reacting a group and / or an amino group, additionally a compound having a carbon-carbon double bond or triple bond is disclosed.

  As described above, the adhesion of the rubber to the adherend is a very complicated adhesion process, and the organic solvent contained in the solution of the rubber-based adhesive used for the adhesion causes deterioration of the working environment. Yes.

  On the other hand, an attempt has been made to bond a rubber and an adherend using a hot melt adhesive. For example, JP-A-10-183082 (Patent Document 3) discloses (a) 10 to 80% by weight of polyamide, (b) 10 to 90% by weight of saponified ethylene-vinyl acetate copolymer, (c) anhydrous poly A hot melt adhesive composition for rubber bonding comprising 0.01 to 10% by weight of a carboxylic acid and (d) 0 to 50% by weight of a plasticizer and / or an adhesive is disclosed.

When such a hot melt adhesive is used, rubber can be bonded without using an organic solvent. However, even when such a composition is used, the rubber and the adherend cannot be bonded with sufficient adhesive strength depending on the combination of the rubber and the adherend. In addition, such a composition requires a saponified ethylene-vinyl acetate copolymer or polycarboxylic anhydride, and is complicated to prepare.
JP-A-7-118401 (Patent Document 1) JP 2002-309224 A (Patent Document 2) JP-A-10-183082 (Claim 1)

  Accordingly, an object of the present invention is to provide a hot-melt adhesive for rubber bonding that can reliably bond rubber and an adherend (rubber, plastic, metal, etc.) with high adhesive strength, a bonding method using this adhesive, and this bonding. An object of the present invention is to provide a composite of a rubber and an adherend bonded by a method.

  Another object of the present invention is to provide a hot-melt adhesive for rubber bonding that can easily and efficiently firmly bond a rubber and an adherend without using a solvent (organic solvent), and adhesion using this adhesive. And a composite of a rubber and an adherend bonded by the bonding method.

  As a result of intensive investigations to achieve the above-mentioned problems, the inventors of the present invention have made a hot melt adhesive (or a composition thereof) having a specific concentration of functional groups between the rubber and the adherend. When used for bonding, it was found that the rubber and the adherend can be reliably bonded with high bonding strength without using a conventional organic solvent, and the present invention has been completed.

  That is, the hot melt adhesive for bonding rubber according to the present invention is a hot melt adhesive for bonding rubber and an adherend, and does not contain a saponified ethylene-vinyl acetate copolymer. It is composed of an adhesive resin and has a functional group at a rate of 10 mmol / kg or more. The functional group may be at least one selected from, for example, an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and a carbon-carbon double bond group. In particular, the hot-melt adhesive for rubber bonding may have at least one functional group (A) selected from an amino group, a carboxyl group and a hydroxyl group at a rate of 20 mmol / kg or more.

  The hot melt adhesive may be composed of at least one selected from, for example, a hot melt adhesive polyamide resin and a hot melt adhesive polyester resin. Such a hot melt adhesive includes, for example, a hot melt adhesive polyamide-based resin having at least one functional group selected from an amino group and a carboxyl group at a rate of 30 to 1000 mmol / kg, and a carboxyl group and a hydroxyl group. It may be composed of at least one selected from hot-melt-adhesive polyester resins having at least one functional group selected from the group consisting of 30 to 1000 mmol / kg or more.

  In order to adjust the functional group concentration, the adhesive may be a hot melt adhesive composition further containing a compound having a functional group. For example, such a hot melt adhesive composition includes at least one hot melt adhesive resin selected from a hot melt adhesive polyamide resin and a hot melt adhesive polyester resin, and a compound having a functional group. It may be configured. The compound having a functional group may be at least one selected from a compound having an epoxy group and a compound having a carbon-carbon double bond. The proportion of the compound having a functional group may be about 0.01 to 30 parts by weight with respect to 100 parts by weight of the hot-melt adhesive resin.

  The hot melt adhesive of the present invention includes, for example, any one of the following hot melt adhesives (1) to (4).

(1) A hot melt adhesive composed of a hot melt adhesive polyamide-based resin having an amino group or a carboxyl group at a ratio of 40 mmol / kg or more. (2) It has an amino group or a carboxyl group at a ratio of 40 mmol / kg or more. Hot-melt adhesive comprising a hot-melt adhesive polyamide-based resin and having at least one functional group selected from an epoxy group and a carbon-carbon double bond group at a rate of 40 mmol / kg or more (3) Hydroxyl group Or a hot melt adhesive comprising a hot melt adhesive polyester resin having a carboxyl group at a ratio of 40 mmol / kg or more. (4) a hot melt adhesive polyester having a hydroxyl group or a carboxyl group at a ratio of 40 mmol / kg or more. Made of epoxy resin and Shea groups and carbon - hot-melt adhesive having at least one functional group selected from the carbon-carbon double bond group at a ratio of more than 40 mmol / kg.

  In addition, the representative hot melt adhesive of the present invention may be any of the following (a) to (f).

(A) A hot melt adhesive composed of a hot melt adhesive polyamide resin having an amino group or a carboxyl group at a rate of 100 mmol / kg or more. (B) An amino group or a carboxyl group at a rate of 40 mmol / kg or more. And a hot melt adhesive comprising a hot melt adhesive polyamide-based resin having at least one functional group selected from an epoxy group and a carbon-carbon double bond group at a rate of 40 mmol / kg or more (c ) At least one functional group selected from a hot melt adhesive polyamide resin having an amino group or a carboxyl group at a ratio of 40 mmol / kg or more, a compound having an epoxy group, and a compound having a carbon-carbon double bond group An epoxy group and a carbon-carbon double bond. Hot melt adhesive having at least one functional group selected from a group at a rate of 40 mmol / kg or more (d) Consists of a hot melt adhesive polyester resin having a hydroxyl group or a carboxyl group at a rate of 100 mmol / kg or more (E) a carboxyl group or a hydroxyl group at a rate of 40 mmol / kg or more, and at least one functional group selected from an epoxy group and a carbon-carbon double bond group at 40 mmol / kg (f) Hot melt adhesive polyester resin having a carboxyl group or hydroxyl group at a ratio of 40 mmol / kg or more, and an epoxy group Having carbon and carbon-carbon double bond And at least one functional group selected from an epoxy group and a carbon-carbon double bond group is 40 mmol / kg or more. Hot melt adhesive having a proportion.

  The present invention also includes a method of adhering the rubber and the adherend by interposing the adhesive in a molten state between the rubber and the adherend and bonding the rubber and the adherend. It is. The present invention also includes a composite of a rubber and an adherend obtained by such a method.

  Since the hot melt adhesive for rubber bonding of the present invention has a functional group such as an amino group and a carbon-carbon double bond group at a specific concentration, the rubber and the adherend (rubber, plastic, metal, etc.) Can be securely bonded with high adhesive strength. Moreover, since the hot melt adhesive for rubber bonding of the present invention can be applied in the form of a sheet or powder, the rubber and the adherend can be easily and efficiently used without using a solvent (organic solvent). Can adhere firmly.

  The hot-melt adhesive for rubber bonding of the present invention (hereinafter sometimes simply referred to as hot-melt adhesive, adhesive, etc.) is a hot-melt adhesive for bonding rubber and an adherend. While having a functional group in a proportion or concentration, it is composed of a hot-melt adhesive resin. The hot-melt adhesive for rubber bonding of the present invention does not contain a saponified product of ethylene-vinyl acetate copolymer (such as a saponified product described in JP-A-10-183082).

[Functional groups and their proportions]
The hot-melt adhesive for rubber bonding of the present invention has a functional group at a specific ratio.

As functional groups, amino groups (—NH ₂ ), carboxyl groups (—COOH), acid anhydride groups (—COOCO—), hydroxyl groups (—OH), epoxy groups, unsaturated groups {carbon-carbon double bonds Groups [substituents (for example, vinylene groups, vinyl groups, etc. optionally having hydrocarbon groups such as alkyl groups)], carbon-carbon triple bond groups [ethynylene groups (—C≡C—), ethynyl groups Etc.] etc.}. The said adhesive agent may have these functional groups individually or in combination of 2 or more types.

  Of these functional groups, amino groups, carboxyl groups, hydroxyl groups, epoxy groups, and carbon-carbon double bond groups are particularly effective. Usually, the adhesive of the present invention often has at least one functional group (A) selected from an amino group, a carboxyl group, and a hydroxyl group. Such a functional group contributes to adhesion by participating in a vulcanization reaction at the time of vulcanization in unvulcanized rubber. In vulcanized rubber, interaction with a functional group present on the rubber surface or partial The reaction is considered to contribute to adhesion. In addition, these functional groups greatly contribute to the improvement of hot melt adhesion to an adherend (or a counterpart material) that adheres to rubber, for example, glass tex, metal, fabric, fiber, and wood.

  The ratio of functional groups (or functional group concentration) may be 10 mmol or more (for example, about 10 to 1500 mmol) per 1 kg of the hot-melt adhesive for rubber bonding, for example, 20 mmol or more (for example, about 30 to 1000 mmol). , Preferably 40 mmol or more (for example, about 50 to 700 mmol), more preferably 80 mmol or more (for example, about 100 to 600 mmol), particularly 100 mmol or more (for example, about 120 to 550 mmol).

  The hot melt adhesive may have a combination of a plurality of functional groups as described above, and in particular, at least one functional group selected from an amino group, a carboxyl group and a hydroxyl group ( A) and at least one functional group (B) selected from an epoxy group and a carbon-carbon double bond group may be included. In the case of having such a plurality of functional groups, the total concentration of the plurality of functional groups may be in the above range, and each functional group concentration may independently satisfy the functional group concentration in the above range. For example, when the hot melt adhesive has an amino group and a carbon-carbon double bond group, the ratio of the amino group is in the above range (for example, 10 mmol / kg or more), and the carbon-carbon double bond The ratio of the group may be the above ratio (for example, 10 mmol / kg or more).

  In particular, when the hot melt adhesive has the functional group (A) and the functional group (B), the ratio of the functional group (A) is in the above range [that is, 10 mmol / kg or more (for example, 40 mmol). / Kg or more)] and the ratio of the functional group (B) may be in the above range [that is, 10 mmol / kg or more (for example, 40 mmol / kg or more)].

  The functional group may have the above-mentioned predetermined concentration in the entire hot melt adhesive, and the hot melt adhesive resin itself may have a predetermined functional group concentration, and the concentration can be adjusted by various methods. Good (or better).

  As a method of adjusting the functional group concentration, regardless of whether the hot melt adhesive resin has a predetermined functional group concentration, for example, (i) a method of introducing a functional group into the hot melt adhesive resin, (Ii) A method of forming a mixture of a hot-melt adhesive resin and a compound having a functional group, (iii) a method of combining these methods, and the like.

  As a method (i) for introducing a functional group, (i-1) a method for synthesizing a hot melt adhesive resin using a compound (or monomer) having a functional group as a copolymerization component, and (i-2) reaction A hot-melt adhesive resin having a reactive group (a) [for example, a functional group (especially, a reactive end group) such as a hydroxyl group, a carboxyl group, an amino group, etc.], and the reactive group (a) A compound having a reactive group (b) (hydroxyl group, carboxyl group, epoxy group, isocyanate group and the like) and the functional group (double bond group etc.) (among the compounds having a functional group to be described later, further the reactivity) (I-3) a method of introducing a functional group using various organic reactions (for example, vinyl by a Reppe reaction using acetylene) Base , Introduction of unsaturated bonds using organometallic reagents such as vinyl lithium, introduction of unsaturated bonds by coupling reactions, introduction of epoxy groups by oxidation of unsaturated bonds, etc.).

  These methods may be used alone or in combination of two or more, and the methods (i-1) and / or (i-2) are particularly preferable. In the method (i-2), typical combinations of the reactive group (a) and the reactive group (b) are exemplified below. In addition, the inside of a parenthesis shows the coupling | bonding form of a reactive group (a) and a reactive group (b).

(A1) Hydroxyl group:
(B) Carboxyl group or acid anhydride group (ester bond), isocyanate group (ester bond)
(A2) Carboxyl group:
(B) Hydroxyl group (ester bond), amino group (amide bond), epoxy group (ester bond), isocyanate group (amide bond)
(A3) Amino group:
(B) A carboxyl group or an acid anhydride group (amide bond), an epoxy group (imino bond), or an isocyanate group (amide bond).

  In the method (ii) using a compound having a functional group, the hot melt adhesive resin and the compound having a functional group are mixed by a conventional method (for example, dry blending, melt blending (melt mixing), etc.). Thus, the functional group concentration can be adjusted (or increased). As will be described later, when a compound having a functional group is mixed (especially melt blending), the hot melt adhesive resin and the compound having a functional group form a bond with the mixing (that is, a double bond group). In some cases, a functional group such as is introduced into a hot-melt adhesive resin.

[Hot melt adhesive resin]
The hot melt adhesive resin is not particularly limited in structure as long as it is a resin having thermal adhesiveness. For example, polyamide resin, thermoplastic polyurethane resin, polyester resin, olefin resin (ethylene-vinyl acetate resin) Etc.), rubber-based adhesives or pressure-sensitive adhesives (such as styrene-butadiene rubber (SBR) -based adhesives). The hot melt adhesive resins may be used alone or in combination of two or more.

  Hereinafter, typical hot melt adhesive resins will be described in detail.

(1) Polyamide resin As the hot melt adhesive polyamide resin (thermoadhesive polyamide resin), for example, homopolyamide (polyamide 46, polyamide 66, polyamide 610 obtained by reaction of a dicarboxylic acid component and a diamine component) , Polyamide 612 etc.), homopolyamide obtained by reaction of lactam or aminocarboxylic acid (eg polyamide 6, polyamide 11, polyamide 12 etc.), polyamide obtained by reaction of dimer acid and diamine component, these polyamide components ( Copolyamides (copolymerized polyamides) copolymerized (co-condensed) with diamine components, dicarboxylic acid components, lactams, and aminocarboxylic acids), polyamide-based elastomers (for example, polyoxyalkylenediamines used as soft segments) Mid) and the like.

Examples of the dicarboxylic acid (or its anhydride) include aliphatic dicarboxylic acids (for example, succinic acid, propannic acid, butanenic acid, pentatanic acid, adipic acid, heptanenic acid, octatannic acid, nonannic acid, decannic acid, dodecanoic acid, Alkane dicarboxylic acids having about 4 to 20 carbon atoms such as undecanoic acid), aromatic dicarboxylic acids (C _6-10 arene dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid), alicyclic dicarboxylic acids (for example, 1 , 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methylhexa Hydrophthalic acid, 4-methylhexahydrophthalic acid, etc. C _5-10, such as cycloalkane carboxylic acid), unsaturated dicarboxylic acids (maleic acid, C _2-10 alkene dicarboxylic acid such as maleic anhydride; tetrahydrophthalic acid, tetrahydrophthalic anhydride, 3-methyl-1,2,3, 6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6 _-C5-10 cycloalkene dicarboxylic acid such as tetrahydrophthalic acid, dimer acid, etc.), hydrogenated dimer acid and the like. The dicarboxylic acid components may be used alone or in combination of two or more.

Examples of the diamine component include aliphatic diamines (C _2-12 alkane diamines such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, 2-methyl propane diamine, 3-methyl propane diamine, octamethylene diamine, decane diamine, and dodecane diamine). Diethylenetriamine, tetraethylenetetramine, polyalkylenepolyamine such as pentaethylenetetramine, etc.), aromatic diamine (1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene and other diamino C _6-10 arenes etc.), alicyclic diamines (e.g., 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, diamino C _5-8 cycloalkane such as 1,2-diaminocyclohexane; 1,3-di (Ami Methyl) cyclohexane, 1,4-di (aminomethyl) cyclohexane, 1,2-di (di (amino C _1-4 alkyl, such as aminomethyl) cyclohexane) C _5-8 cycloalkane, 4,4' Jiaminoji Di (amino C _5-8 cycloalkyl) C _1-4 alkanes such as cyclohexylenemethane, 4,4′-diamino-3,3′-dimethyldicyclohexylenemethane, 4,4′-diaminodicyclohexylenepropane; Isophoronediamine, etc.), cyclic amines (2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di (4-piperidyl) -propane, N-aminopropylpiperazine, 1,4-bisaminopropylpiperazine, etc.) And a diamine having a linear or branched structure such as an aromatic group.

  Examples of the lactam include lactams having about 4 to 20 carbon atoms such as ε-caprolactam and ω-laurolactam. Examples of aminocarboxylic acids include aliphatic aminocarboxylic acids (for example, aminocarboxylic acids having about 4 to 20 carbon atoms such as 11-aminododecamethylene carboxylic acid and 12-aminododecamethylene carboxylic acid), cyclic aminocarboxylic acids ( 4-piperidinecarboxylic acid, 3-piperidinecarboxylic acid, 2-piperidinecarboxylic acid, etc.). The diamine components may be used alone or in combination of two or more.

  Of these, preferred polyamide-based resins include at least homo- or copolyamide having units such as polyamide 6, 66, 11, 12, 612, dimer acid, and diamine components (for example, aliphatic diamines such as ethylenediamine and diethylenetriamine). Examples include homo- or copolyamide as a constituent component. Particularly preferred polyamide-based resins include copolyamides having at least one unit selected from polyamides 6, 66, 11, 12, and 612, such as polyamide 6/11, polyamide 6/12, polyamide 66/12, Polyamide 6/66/12, a copolymer of dimer acid, a diamine component, and at least one selected from caprolactam, laurolactam, and aminoundecanoic acid are included.

  In addition, as the polyamide-based resin, a synthesized product or a commercially available product may be used. For example, dimer acid (a dimer of fatty acids such as soybean oil, tung oil, tall oil, etc.) and a homo- or copolyamide having at least a diamine component as components are available from Fuji Kasei Kogyo Co., Ltd., for example, under the trade name “Tomide 390, 394”. , 500, 509, 535, 558, 560, 575, 1310, 1350, 1360, 1396, 1400, TXC232C, etc., from Sanwa Chemical Industry Co., Ltd., trade names “Sunmide 15-K5, HT-140PK-20”, etc. As a trade name from ACI Japan, as “Evergrip PA131H, PA-79BT”, etc. As a product name from Harima Kasei, “Newmide 945, 2152, 3008”, etc. "Macromelt 6239, 6240, 6301, 6801, 681 , Available as such as JP-116 ".

  A homo- or copolyamide having at least a dimer acid and a diamine component as particularly preferable components has a viscosity at 200 ° C. of 3000 mPa · s or more [eg 3000 to 15000 mPa · s], or a softening point of 130 ° C. or more (eg 130 to Polyamide resin at about 250 ° C.). Examples of polyamide resins belonging to these categories include “Tomide TXC232C”, “Sunmide HT-140PK-20”, “Evergrip PA-79BT”, “Newmide 3008”, “Macromelt 6239”, and the like.

  Moreover, as a copolyamide resin that is particularly preferably used, a relative viscosity of about 1.0 to 2.5 (preferably 1.2 to 2.0), a melting point of about 60 to 220 ° C. (preferably 90 to 170 ° C.). The copolymerized polyamide resin can be mentioned. Such a copolyamide can be obtained, for example, as “VESTAMELT” from Degussa, as “PLATAMID” from ATOFINA, as “GRlLTEX” from EMS, and as “SCHATTI FlX” from SCHAETTI.

  In the hot melt adhesive polyamide resin, the ratio of amino group (terminal amino group) and carboxyl group (terminal carboxyl group) is selected from the range of the former / the latter (molar ratio) = 0/100 to 100/0. For example, it may be 10/90 to 90/10, preferably 15/85 to 85/15, and more preferably about 20/80 to 80/20.

  These polyamide-based resins (dimer acid-based polyamides and copolymerized polyamides) are obtained by polymerization of dicarboxylic acid and an amine component, and usually have amino groups or carboxyl groups remaining at the ends. These functional groups contribute to adhesion.

  In addition, as part of the diamine component and / or dicarboxylic acid component, a compound having another functional group (such as a double bond group) [for example, an unsaturated compound having a carboxyl group described later (unsaturated dicarboxylic acid such as maleic anhydride) Acid or anhydride thereof, reaction product of long-chain unsaturated aliphatic monocarboxylic acid and unsaturated aliphatic carboxylic acid (maleic acid, etc.) (dimer acid, etc., unsaturated alicyclic dicarboxylic acid, etc.)] When used, other functional groups (especially double bond groups) can be introduced. For example, polyamides composed of dimer acid or unsaturated dicarboxylic acid (maleic acid, etc.) have double bonds in the molecular structure, and these unsaturated bonds particularly vulcanize unvulcanized rubber. It greatly contributes to the adhesion between rubber and hot melt resin during bonding.

  Further, a compound having a reactive group (for example, a reactive terminal group such as a carboxyl group or an amino group) of a polyamide-based resin and these groups and an unsaturated bond (double bond) group or an epoxy group. By reacting with an unsaturated compound having a carboxyl group, an unsaturated compound having a hydroxyl group, an unsaturated compound having an amino group, an unsaturated compound having an epoxy group, an unsaturated compound having an isocyanate group, etc. A double bond or an epoxy group can also be introduced.

(2) Thermoplastic polyurethane-based resin Examples of the thermoplastic polyurethane-based resin include thermoplastic resins and thermoplastic elastomers obtained by a reaction between a diisocyanate component and a diol component.

  Examples of the diisocyanate component include aromatic diisocyanates (eg, phenylene diisocyanate, tolylene diisocyanate), araliphatic diisocyanates (eg, xylylene diisocyanate), alicyclic diisocyanates (eg, isophorone diisocyanate), aliphatic diisocyanates (eg, 1,6-hexamethylene diisocyanate, lysine diisocyanate, etc.). The diisocyanate component may be an adduct or may be used in combination with a polyisocyanate component such as triphenylmethane triisocyanate as necessary. A diisocyanate component can be used individually or in combination of 2 or more types.

  Examples of the diol component include polyester diol, polyether diol (polyalkylene glycol such as polytetramethylene ether glycol) and the like. A diol component can be used individually or in combination of 2 or more types.

The polyester diol is not limited to the reaction with a diol, dicarboxylic acid or a reactive derivative thereof (lower alkyl ester, acid anhydride), and may be derived from a lactone. Examples of the diol include aliphatic diols (for example, C _2-10 alkanes such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and neopentyl glycol). Diol, diethylene glycol, triethylene glycol, poly C _2-4 alkylene glycol such as polyethylene glycol), alicyclic diol, aromatic diol and the like. These diols can be used alone or in combination of two or more. The diol may be used in combination with a polyol such as trimethylolpropane or pentaerythritol, if necessary. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (for example, C _4-14 aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid), alicyclic dicarboxylic acids, and aromatics. Dicarboxylic acids (for example, phthalic acid, terephthalic acid, isophthalic acid, etc.) are included. These dicarboxylic acids can be used alone or in combination of two or more. If necessary, the dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid. Lactones include, for example, butyrolactone, valerolactone, caprolactone, laurolactone and the like. These lactones can be used alone or in combination of two or more.

  The thermoplastic polyurethane resin may be a thermoplastic elastomer using a diamine component as a chain extender as necessary. Examples of the thermoplastic urethane-based elastomer include an elastomer having an aliphatic polyether or polyester as a soft segment and a short-chain glycol polyurethane unit as a hard segment. These thermoplastic polyurethane resins can be used alone or in combination of two or more.

(3) Polyester resin As the heat-adhesive polyester resin, a homo- or copolyester resin comprising a diol component and a dicarboxylic acid component as constituents [usually at least an aliphatic diol and / or an aliphatic dicarboxylic acid was used. Homopolyester resin or copolyester resin] and polyester elastomers.

  Examples of the diol component include diols (such as aliphatic diols) exemplified in the section of the thermoplastic polyurethane resin. If necessary, the diol component may be used in combination with a polyol such as trimethylolpropane or pentaerythritol. Further, as a part of the diol component, a diol having an unsaturated bond (for example, an alkene diol such as 1,4-butenediol) may be used as necessary.

  As the dicarboxylic acid component, the dicarboxylic acid component exemplified in the section of the polyamide-based resin, for example, aliphatic dicarboxylic acid (such as adipic acid, azelaic acid, dodecanoic acid), aromatic dicarboxylic acid (such as terephthalic acid, isophthalic acid), Examples thereof include alicyclic dicarboxylic acids (such as 1,4-cyclohexanedicarboxylic acid) and unsaturated dicarboxylic acids (such as maleic acid and dimer acid). If necessary, the dicarboxylic acid component may be used in combination with a polyvalent carboxylic acid such as trimellitic acid. Polyester resins may be used alone or in combination of two or more.

Typical homopolyester resins include, for example, aliphatic diols (C _2-10 alkane diols and poly C _2-4 alkanes described in the section of polyurethane resins such as butanediol, neopentyl glycol, hexamethylene glycol). Diol), an aliphatic dicarboxylic acid (such as the C _4-14 aliphatic dicarboxylic acid), and a saturated aliphatic polyester resin produced by reaction with a lactone if necessary. In addition, a diol can be used individually or in combination of 2 or more types.

The typical copolyester resin includes a part of constituent components (diol and / or terephthalic acid) of polyalkylene terephthalate (usually polyethylene terephthalate or polybutylene terephthalate) and other diols (ethylene glycol, propylene glycol, 1, 4-butanediol, C _2-6 alkylene glycol such as 1,6-hexamethylene glycol, aliphatic diol such as polyalkylene glycol such as diethylene glycol and triethylene glycol; alicyclic diol such as cyclohexanedimethanol) or dicarboxylic Substitution with acid (asymmetric aromatic dicarboxylic acid such as aliphatic dicarboxylic acid, phthalic acid, isophthalic acid etc.) or lactone (butyrolactone, valerolactone, caprolactone, laurolactone etc.) Saturated polyester resin and the like.

Examples of the polyester-based elastomer include elastomers having C _2-4 alkylene arylate (ethylene terephthalate, butylene terephthalate, etc.) as a hard segment and (poly) alkylene glycol or the like as a soft segment. Moreover, as a polyester-type resin, you may use the polyester resin containing a urethane bond, for example, the resin which made the polyester resin high molecular weight with the said diisocyanate.

  Preferred polyester-based resins include copolymer polyesters (or copolyester resins) [particularly those having a number average molecular weight of about 5000 to 50000 (preferably 8000 to 35000) and a melting point of about 60 to 250 ° C. (preferably 90 to 150 ° C.). Polymerized polyester resin]. As the polyester resin (copolyester resin), commercially available products may be used. For example, “VESTAMELT” from Degussa, “PLATAMID” from ATOFINA, “GRILTEX” from EMS, “SCHATTI FlX” from SCAETTI The polyester grade, Degussa's "Dinapol", Toyobo's "Byron", Toa Gosei's "Aron Melt PES", etc. are available.

  In the hot melt adhesive polyester resin, the ratio of hydroxyl group (terminal hydroxyl group) to carboxyl group (terminal carboxyl group) is selected from the range of the former / the latter (molar ratio) = 0/100 to 100/0. For example, it may be 10/90 to 90/10, preferably 15/85 to 85/15, and more preferably about 20/80 to 80/20.

  The polyester-based resin is obtained by polymerization of a dicarboxylic acid component and a diol component. Usually, a hydrosyl group or a carboxyl group remains at the terminal, and these functional groups contribute to adhesion. it can. The amount of such a carboxyl group or hydroxyl group can be controlled by utilizing the composition ratio and terminal group at the time of polyester polymerization. For example, the hydroxyl group concentration of the polyester resin can be increased by modifying the carboxyl group remaining at the terminal with a hydroxycarboxylic acid (such as 12-hydroxycarboxylic acid).

  In addition, as part of the diol component and / or dicarboxylic acid component, a compound having another functional group (such as a double bond group) [for example, an unsaturated compound having a carboxyl group described later (unsaturated dicarboxylic acid such as maleic anhydride) Acid or anhydride thereof, reaction product of long chain unsaturated aliphatic monocarboxylic acid and unsaturated aliphatic carboxylic acid (maleic acid etc.) (dimer acid etc.), unsaturated alicyclic dicarboxylic acid etc.), hydroxyl group When an unsaturated compound (such as an unsaturated diol or the like) having the above is used, another functional group (particularly a double bond group) can be introduced.

  For example, a component having an unsaturated bond (for example, a diol component such as alkenediol, dimer acid, maleic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, 3-methyl-1,2 , 3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2 , 3,6-tetrahydrophthalic acid, 3-methyl-hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid and other dicarboxylic acid components) By using it as a component (polymerization component), double bond groups can be introduced into the molecular structure as in the case of polyamide. Such double-bonded group greatly contributes to adhesion between the rubber and hot melt resin especially when vulcanized unvulcanized rubber.

  In addition, a compound having a reactive group (for example, a reactive terminal group such as a carboxyl group or a hydroxyl group) of a polyester resin and having these groups and an unsaturated bond (double bond) group or an epoxy group. By reacting with an unsaturated compound having a carboxyl group, an unsaturated compound having a hydroxyl group, an unsaturated compound having an amino group, an unsaturated compound having an epoxy group, an unsaturated compound having an isocyanate group, etc. A double bond or an epoxy group can also be introduced.

  Such a polyester resin is extremely useful for adhesion between rubber and fiber, polyester resin, polyvinyl chloride, metal, and the like.

(4) Olefin resin As the heat-adhesive olefin resin, α such as ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene, 1-octene and the like is used. Examples thereof include olefins (particularly α-C _2-10 olefins) or copolymers and olefin elastomers.

  Examples of the α-olefin homopolymer or copolymer include polyolefin (polyethylene such as low density polyethylene and linear low density polyethylene, ethylene-propylene copolymer, atactic polypropylene, etc.), modified polyolefin [ethylene-butene- 1 copolymer, ethylene- (4-methylpentene-1) copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer or its ionomer, ethylene-ethyl acrylate copolymer, etc. Ethylene- (meth) acrylate copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, maleic anhydride-grafted polypropylene, etc.]. Examples of the olefin-based elastomer include elastomers having polyethylene or polypropylene as a hard segment and ethylene-propylene rubber (EPR) or ethylene-propylene-diene rubber (EPDM) as a soft segment.

  These olefin resins can be used alone or in combination of two or more.

  These hot melt adhesive resins can be used alone or in combination of two or more. Note that the hot-melt adhesive resin may usually be water-insoluble.

  Of these hot melt adhesive resins, polyamide resins and polyester resins are preferred from the viewpoints of adhesiveness and functional group concentration. In addition, since the hot melt adhesive of the present invention has a functional group at a predetermined concentration, it has high adhesive strength regardless of the type of adherend (or counterpart material) and the combination of rubber and adherend. Although it can be bonded, polyamide resins and polyester resins often have good adhesion to fibers, metals, glass tex, etc., and hot melt adhesive resins such as ethylene-vinyl acetate resin and styrene butadiene rubber (SBR) Often have good adhesion to wood and paper.

  The hot melt adhesive resins may be used alone or in combination of two or more.

[Compound having functional group]
As described above, the hot melt adhesive of the present invention is a mixture (resin composition) of the hot melt adhesive resin and a compound having a functional group (the exemplified functional group such as an amino group or a double bond group). ). When a compound having such a functional group is used, the functional group concentration of the hot melt adhesive can be adjusted or increased easily and efficiently.

  The compound having a functional group may be a low molecular compound, an oligomer, or a polymer (resin). Examples of compounds having typical functional groups (compounds having an amino group, compounds having a carboxyl group, compounds having a hydroxyl group, compounds having a carbon-carbon double bond group, compounds having an epoxy group) are shown below. The compound having a functional group may be a compound having different functional groups (for example, a carboxyl group and an amino group, a carboxyl group, and a carbon-carbon double bond).

(Compound having an amino group)
As the compound having an amino group, a low molecular weight polyamide resin or polyamide oligomer having an amino group (for example, an aliphatic polyamide resin such as polyamide 12, a copolymerized polyamide resin, or dimer acid) is used as a constituent component. Polyamide resins, etc.), low molecular compounds having amino groups [the diamine components exemplified above (aliphatic, alicyclic, aromatic diamines, etc.), polyamines (polyetheramine, polyethyleneimine, polyallylamine, etc.), polyamides Amines etc.]. In addition, as the compound having such an amino group, for example, a compound known as an epoxy curing agent (amine curing agent) can also be used. The compounds having an amino group may be used alone or in combination of two or more.

(Compound having a carboxyl group)
Corresponding to the polyamide-based resin, a low molecular weight polyamide resin or polyamide oligomer having a carboxyl group (for example, an aliphatic polyamide resin such as polyamide 12 oligomer, a copolymerized polyamide resin, a polyamide resin having a dimer acid as a constituent component), Polycarboxylic acid or its anhydride [aliphatic polycarboxylic acid or its anhydride (C _4-20 saturated or unsaturated aliphatic dicarboxylic acid or its anhydride such as maleic anhydride), aromatic polycarboxylic acid or its anhydride (Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 3,3 ′ or 4,4′-benzophenone tetracarboxylic acid or anhydride, biphenyltetracarboxylic acid or anhydride, 2,2 -Bis (3,4-dicarboxyphenyl) propane or its anhydride, 2,2-bi ( _C8-20 aromatic tri to tetracarboxylic acid or anhydride thereof such as bis (3,4-carboxyphenyl) hexafluoropropane or its anhydride)], polycarboxylic acid (or its anhydride) derivatives [for example And polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride or anhydrides thereof and polyhydric alcohols (for example, C _2-4 alkylene glycol such as ethylene glycol; alkanes such as glycerin, trimethylolpropane, pentaerythritol, etc.) A partial ester of a polycarboxylic acid (or an anhydride thereof) such as an ester (a diester, a triester, etc.), a hydroxycarboxylic acid (for example, glycolic acid, lactic acid, hydroacrylic acid, α-oxy) Such as butyric acid, glyceric acid, 12-hydroxydodecanoic acid Roxyaliphatic carboxylic acid), a monomer having a carboxyl group, or a copolymer [for example, a carboxyl group-containing monomer (acrylic acid, methacrylic acid, β-carboxyethyl acrylate (β-CEA), etc.)] Acrylic resin (for example, poly (meth) acrylic acid) as a component, resin having maleic anhydride as a constituent (for example, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, methyl vinyl ether) -Maleic anhydride copolymer etc.)] and the like. A diester of trimellitic anhydride and ethylene glycol [ethylene glycol bis (anhydrotrimellitate)] can also be obtained from Shin Nippon Rika Co., Ltd. under the trade name “Licacid TMEG”.

  The compounds having a carboxyl group may be used alone or in combination of two or more.

(Compound having a hydroxyl group)
Examples of the compound having a hydroxyl group include polyols [the above-exemplified diol components, trifunctional or higher aliphatic polyols (for example, C _3-10 alkanetri to hexaol such as glycerin, trimethylolpropane, pentaerythritol; Glycerin, ditrimethylolpropane, dipentaerythritol, triglycerin and other poly C _3-10 alkanetri to _hexaol ), cyclic polyol (trihydroxy C _1-10 alkyl isocyanurate such as trihydroxyethyl isocyanurate), etc.] polyols, alkylene oxide of these polyols or a lactone (.epsilon.-caprolactone, etc.) adducts (C _2-4 alkylene oxides such as ethylene oxide), hydroxycarboxylic acids (such as hydroxy carboxylic acids exemplified above) In addition, a monomer having a hydroxyl group or a polymer [for example, a low molecular weight resin (or oligomer) such as an acrylic polyol, a polyester polyol, or a polyether polyol using an acrylic monomer having a hydroxyl group) may be mentioned. It is done.

  The compounds having a hydroxyl group may be used alone or in combination of two or more.

(Compound having a carbon-carbon double bond group)
Examples of the compound having a carbon-carbon double bond group include a monomer, oligomer or resin having at least one relatively stable carbon-carbon double bond in the molecule.

Examples of the compound having a carbon-carbon double bond group include (meth) acrylic monomers [poly (meth) acrylates (ethylene glycol di (meth) acrylate, diethylene glycol) of polyols (such as the polyols exemplified above)] Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate such as (poly) C _2-10 alkylene glycol di (meth) acrylate Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Di to hexa (meth) acrylate of (poly) tri to hexahydroxyalkane such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc.), allyl group-containing compounds (triallyl (iso) cyanurate, diallyl phthalate, triallyl phosphate, etc.), having a carbon-carbon double bond Resin or rubber (or thermoplastic elastomer) [diene resin or rubber (liquid or solid polybutadiene, styrene butadiene copolymer, polyisoprene, polypentenamer, polyheptenamer, polyoctenamer, poly (3-methyloctenamer), polydecenamer, poly ( 3-methyldecenamer), poly C _4-15 alkenylene such as polydodecenamer; copolymer of C _4-15 alkadiene such as butadiene-isoprene copolymer; rubber-modified polyolefin such as butadiene-modified polyethylene; styrene-butadiene block copolymer; Hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block Styrene diene blocks such as copolymers, hydrogenated styrene-isoprene block copolymers (SEP), styrene-isoprene-styrene block copolymers (SIS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS) Copolymers, etc.), modified products of these resins or rubbers (for example, acid-modified resins or rubbers such as maleated polybutadiene (maleic acid-modified polybutadiene), boiled polybutadiene, modified SEBS, etc.)] and the like.

  The unmodified or modified resin (or rubber) may be a commercially available product. For example, liquid polybutadiene resin is available from Nippon Soda Co., Ltd. under the trade names “B-1000”, “B-2000”, “ As for “B-3000” and the like, the maleated polybutadiene resin can be obtained from Nippon Soda Co., Ltd. under the trade name “BN1015”, and the boiled polybutadiene resin can be obtained from Nippon Soda Co., Ltd. as “GQ-1000”. The poly (meth) acrylate and allyl group-containing compounds are widely used as vulcanization aids for unvulcanized rubber.

  The compound having a carbon-carbon double bond has the above-described functional group or reactive group (carboxyl group, amino group, hydroxyl group, epoxy group, isocyanate group, etc.) in addition to the carbon-carbon double bond. It may be. The compound having such a reactive group may form a bond with the hot-melt adhesive resin (such as a terminal thereof).

Examples of the compound having a functional group or a reactive group and a carbon-carbon double bond include an unsaturated compound having a carboxyl group {for example, an unsaturated monocarboxylic acid [(meth) acrylic acid, crotonic acid, (meth) acrylic]. Unsaturated aliphatic monocarboxylic acids and long-chain unsaturated aliphatic monocarboxylic acids (for example, oleic acid, linoleic acid, linolenic acid, etc.) that may form a salt such as aluminum acid and zinc (meth) acrylate _10-34 unsaturated aliphatic monocarboxylic acids), unsaturated aromatic monocarboxylic acids such as vinyl benzoic acid, etc.], unsaturated dicarboxylic acids or anhydrides thereof [eg unsaturated aliphatic dicarboxylic acids or anhydrides thereof (maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, C _4-10, such as mesaconic acid Arukenjika Bonic acid or its anhydride), reaction product of long chain unsaturated aliphatic monocarboxylic acid and unsaturated aliphatic carboxylic acid (maleic acid etc.) (dimer acid etc.)], unsaturated alicyclic dicarboxylic acid (For example, tetrahydrophthalic acid, tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl- 1,5,3,6-tetrahydrophthalic acid, C _5-10 cycloalkene dicarboxylic acid such as 4-methyl-1,2,3,6-tetrahydrophthalic acid, or the like)], acid-modified resins ( The maleated polybutadiene resin and the like}, an unsaturated compound having a hydroxyl group [unsaturated monoalcohol (eg, allyl alcohol, 2-buten-1-ol, 3-butyl). C _3-6 alkenol such as emission-2-ol; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) hydroxyalkyl C _2-10 alkyl (meth) acrylates such as acrylate; butanediol mono (meth) acrylate (Poly) C _2-6 alkylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate; glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Compounds having a hydroxyl group among the poly (meth) acrylates of the exemplified polyols such as tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate; 4-hydroxystyrene, 4-hydroxy -Α- methyl styrene, C _2-6 alkenyl such as vinyl naphthol - including hydroxy C _6-10 arene), unsaturated diols (e.g., C _4-10 alkene diols such as 1,4-butenediol, dihydroxy styrene, etc.) ], Unsaturated compounds having an amino group (C _3-6 alkenylamine such as allylamine, 4-aminostyrene, diaminostyrene, etc.), unsaturated compounds having an epoxy group (such as allyl glycidyl ether, glycidyl (meth) acrylate), Examples thereof include unsaturated compounds having an isocyanate group (for example, vinyl isocyanate).

  The compounds having a carbon-carbon double bond may be used alone or in combination of two or more.

(Compound having an epoxy group)
Examples of the compound having an epoxy group include a monomer, oligomer or resin having at least one epoxy group in the molecule. Such a compound having an epoxy group may have the above-described functional group or reactive group (amino group, hydroxyl group, etc.) in addition to the epoxy group.

Examples of the compound having an epoxy group include epoxy resins [for example, glycidyl ether type epoxy resins (mono or polyglycidyl ethers such as the diol component and the polyols, bisphenol type epoxy resins, novolac type epoxy resins, etc.), glycidyl ester type epoxies. Resin (mono or polyglycidyl ether of compound having carboxylic acid as exemplified above), glycidylamine type epoxy resin (aniline, toluidine, diaminobenzene, xylylenediamine, aminohydroxybenzene, diaminodiphenylmethane, etc.) Epoxy resins such as tetraglycidyldiaminodiphenylmethane)], monomers having epoxy groups (glycidyl (meth) acrylate, allyl glycidyl ether) Etc.), a monomer having an epoxy group or a copolymer (ethylene-glycidyl (meth) acrylate copolymer, ethylene-vinyl acetate-glycidyl (meth) acrylate copolymer, styrene-glycidyl (meth) acrylate copolymer) Polymer, styrene-3,4-epoxycyclohexyl (meth) acrylate copolymer, etc.), compound obtained by epoxidizing unsaturated group (double bond group) of unsaturated compound [for example, cycloalkene ring (cyclopentene, cyclohexene, C _4-20 cycloalkene ring such as cyclooctene, bridged cyclic cycloalkane ring such as norbornene ring, etc.) alicyclic epoxy compound or epoxy resin having at least an epoxy group obtained by oxidizing or epoxidizing a double bond), epoxy Diene resins such as modified polybutadiene and epoxidized SEBS Or an epoxy compound obtained by epoxidizing a double bond of (or rubber)].

  Examples of bisphenol type epoxy resins include glycidyl ethers (diglycidyl ethers) obtained by reaction of bisphenols (4,4-biphenol, 2,2-biphenol, bisphenol F, bisphenol AD, bisphenol A, etc.) and epichlorohydrin. Class).

The novolak type epoxy resin is usually obtained by a reaction between a novolak resin and epichlorohydrin. Examples of novolak resins include phenols (C _1-4 alkylphenols such as phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, resorcinol, naphthol) and aldehydes (formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde). And a novolak resin obtained by a reaction with an aromatic aldehyde such as benzaldehyde and salicylaldehyde).

  The compound having an epoxy group may be liquid or solid.

  As the compound having an epoxy group, a commercially available product may be used. For example, a solid or liquid bisphenol A type epoxy resin is manufactured by Asahi Ciba Co., Ltd. “Araldite Series”, JER (Japan Epoxy Resin) Co., Ltd. As the “Epicoat” series, the liquid alicyclic epoxy compound is “Celoxide 2021, 2080” from Daicel Chemical Industries, Ltd., and the solid alicyclic epoxy resin is “EHPE” from Daicel Chemical Industries, Ltd. Etc., polyfunctional epoxy resins are available from Nagase Kasei Co., Ltd. as “Denacol EX611, EX512, EX411, EX321, Ex-201, Ex-252, Ex-810, Ex-721, EX-711”, etc. it can. In addition, by using a compound having a double bond and an epoxy group [for example, epoxidized polybutadiene, epoxidized SEBS, “CY182” of Asahi Ciba Co., Ltd., “Denalex R-45EPT” of Nagase Kasei Co., Ltd.] Not only the epoxy group concentration but also the double bond concentration can be increased.

  The compounds having an epoxy group may be used alone or in combination of two or more. The epoxy group is a functional group having a relatively high reactivity and easily reacts with a group such as a carboxyl group, a silanol group, or a thiol group. Therefore, hot melt adhesives containing epoxy groups appear to be able to improve adhesion by effectively reacting or interacting with vulcanized or unvulcanized rubbers having these functional groups.

  In the hot melt adhesive, part or all of the functional group-containing compound may form a bond with the hot melt adhesive resin. Specifically, when the hot melt adhesive resin is a resin having a reactive group with respect to a functional group of a compound having a functional group [for example, a hot melt adhesive polyester resin having a hydroxyl group as a reactive group and a functional group. When a compound having a carboxyl group (or acid anhydride) (such as maleic anhydride) is used as a group], these resins and the compound may form a bond (in this example, an ester bond). Therefore, in the present specification, a part or all of the hot melt adhesive and the functional group compound forms a bond in the composition (mixture) composed of the hot melt adhesive and the functional group compound. Resins (or compositions) are also included. Such a bond often occurs when a hot-melt adhesive resin and a compound having a functional group are mixed (especially, melt-mixing or melt-kneading). Functional groups can also be introduced into the adhesive resin.

  Although the ratio of the compound having a functional group depends on the type of the compound having a functional group (low molecular compound, oligomer, resin, etc.), for example, 0.01 to 50 with respect to 100 parts by weight of the hot melt adhesive resin. Parts by weight (for example, 0.01 to 30 parts by weight), preferably 0.05 to 20 parts by weight (for example, about 0.1 to 15 parts by weight), more preferably 0.2 to 10 parts by weight (for example, 0 About 5 to 5 parts by weight).

[Hot melt adhesive]
The melting point (or softening point) of the hot melt adhesive (or hot melt adhesive resin) of the present invention can be selected from the range of about 50 to 250 ° C., for example, 60 to 200 ° C., preferably 80 to 180 ° C. Preferably, it may be about 100 to 160 ° C. (for example, 120 to 150 ° C.).

  The melt index of the hot melt adhesive (or hot melt adhesive resin) of the present invention is, for example, 1 to 250 g / 10 minutes, preferably 2 to 200 g / 10 minutes, and more preferably about 3 to 150 g / 10 minutes. It may be. The melt index can be determined under conventional conditions (for example, conditions of 160 ° C. and a load of 2.16 kg).

  Furthermore, the number average molecular weight of the adhesive (or hot melt adhesive resin) may be, for example, 2000 to 100000, preferably 3000 to 50000, and more preferably about 5000 to 30000.

  The hot melt adhesive (composition) includes various additives such as stabilizers (thermal stabilizers, ultraviolet absorbers, antioxidants, etc.), plasticizers, lubricants, fillers, colorants, flame retardants, It may contain an antistatic agent or the like. The additives may be used alone or in combination of two or more.

  Typical hot melt adhesives of the present invention include the following (1) to (4) [further, (a) to (f)].

(1) A hot melt adhesive composed of a hot melt adhesive polyamide-based resin having an amino group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)] (or its Composition)
In such a hot melt adhesive (1), for example, (a) hot melt adhesive having an amino group or a carboxyl group in the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 100 mmol / kg or more)]. A hot melt adhesive composed of a polyamide resin is included.

(2) It is composed of a hot-melt adhesive polyamide-based resin having an amino group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, a ratio of 40 mmol / kg or more)], and an epoxy group and carbon-carbon two Hot-melt adhesive (or composition thereof) having at least one functional group selected from a heavy bond group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)]
Such a hot melt adhesive (2) has, for example, (b) an amino group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)], and an epoxy A hot melt adhesive polyamide-based resin having at least one functional group selected from a group and a carbon-carbon double bond group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)] A configured hot melt adhesive, and (c) a hot melt adhesive polyamide-based resin having an amino group or a carboxyl group in the above ratio [that is, a ratio of 10 mmol / kg or more (for example, a ratio of 40 mmol / kg or more)], At least selected from compounds having an epoxy group and compounds having a carbon-carbon double bond group And at least one functional group selected from an epoxy group and a carbon-carbon double bond group in the above-mentioned ratio [that is, 10 mmol / kg or more (for example, 40 mmol / kg). The above-mentioned ratio] includes a hot melt adhesive (hot melt adhesive polyamide resin composition) and the like.

(3) Hot-melt adhesive (or its) comprising a hot-melt adhesive polyester-based resin having a hydroxyl group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)] Composition)
In such a hot melt adhesive (3), for example, (d) hot melt adhesive having a hydroxyl group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 100 mmol / kg or more)]. A hot melt adhesive composed of a polyester resin is included.

(4) It is composed of a hot-melt adhesive polyester-based resin having a hydroxyl group or a carboxyl group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, a ratio of 40 mmol / kg or more)], and an epoxy group and carbon-carbon two. Hot melt adhesive having at least one functional group selected from heavy bond groups at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)] Such a hot melt adhesive (4) For example, (e) having a carboxyl group or a hydroxyl group in the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)], and from an epoxy group and a carbon-carbon double bond group At least one selected functional group is added in the above-mentioned ratio [ie, 10 mmol / kg or less. A hot-melt adhesive comprising a hot-melt adhesive polyester-based resin having the above (for example, a ratio of 40 mmol / kg or more), or (f) a carboxyl group or a hydroxyl group at the above-mentioned ratio [ie, 10 mmol / kg or more. A hot-melt adhesive polyester-based resin having a ratio of (for example, 40 mmol / kg or more), and at least one functional group selected from a compound having an epoxy group and a compound having a carbon-carbon double bond group And at least one functional group selected from an epoxy group and a carbon-carbon double bond group at the above-mentioned ratio [that is, a ratio of 10 mmol / kg or more (for example, 40 mmol / kg or more)]. Hot melt adhesive (hot melt adhesive polyester resin composition) Murrell.

  The shape of the hot melt adhesive of the present invention can be appropriately selected according to the shape or combination of the rubber or the adherend, and is not particularly limited, and may be in the form of powder, sheet (or film), etc. It may be. The thickness of the sheet-like hot melt adhesive (hot melt adhesive sheet) is, for example, 0.01 to 20 mm, preferably 0.03 to 10 mm (for example, 0.05 to 5 mm), more preferably 0.1 to 0.1 mm. It may be about 3 mm (for example, 0.2 to 2 mm).

[Rubber and adherend]
The hot melt adhesive of the present invention is useful for bonding rubber (or thermoplastic elastomer) and an adherend to the rubber. The rubber used for adhesion to the adherend may be unvulcanized rubber or vulcanized rubber.

(Rubber)
Examples of rubber include diene rubber, olefin rubber, acrylic rubber, fluoro rubber, urethane rubber, epichlorohydrin rubber (epichlorohydrin homopolymer CO, copolymer ECO of epichlorohydrin and ethylene oxide). , Copolymers obtained by further copolymerizing allyl glycidyl ether), chlorosulfonated polyethylene, propylene oxide rubber (GPO), ethylene-vinyl acetate copolymer (EAM), polynorbornene rubber, modified rubbers (acid-modified) Rubber etc.), thermoplastic elastomers and the like. These rubbers can be used alone or in combination of two or more.

  Examples of the diene rubber include the weight of diene monomers such as natural rubber (NR), isoprene rubber (IR), isobutylene isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), and chloroprene rubber (CR). Copolymer; for example, acrylonitrile-diene copolymer rubber such as acrylonitrile butadiene rubber (nitrile rubber) (NBR), nitrile chloroprene rubber (NCR), nitrile isoprene rubber (NIR); styrene butadiene rubber (SBR, for example, styrene and butadiene Random copolymers, SB block copolymers composed of styrene blocks and butadiene blocks, etc.), styrene-diene copolymer rubbers such as styrene chloroprene rubber (SCR) and styrene isoprene rubber (SIR) are included. The diene rubber includes hydrogenated rubber such as hydrogenated nitrile rubber (HNBR).

  Examples of the olefin rubber include ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM and the like), polyoctenylene rubber and the like.

  Examples of the acrylic rubber include rubbers mainly composed of alkyl acrylate, such as a copolymer ACM of an alkyl acrylate and a chlorine-containing crosslinkable monomer, and a copolymer ANM of an alkyl acrylate and acrylonitrile. Examples thereof include a copolymer of an acrylic acid alkyl ester and a carboxyl group and / or an epoxy group-containing monomer, and ethylene acrylic rubber.

  As the fluororubber, a rubber using a fluorine-containing monomer, for example, a copolymer FKM of vinylidene fluoride and perfluoropropene and, if necessary, tetrafluoroethylene, a copolymer of tetrafluoroethylene and propylene, A copolymer FFKM of tetrafluoroethylene and perfluoromethyl vinyl ether can be exemplified.

  Examples of the urethane rubber (U) include a polyester type urethane elastomer and a polyether type urethane elastomer.

  Examples of the modified rubber include acid-modified rubbers such as carboxyl groups such as carboxylated styrene butadiene rubber (X-SBR), carboxylated nitrile rubber (X-NBR), and carboxylated ethylene propylene rubber (X-EP (D) M). Alternatively, rubber having an acid anhydride group is included.

  Thermoplastic elastomers include polyamide elastomers (copolymers with polyamide as the hard phase and aliphatic polyether as the soft phase), polyester elastomers (polyalkylene arylate as the hard phase, aliphatic polyether and aliphatic polyester). ), Polyurethane elastomers (copolymers having short-chain glycol polyurethane as the hard phase and aliphatic polyether or aliphatic polyester as the soft phase, for example, polyester urethane elastomer, polyether urethane) Elastomers), polystyrene elastomers (eg, styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer, hydrogenated polystyrene). Polystyrene block such as lene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS) as a hard phase, and diene polymer Block or block copolymer with hydrogenated block as soft phase), polyolefin elastomer (polystyrene or polypropylene as hard phase, elastomer with ethylene-propylene rubber or ethylene-propylene-diene rubber as soft phase, crystallinity Olefin elastomer composed of a hard phase and a soft phase different from each other), polyvinyl chloride elastomer, fluorine thermoplastic elastomer, and the like. When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited, and may be a triblock structure, a multiblock structure, a star block structure, or the like.

  For rubber (unvulcanized or vulcanized rubber), additives such as fillers or reinforcing materials (such as inorganic fillers such as mica, clay, talc, silicic acids, silica, calcium carbonate, magnesium carbonate, carbon black, ferrite) , Plasticizers or softeners, vulcanizing agents (eg, radical generators such as sulfur, organic peroxides, azo compounds), co-vulcanizing agents (such as metal oxides such as zinc oxide), vulcanization accelerators or additives Sulfur aids, anti-aging agents (anti-aging agents, anti-ozonants, antioxidants, UV absorbers, etc.), tackifiers, processing aids, extender oils, lubricants (stearic acid, metal stearates, waxes) Etc.), a colorant, a foaming agent, a dispersant, a flame retardant, an antistatic agent, and the like. The additives may be used alone or in combination of two or more.

  The vulcanizing agent can be selected from sulfur vulcanizing agents, organic peroxides, azo compounds (such as azobisisobutyronitrile), and the like. Vulcanizing agents can be used alone or in combination of two or more.

  Sulfur-based vulcanizing agents include sulfur, sulfur chloride, sulfur-containing organic compounds and the like. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Examples of sulfur chloride include sulfur monochloride and sulfur dichloride. Examples of sulfur-containing organic compounds include tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), dipentamethylenethiuram tetrasulfide (DPTT), morpholine. Examples include thiurams such as phosphorus disulfide and alkylphenol disulfide.

  Examples of organic peroxides include diacyl peroxides (lauroyl peroxide, benzoyl peroxide, etc.), dialkyl peroxides (dicumyl peroxide, etc.), and alkyl peroxides (t-butyl hydroperoxide, cumene hydroperoxide). Etc.), alkylidene peroxides (such as ethyl methyl ketone peroxide), peracid esters (such as t-butyl peracetate), and the like.

  Further, if photoirradiation is possible, a photopolymerization initiator can also be used. Examples of the photopolymerization initiator include benzophenone or a derivative thereof (such as 4,4′-dimethoxybenzophenone), an alkylphenyl ketone or a derivative thereof (acetophenone, Examples include diethoxyacetophenone), anthraquinone or a derivative thereof (such as 2-methylanthraquinone), thioxanthone or a derivative thereof (such as 2-chlorothioxanthone), a benzoin ether or a derivative thereof (such as benzoin), a phosphine oxide or a derivative thereof. Further, the vulcanizing agent includes inorganic peroxides such as persulfates (such as ammonium persulfate and potassium persulfate).

  The proportion of the vulcanizing agent can be selected from the range of, for example, about 0.5 to 15 parts by weight with respect to 100 parts by weight of rubber, and is usually about 1 to 10 parts by weight, preferably 1 to 8 parts by weight (for example, 2 to 7 parts by weight).

  Vulcanization accelerator (or vulcanization aid or vulcanization activator) can be selected according to the vulcanizing agent used, ammonia derivatives (aldehyde-ammonia, aldehyde-amine, guanidine, etc.), disulfide Carbon derivatives (thioureas, dithiocarbamates, thiazoles, sulfenamides, xanthates, etc.), organic compounds having a polymerizable unsaturated bond [for example, vinyl monomers (such as divinylbenzene), allyl Monomers (diallyl phthalate, triallyl (iso) cyanurate, etc.), (meth) acrylic monomers (poly (meth) acrylates of the polyols exemplified above, such as ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentae Sri Tall tetra (meth) acrylate, polyfunctional dipentaerythritol tetra (meth) acrylate (meth) acrylates), maleimide-based compound], and the like. These vulcanization accelerators can be used alone or in combination of two or more.

  The amount of vulcanization accelerator used is, for example, about 0.1 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, and more preferably about 0.1 to 3 parts by weight with respect to 100 parts by weight of rubber. You can select from a range.

  The shape of the rubber can be appropriately selected according to the shape of the composite as the final molded product, and is not particularly limited. Two-dimensional shapes such as a sheet shape and a plate shape (board shape), a column shape (a columnar shape, a corner shape) It may be a three-dimensional shape such as a columnar shape or a rod shape.

  The thickness of the two-dimensional rubber (for example, sheet rubber) is, for example, 0.1 to 100 mm, preferably 0.5 to 50 mm (for example, 0.05 to 5 mm), and more preferably 1 to 30 mm (for example, 3-20 mm).

(Adherent)
In the present invention, since a hot melt adhesive having a predetermined concentration of functional groups is used, rubber and a wide range of adherends (or counterpart materials) can be bonded with high adhesive force.

  For this reason, the adherend (or the material of the adherend) is not particularly limited. For example, rubber [the rubber exemplified above (unvulcanized or vulcanized rubber, thermoplastic elastomer, etc.)], plastic [For example, polyamide resins (for example, aliphatic polyamides such as polyamide 6 and polyamide 12), polyester resins (polyalkylene arylates such as polyethylene terephthalate or copolyesters thereof), polycarbonate resins, polysulfone resins, polyimide resins. , Polyketone resins, olefin resins (copolymers of olefins such as polyethylene, polypropylene, ethylene-propylene copolymers or copolymers, ethylene-vinyl acetate copolymers and copolymerizable monomers Coalescence, modified polyolefin, etc.), styrene Fat (polystyrene, impact-resistant polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene block copolymer, etc.), acrylic resin (polymethyl methacrylate, methyl methacrylate-styrene copolymer, etc.), halogen-containing Vinyl resins (such as soft polyvinyl chloride, hard polyvinyl chloride, chlorine-containing vinyl resins such as vinyl chloride-vinyl acetate copolymer, fluorine-containing vinyl resins), glass (or glass), metals (steel, etc.) ), Wood, paper, etc. When rubber is used as the adherend, the same or different rubber may be used for adhesion. Further, the rubber as the adherend is usually a vulcanized rubber in many cases.

  The shape of the adherend can be selected according to the shape of the composite as in the case of rubber, such as a one-dimensional shape such as a fiber shape, a sheet shape, a plate shape, a cloth shape (woven fabric shape, non-woven fabric shape), etc. It may be a two-dimensional shape, a columnar shape (such as a columnar shape or a prismatic shape), or a three-dimensional shape such as a rod shape.

(Adhesion method and composite)
As described above, when the hot melt adhesive of the present invention is used, the rubber and the adherend can be bonded. Adhesion between rubber (unvulcanized or vulcanized rubber) and adherend is to press the rubber and adherend between the rubber and adherend with a hot melt adhesive in a molten state. It can be performed by a general bonding method in hot melt bonding.

  For example, (i) the hot melt adhesive is applied in a molten state to one of the materials (or the contact surfaces of the materials) of rubber and adherend, and applied to the one material to which this adhesive is applied. , A method of pressure-bonding (or heat-bonding) the other material, and (ii) a hot-melt adhesive sandwiching the hot-melt adhesive (powder or sheet-like adhesive) between the rubber and the adherend. The rubber and the adherend are bonded by a method of melting and pressure bonding (or heat pressure bonding) [for example, a method of melting (and pressing) a hot melt adhesive using a hot air furnace, a heat press, high frequency, etc.] Can be glued.

  Further, the above method can be applied to any of unvulcanized rubber and vulcanized rubber, and when unvulcanized rubber is used, it can be vulcanized at an appropriate stage. For example, when using an unvulcanized rubber, in the above method (i), the unvulcanized rubber may be vulcanized after the application of the hot melt adhesive, together with the pressure bonding or after the pressure bonding (or after the bonding). In the above method (ii), the unvulcanized rubber may be vulcanized together with melting of the hot melt adhesive, after melting (or after bonding), or together with pressure bonding. In a preferred embodiment, the pressure bonding and melting of the hot melt adhesive are performed in accordance with the vulcanization conditions (such as the vulcanization temperature) of the unvulcanized rubber, so that the unvulcanized rubber is melted together with the pressure bonding and the melting of the hot melt adhesive. May be vulcanized. In a typical method, for example, an unvulcanized rubber, a hot melt adhesive and an adherend (such as plastic) are accommodated in a mold (or cavity) corresponding to the shape of the composite, and vulcanized (and hot melt bonded). If necessary, a mold-release material such as a polytetrafluoroethylene sheet and a hot melt adhesive (such as an adhesive sheet) are accommodated in the mold, and unvulcanized rubber is molded into the mold. And then vulcanize (and melt the hot melt adhesive) to prepare a rubber (vulcanized rubber) to which the hot melt adhesive is applied, and remelt the hot melt adhesive applied to the rubber. Then, the adherend may be pressure-bonded.

  When unvulcanized rubber is used, conventional molding machines (injection molding machine, hot press molding machine, transfer molding machine, extrusion molding) are used for molding of unvulcanized rubber (and hot melt adhesion to the adherend). Machine).

  In the above-mentioned method (i), the hot melt adhesive may be applied by melting the hot melt adhesive after contacting (or adhering) the hot melt adhesive to one of the materials by laminating or spraying. You may apply what was made by application | coating etc. Further, the pressure bonding (or contact) may be heat pressure bonding, for example, may be performed under heat using a hot press or the like. Furthermore, in the method (ii), when the hot melt adhesive is melted by hot pressing or the like, the heating may be performed from both sides of the rubber and the adherend, or may be performed from either one side. For example, when the adherend is a non-rubber material (metal, plastic, etc.), it may be suitably heated from the adherend side.

  In the pressure bonding, the pressure applied between the rubber and the adherend can be appropriately selected according to the kind of the rubber and the adherend, and is, for example, 0.01 to 300 MPa, preferably 0.02 to 100 MPa, and more preferably. May be about 0.03 to 50 MPa (for example, 0.05 to 20 MPa). The pressure bonding time (the time for pressure bonding between the rubber and the adherend) is, for example, about 5 seconds to 30 minutes, preferably 10 seconds to 20 minutes, and more preferably about 30 seconds to 10 minutes (for example, 30 seconds to 8 minutes). There may be. Moreover, when heating in pressure bonding, heating temperature may be 70-250 degreeC, for example, Preferably it is 100-230 degreeC, More preferably, about 130-220 degreeC may be sufficient. Furthermore, when unvulcanized rubber is used, the vulcanization temperature (pressure bonding temperature, hot melt adhesive melting temperature) is, for example, about 70 to 250 ° C, preferably 100 to 230 ° C, and more preferably about 150 to 220 ° C. There may be.

  In addition, in order to improve the adhesive strength between the rubber and the adherend, the surface of the rubber and / or the adherend is pretreated (for example, cleaning treatment, blast treatment, primer application, etc.) prior to adhesion as necessary. Processing). Moreover, an applicator, a hot melt gun, or the like may be used for application (application, etc.) of the hot melt adhesive.

  In the composite of the rubber and the adherend of the present invention obtained by such a method (adhesion method), the rubber and the adherend are firmly bonded to each other by the hot melt adhesive. The adhesive strength between the rubber and the adherend is, for example, 50 N / cm to cohesive failure (one of the rubber and the adherend is broken or broken), preferably about 100 N / cm to cohesive failure. In many cases, it is broken, and it adheres very firmly.

  In the composite of the present invention, it is sufficient that at least the rubber and the adherend are bonded by the hot melt adhesive interposed therebetween, and the rubber and the adherend are at one or a plurality of places. A plurality of rubbers (the same or different types of rubber) and / or a multilayer structure in which a plurality of adherends (the same or different types of adherends) are bonded (for example, rubber / adherent / rubber, (Adherent / Rubber / Adherent, Rubber / Adherent / Rubber / Adherent, etc.)

  The hot melt adhesive of the present invention can be easily formed into a film, a sheet, etc., and can also be made into a granular form, so that it can be used as a conventional rubber adhesive or rubber vulcanized adhesive. It can be used without being dissolved in a solvent, and is extremely useful for bonding rubber (unvulcanized or vulcanized rubber) and various adherends (rubber, plastic, metal, etc.). Therefore, the environment of use is not limited, toxicity is extremely reduced, and a wide range of rubber and adherend combinations can be easily and efficiently and firmly bonded.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Hot melt adhesive)
The hot melt adhesive used in Examples and Comparative Examples is shown below.

(1) Hot melt adhesive polyamide resin A (polyamide copolymer containing approximately the same amount of polyamide 6, 66, 12; melting point 130 ° C., melt index MI (160 ° C., 2.16 kg) = 8 g / 10 min, relative (Viscosity 1.5, amino group concentration 150 mmol / kg)
The hot melt adhesive polyamide resin A was prepared as follows.

  A 1 L autoclave equipped with a stirrer was charged with 200 g of caprolactam, 200 g of lauryl lactam, and 200 g of hexamethylenediamine adipate as raw materials, and the inside was purged with nitrogen. Subsequently, the temperature was gradually raised to 250 ° C. in 5 hours, and maintained at a pressure of 20 bar (2 MPa) for about 8 hours. After the temperature was lowered to 240 ° C., the pressure was gradually reduced to 0.1 bar in order to proceed with condensation, and the reaction was allowed to proceed for 2 hours.

  Finally, in order to take out the product, nitrogen was introduced and the copolyamide was taken out as a strand while slightly pressurizing. After cooling with water, it was cut into pellets with a pelletizer.

(2) Hot-melt-adhesive polyamide resin B (hot-melt-adhesive polyamide resin obtained by melt-kneading 4 parts by weight of triallyl isocyanurate in 100 parts by weight of the above-mentioned polyamide-based hot-melt resin A. Melting point 130 ° C., melt index MI (160 ° C. 2.16 kg) = 15 g / 10 min, relative viscosity 1.5, amino group concentration 145 mmol / kg, double bond group concentration 450 mmol / kg)
(3) Copolymer polyamide synthesized by dehydration condensation reaction from hot melt adhesive polyamide resin C (dimer acid / ethylenediamine / adipic acid / hexamethylenediamine / lauryl lactam / caprolactam = 209 g / 22 g / 54 g / 652 g / 17 g / 43 g) Resin, melting point 145 ° C., MI (160 ° C., 2.16 kg) = 10 g / 10 min, amino group concentration 52 mmol / kg, double bond group concentration 732 mmol / kg)
The hot melt adhesive polyamide resin C was prepared as follows.

  A 1 L autoclave equipped with a stirrer was charged with dimer acid / ethylenediamine / adipic acid / hexamethylenediamine / lauryllactam / caprolactam = 209 g / 22 g / 54 g / 652 g / 17 g / 43 g, and the inside was purged with nitrogen. The temperature was then gradually raised to 210 ° C. in 5 hours and held at a pressure of 20 bar for about 6 hours. For further condensation, the pressure was gradually reduced to 0.1 bar and the reaction was allowed to proceed for 1 hour.

  Finally, in order to take out the product, nitrogen was introduced and the copolyamide was taken out as a strand while slightly pressurizing. After cooling with water, it was cut into pellets with a pelletizer.

(4) Hot-melt adhesive polyester resin A (terephthalic acid / isophthalic acid / 1,4-butanediol / 1,6-hexamethylene glycol / adipic acid / neopentyl glycol = 309 g / 155 g / 126 g / 110 g / 96 g / 145 g A polyester resin comprising a melting point of 129 ° C., MI (160 ° C., 2.16 kg) = 5 g / 10 minutes, hydroxyl concentration of 182 mmol / kg, carboxyl group concentration of 3 mmol / kg)
The hot melt adhesive polyester resin A was prepared as follows.

  To a 1 L autoclave equipped with a stirrer, terephthalic acid / isophthalic acid / 1,4-butanediol / 1,6-hexamethylene glycol / adipic acid / neopentyl glycol = 309 g / 155 g / 126 g / 110 g / 96 g / 145 g was charged and the inside was purged with nitrogen. Next, the temperature was gradually raised to 200 ° C. in 2 hours and maintained at normal pressure for about 3 hours. After raising the temperature to 240 ° C., the pressure was gradually reduced to 0.1 bar and the reaction was allowed to proceed for 2 hours in order to proceed with the condensation.

  Finally, in order to take out the product, nitrogen was introduced and the copolyamide was taken out as a strand while slightly pressurizing. After cooling with water, it was cut into pellets with a pelletizer.

  (5) Hot-melt adhesive polyester resin B (a resin obtained by blending 2 parts by weight of maleic anhydride with 100 parts by weight of the hot-melt adhesive polyester resin A and melting and kneading. Melting point 128 ° C., MI (160 ° C., 2. 16 kg) = 6 g / 10 min, carboxyl group concentration 310 mmol / kg, hydroxyl concentration 5 mmol / kg, double bond group concentration 200 mmol / kg).

  (6) Hot-melt adhesive polyamide resin D (Degussa's “VESTAMELT 3041” was used as it was. Melting point 140 ° C., Ml (160 ° C., 2.16 kg) = 45 g / 10 min, carboxyl group concentration 205 mmol / kg) .

  (7) Hot melt adhesive polyamide resin E (a resin obtained by melting and kneading 5 parts by weight of a maleated polybutadiene resin (“BN-1015” manufactured by Nippon Soda Co., Ltd.) in 100 parts by weight of the above hot melt adhesive polyamide resin D. Melting point 140 ° C., MI (160 ° C., 2.16 kg) = 45 g / 10 min, double bond concentration 798 mmol / kg, carboxyl group concentration 198 mmol / kg).

  (8) Hot melt adhesive polyamide resin F (a resin obtained by melting and kneading 3 parts by weight of a phenol novolac type epoxy resin (“EPN1180” manufactured by Asahi Ciba Co., Ltd.) in 100 parts by weight of the above hot melt adhesive polyamide resin D. 135 ° C., MI (160 ° C., 2.16 kg) = 53 g / 10 min, carboxyl group concentration 142 mmol / kg, epoxy group concentration 148 mmol / kg).

  (9) Hot-melt adhesive polyamide resin G (resin in which the terminal group of the hot-melt adhesive polyamide resin A is blocked with lauric acid and terminal alkylated. Melting point 118 ° C., MI (160 ° C., 2.16 kg) = 10 g / 10 min, amino group concentration 3 mmol / kg).

  (10) Hot melt adhesive polyamide resin H (synthesized by dehydration condensation reaction from hydrogenated dimer acid / ethylenediamine / adipic acid / hexamethylenediamine / lauryl lactam / caprolactam = 209 g / 22 g / 54 g / 652 g / 17 g / 43 g) Copolymer polyamide resin, melting point 122 ° C., MI (160 ° C., 2.16 kg) = 10 g / 10 min, amino group concentration 4 mmol / kg, double bond group concentration 4 mmol / kg).

  (11) Hot-melt adhesive polyester resin C (resin in which the terminal of the hot-melt adhesive polyester resin A is blocked with stearic acid and terminally alkylated. Melting point 140 ° C., MI (160 ° C., 2.16 kg) = 5 g / 10 min, hydroxyl concentration 8 mmol / kg).

  (12) Hot-melt adhesive polyamide resin I (copolymerized polyamide resin obtained by adding butanol to hot-melt adhesive polyamide resin D and condensing and alkylating the terminal. Melting point: 138 ° C., Ml (160 ° C., 2.16 kg) = 49 g / 10 min, carboxyl group concentration 7 mmol / kg).

  In addition, characteristic values, such as a functional group, were measured as follows.

(1) Functional group concentration Amino group ([NH ₂ ]) concentration: 0.5 g of a sample resin was dissolved in 50 ml of a mixed solvent of phenol / methanol (weight ratio) = 10/1 at room temperature, and 1 / 100N hydrochloric acid was used. Quantification was performed using a titrator.

  Carboxyl group concentration: 0.5 g of sample resin was dissolved in 50 ml of benzyl alcohol by heating with a 150 ° C. oil bath, and quantified with 1/100 N NaOHaq (aqueous sodium hydroxide solution) using a titrator.

  Hydroxyl group concentration: Quantified by phthalic anhydride method according to JIS K5117.

  Double bond group concentration: Quantified by iodine value method according to JIS K0070.

  Epoxy group concentration: Epoxy equivalent was measured according to JIS K7236.

(2) Melting point (T _m ): Melting point was measured by DSC method according to JIS K7121.

  (3) Melt index: measured at 160 ° C. according to JIS K7210.

  Table 1 summarizes the melting point, melt index and functional group concentration of the hot melt adhesives used in the examples and comparative examples.

(Rubber)
The composition of the rubber used in the examples and comparative examples is shown below.

[Silicone rubber (VMQ) composition 1]
Silicone rubber (“SH851U” manufactured by Toray Dow Corning Silicon Co., Ltd.) 100 parts by weight Organic peroxide (2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, Nippon Oil & Fat Co., Ltd. 1.5 parts by weight of vulcanization accelerator (trimethylolpropane trimethacrylate, manufactured by Seiko Chemical Co., Ltd., “Hicross M”) 0.5 parts by weight.

[Fluoro rubber (FKM) composition 2]
Fluororubber (Daikin Kogyo Co., Ltd., “DaiEIGgO2”) 100 parts by weight Carbon black (Daicel Degussa Co., Ltd., “MT (N990)”) 10 parts by weight Crosslinking agent (du Pont Co., Ltd., “Diak” No. 7 ") 4 parts by weight Organic peroxide (manufactured by Atofina," Luperox 101XL45 ") 3 parts by weight.

[Styrene Butadiene Rubber / Natural Rubber (SBR / NR) Composition 3]
Natural rubber (NR) 80 parts by weight SBR (manufactured by JSR Corporation, “# 0202”) 20 parts by weight Zinc white 4 parts by weight Stearic acid 1 part by weight Anti-aging agent (manufactured by Kawaguchi Chemical Co., Ltd., “6C”) 2 Part by weight Anti-aging agent (manufactured by Kawaguchi Chemical Co., Ltd., “RD”) 1.2 parts by weight Wax (microcrystal wax) 2 parts by weight Process oil (“N-2”) 1 part by weight Carbon black (FEF) (Tokai Carbon Corporation, “N550”) 50 parts by weight Vulcanization accelerator (manufactured by Kawaguchi Chemical Co., Ltd., “CZ”) 0.7 part by weight Vulcanization accelerator (manufactured by Kawaguchi Chemical Co., Ltd., “PVI”) 0.2 parts by weight Sulfur powder 2.5 parts by weight.

[Acid-modified nitrile butadiene rubber (X-NBR) composition 4]
X-NBR (manufactured by Nippon Zeon Co., Ltd., “Nipollo 27J”) 100 parts by weight Clay (manufactured by Hoffman Mineral Co., Ltd., “SiItin Z86”) 80 parts by weight Carbon black (manufactured by Tokai Carbon Co., Ltd., “N660”) 3 parts by weight Plasticizer (Bayer Co., Ltd., “Valkanol 88”) 10 parts by weight Stearic acid 1 part by weight Organic peroxide (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”) 6 parts by weight 2 parts by weight of agent (trimethylolpropane trimethacrylate, manufactured by Seiko Chemical Co., Ltd., “High Cloth M”).

[Hydrogenated Nitrile Butadiene Rubber (H-NBR) Composition 5]
H-NBR (manufactured by Nippon Zeon Co., Ltd., “Zetpol 3110”) 100 parts by weight Clay (manufactured by Hoffman Mineral Co., Ltd., “SiItin Z86”) 50 parts by weight Carbon black (manufactured by Tokai Carbon Co., Ltd.) “N550”) 10 parts by weight Plasticizer (manufactured by Bayer Co., Ltd., “Valkanol 88”) 10 parts by weight Zinc white 2 parts by weight Organic peroxide (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”) 7 parts by weight Part Vulcanization accelerator (manufactured by Kayaku Akzo Co., Ltd., “HVA-2 / Vulnoc PM-P”) 4 parts by weight.

[Ethylene propylene diene rubber (EPDM) composition 6]
EPDM (DSM Japan Co., Ltd., “Keltan 378”) 50 parts by weight EPDM (DSM Japan Co., Ltd., “Keltan 509 × 100”) 100 parts by weight Zinc Hana 3 types (manufactured by Wako Pure Chemical Industries, Ltd.) 5 Part by weight Stearic acid 1 part by weight Magnesium silicate (manufactured by Nippon Mytron Co., Ltd., “Mistron Vapor”) 50 parts by weight Silica (manufactured by Nippon Silica Co., Ltd., “Nip Seal VN3”) 25 parts by weight White Glossy CC 30 parts by weight Polyethylene 2 parts by weight of glycol (manufactured by NOF Corporation, “PEG4000”) 20 parts by weight of carbon black (“HAF”, manufactured by Tokai Carbon Co., Ltd.)

[Butyl rubber (BR) composition 7]
Butyl rubber (manufactured by JSR Corporation, “BR10”) 100 parts by weight Silica (manufactured by Shionogi & Co., Ltd., “Carplex FPS-101”) 60 parts by weight Plasticizer (triethylene glycol di (2-ethylhexoate) )) 10 parts by weight Organic peroxide (2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, manufactured by NOF Corporation, “Perhexa 25B40”) 1 part by weight Vulcanization accelerator ( Trimethylolpropane trimethacrylate, manufactured by Seiko Chemical Co., Ltd., “Hicross M”) 0.5 part by weight Stearic acid 1 part by weight.

[Styrene Butadiene Rubber (SBR) Composition 8]
SBR (manufactured by Nippon Synthetic Rubber Co., Ltd., “SBR1500”) 100 parts by weight Alkylphenol resin (manufactured by Taoka Chemical Co., Ltd., “Tackiol 201”) 10 parts by weight Carbon black (manufactured by Tokai Carbon Co., Ltd., “HAF carbon”) 50 parts by weight Stearic acid 2 parts by weight Zinc flower (No. 1) 3 parts by weight Sulfur 2 parts by weight Vulcanization accelerator (manufactured by Kawaguchi Chemical Co., Ltd., “Soccinol CZ”) 1 part by weight Process oil (manufactured by Cosmo Oil Co., Ltd.) "Cormolex No. 2") 6 parts by weight.

(Adherent)
The adherend (partner material) used in the examples and comparative examples is shown below.

(A) Rigid polyvinyl chloride plate (b) Polyester fabric (c) Steel plate 1 (Blasted with Alundum 80, degreased, and coated with an epoxy phenol primer (manufactured by Daicel Degussa Co., Ltd., “E1R”)) Primer-treated steel sheet)
(D) Steel plate 2 (Primer-treated steel plate blasted with Alundum 80, degreased, and coated with a polybutadiene-based primer ("F3" manufactured by Daicel Degussa Co., Ltd.))
(E) Soft polyvinyl chloride sheet (f) Styrene butadiene rubber / natural rubber (SBR / NR) (vulcanized rubber obtained by vulcanizing the rubber composition 3)
(G) Fluoro rubber (vulcanized rubber obtained by vulcanizing the rubber composition 2)
(H) Ethylene propylene diene rubber (vulcanized rubber obtained by vulcanizing the rubber composition 6)
(I) Styrene butadiene rubber (vulcanized rubber obtained by vulcanizing the rubber composition 8).

(Examples 1-18, Comparative Examples 1-18)
Each of the hot melt adhesive resins (1) to (10) was used to prepare a sheet (hot melt adhesive resin sheet) having a thickness of 0.5 mm with a hot press.

  First, in Examples 1 to 10 and Comparative Examples 1 to 10, the rubber compositions 1 to 8 were each vulcanized to form a vulcanized rubber sheet having a thickness of 5 mm. Then, the vulcanized rubber sheet and the adherend were bonded using a hot melt adhesive resin sheet in the combinations, bonding methods, and bonding conditions shown in Tables 2 and 3.

  In Examples 11 to 18 and Comparative Examples 11 to 18, first, the rubber was placed on a mold of a cavity of 3 cm × 15 cm × 5 mm thickness in which the polytetrafluoroethylene sheet and the hot melt adhesive resin sheet were arranged. The compositions (unvulcanized rubber compositions) 1 to 8 were injection molded under the conditions shown in Table 3, and the hot melt adhesive resin sheet was melted to form a vulcanized rubber sheet to which the hot melt adhesive was adhered. . Then, the vulcanized rubber sheet to which the hot melt adhesive was adhered and the adherend were bonded using the combinations, bonding methods, and bonding conditions shown in Tables 4 and 5.

  In addition, in the heat press of rubber (unvulcanized or vulcanized rubber) and cloth (cloth) or a steel plate, heating was performed by heating from the side of the fabric or steel plate. Further, in the hot press between rubbers, immediately after the hot melt adhesive sheet melted, the rubber as the adherend was pressed and held under the conditions shown in the table.

  And the adhesion test of the composite_body | complex of the rubber | gum and adherend which were obtained in the Example and the comparative example was done with the following method.

  Adhesion test: After a composite of rubber and adherend is stored in an air-conditioned room at 23 ° C. and 50% RH for about 1 day, a 2.5 cm wide test piece is prepared (however, a composite of rubber and steel plate is used) Then, only the vulcanized rubber sheet portion to which the hot melt adhesive is adhered is cut to a width of 2.5 cm), and a tensile tester (“RTA-1T” manufactured by A & D Co., Ltd.) is used with this test piece. A peel test (tensile speed of 100 mm / min) was performed to measure the adhesive strength between the rubber and the adherend.

  The result of an Example and a comparative example is shown to Tables 2-5.

Claims (11)

  A hot melt adhesive for adhering a rubber and an adherend, which is composed of a hot melt adhesive resin without containing a saponified ethylene-vinyl acetate copolymer, and having a concentration of 10 mmol / kg or more Hot-melt adhesive for rubber bonding having functional groups in proportion.   The adhesive according to claim 1, wherein the functional group is at least one selected from an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and a carbon-carbon double bond group.   The adhesive according to claim 1, having at least one functional group (A) selected from an amino group, a carboxyl group and a hydroxyl group at a rate of 20 mmol / kg or more.   A hot-melt adhesive polyamide-based resin having at least one functional group selected from an amino group and a carboxyl group at a rate of 30 to 1000 mmol / kg, and at least one functional group selected from a carboxyl group and a hydroxyl group; The adhesive according to claim 1, comprising at least one selected from hot-melt adhesive polyester resins having a ratio of 30 to 1000 mmol / kg or more.   The adhesive according to claim 1, comprising at least one hot-melt adhesive resin selected from a hot-melt adhesive polyamide-based resin and a hot-melt adhesive polyester-based resin, and a compound having a functional group.   The adhesive according to claim 5, wherein the compound having a functional group is at least one selected from a compound having an epoxy group and a compound having a carbon-carbon double bond.   The adhesive according to claim 5, wherein the ratio of the compound having a functional group is 0.01 to 30 parts by weight with respect to 100 parts by weight of the hot-melt adhesive resin. The adhesive according to claim 1, which is any one of the following (1) to (4).
(1) A hot melt adhesive composed of a hot melt adhesive polyamide-based resin having an amino group or a carboxyl group at a ratio of 40 mmol / kg or more. (2) It has an amino group or a carboxyl group at a ratio of 40 mmol / kg or more. Hot-melt adhesive comprising a hot-melt adhesive polyamide-based resin and having at least one functional group selected from an epoxy group and a carbon-carbon double bond group at a rate of 40 mmol / kg or more (3) Hydroxyl group Or a hot melt adhesive comprising a hot melt adhesive polyester resin having a carboxyl group at a ratio of 40 mmol / kg or more. (4) a hot melt adhesive polyester having a hydroxyl group or a carboxyl group at a ratio of 40 mmol / kg or more. Made of epoxy resin and Shea groups and carbon - hot-melt adhesive having at least one functional group selected from the carbon-carbon double bond group at a ratio of more than 40 mmol / kg The adhesive according to claim 1, which is any of the following (a) to (f).
(A) A hot melt adhesive composed of a hot melt adhesive polyamide resin having an amino group or a carboxyl group at a rate of 100 mmol / kg or more. (B) An amino group or a carboxyl group at a rate of 40 mmol / kg or more. And a hot melt adhesive comprising a hot melt adhesive polyamide-based resin having at least one functional group selected from an epoxy group and a carbon-carbon double bond group at a rate of 40 mmol / kg or more (c ) At least one functional group selected from a hot melt adhesive polyamide resin having an amino group or a carboxyl group at a ratio of 40 mmol / kg or more, a compound having an epoxy group, and a compound having a carbon-carbon double bond group An epoxy group and a carbon-carbon double bond. Hot melt adhesive having at least one functional group selected from a group at a rate of 40 mmol / kg or more (d) Consists of a hot melt adhesive polyester resin having a hydroxyl group or a carboxyl group at a rate of 100 mmol / kg or more (E) a carboxyl group or a hydroxyl group at a rate of 40 mmol / kg or more, and at least one functional group selected from an epoxy group and a carbon-carbon double bond group at 40 mmol / kg (f) Hot melt adhesive polyester resin having a carboxyl group or hydroxyl group at a ratio of 40 mmol / kg or more, and an epoxy group Having carbon and carbon-carbon double bond And at least one functional group selected from an epoxy group and a carbon-carbon double bond group is 40 mmol / kg or more. Hot melt adhesive with proportion   A method of adhering a rubber and an adherend by interposing the adhesive according to claim 1 in a molten state between the rubber and the adherend and bonding the rubber and the adherend.   A composite of rubber and an adherend obtained by the method according to claim 10.