Emulsion adhesive composition, coating film, and bonded object

Abstract

An emulsion adhesive composition comprising an acid-modified polyolefin resin, an alcohol-soluble nylon resin, and an alcohol solvent, wherein the mass ratio of the acid-modified polyolefin resin to the alcohol-soluble nylon resin (acid-modified polyolefin resin) / (alcohol-soluble nylon resin) is 90 / 10 to 30 / 70 and the acid-modified polyolefin resin is dispersed in the alcohol solvent, and a coating film and a bonded object both obtained from or using the emulsion adhesive composition.

Description

Emulsion adhesive composition, coating film, and adhesive

[0001] The present disclosure relates to emulsion adhesive compositions, coatings, and adhesives.

[0002] A glass sheet for an automobile window is integrated with a resin or rubber member that is interposed between the glass sheet and the vehicle body, seals the gap between the glass sheet and the vehicle body, and, if necessary, also has a decorative function. Such functional members are called by various names, such as molding, frame material, gasket, and molding, but in this disclosure, they are all referred to as molding. Traditionally, polyvinyl chloride (PVC) has been widely used as a molding material due to its excellent scratch resistance and moldability. However, in recent years, from the perspective of environmental protection, the use of thermoplastic elastomers (TPEs), such as thermoplastic polyolefins, has been proposed.

[0003] For example, Patent Document 1 describes an adhesive composition used for bonding a thermoplastic elastomer to a glass article, which is characterized by containing a chlorinated polyolefin, an epoxy group-containing compound, and a silane coupling agent.

[0004] Furthermore, Patent Document 2 describes an aqueous dispersion characterized by containing an acid-modified polyolefin resin (A), a modified nylon resin (B), and an aqueous medium.

[0005] International Publication No. 2004 / 024843 Japanese Patent Application Laid-Open No. 2009-286918

[0006] However, TPE is not easily bonded to glass due to its poor surface adhesion and polarity. Therefore, conventionally used adhesive compositions have not always been suitable for bonding glass to TPE. To solve this problem, as described in Patent Document 1, chlorinated resins have been used in adhesive compositions, or two- or three-component adhesive compositions have been developed.

[0007] The problem to be solved by the present disclosure is to provide an emulsion adhesive composition that has excellent adhesion between a thermoplastic elastomer and glass. Another problem to be solved by the present disclosure is to provide a coating film and an adhered object using the emulsion adhesive composition.

[0008] Specific means for solving the above problems include the following aspects. <1> An emulsion adhesive composition which is a solution containing an acid-modified polyolefin resin, an alcohol-soluble nylon resin, and an alcohol, wherein the mass ratio of the acid-modified polyolefin resin to the alcohol-soluble nylon resin (acid-modified polyolefin resin / alcohol-soluble nylon resin) is 90 / 10 to 30 / 70, and the acid-modified polyolefin resin is dispersed in an alcohol solvent. <2> The emulsion adhesive composition according to <1>, which has a resin solids content of 20 mass% or less. <3> The emulsion adhesive composition according to <1> or <2>, which further contains water. <4> The emulsion adhesive composition according to any one of <1> to <3>, which further contains a polymeric multifunctional silane coupling agent having two or more epoxy groups. <5> The emulsion adhesive composition according to <4>, wherein the mass ratio of the total mass of the resin solids of the acid-modified polyolefin resin and the alcohol-soluble nylon resin to the polymeric multifunctional silane coupling agent having two or more epoxy groups (acid-modified polyolefin resin + solvent-soluble nylon resin / polymeric multifunctional silane coupling agent having two or more epoxy groups) is 100 / 0.5 to 100 / 10. <6> The emulsion adhesive composition according to any one of <1> to <5>, wherein the acid-modified polyolefin resin is an acid-modified product of at least one resin selected from the group consisting of an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer. <7> The emulsion adhesive composition according to any one of <1> to <6>, wherein the acid-modified polyolefin resin is an itaconic anhydride and / or maleic anhydride-modified polyolefin resin. <8> The emulsion adhesive composition according to any one of <1> to <7>, wherein the acid-modified polyolefin resin has a melting point of 50° C. to 135° C. <9> The emulsion adhesive composition according to any one of <1> to <8>, wherein the alcohol-soluble nylon resin contains 20 mol % or more of piperazine, and has an amine value of 1 mgKOH / g to 6 mgKOH / g and an acid value of 4 mgKOH / g to 10 mgKOH / g, when the total amount of diamine components constituting the alcohol-soluble nylon resin is taken as 100 mol %.<10> The emulsion adhesive composition according to <4> or <5>, wherein the polymeric polyfunctional silane coupling agent has an alkoxysilyl group and two or more epoxy groups and has a weight average molecular weight of 200 to 10,000. <11> The emulsion adhesive composition according to any one of <1> to <10>, which is for use on automobile window glass. <12> A coating film obtained by drying, or by drying and curing, the emulsion adhesive composition according to any one of <1> to <11>. <13> An adhered article having an adhesive layer obtained by drying and curing the emulsion adhesive composition according to any one of <1> to <11>.

[0009] The present disclosure provides an emulsion adhesive composition that exhibits excellent adhesion between a thermoplastic elastomer and glass. The present disclosure also provides a coating film and an adhered object using the emulsion adhesive composition.

[0010] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of preferred embodiments is a more preferred embodiment. In the description of a group (atomic group) in the present disclosure, a description that does not specify whether it is substituted or unsubstituted includes both unsubstituted and substituted groups. In the present disclosure, unless otherwise specified, each component may be used alone or in combination of two or more types.

[0011] (Emulsion Adhesive Composition) The emulsion adhesive composition according to the present disclosure (hereinafter also simply referred to as the "adhesive composition according to the present disclosure") comprises an acid-modified polyolefin resin, an alcohol-soluble nylon resin, and an alcohol solvent, wherein the mass ratio of the acid-modified polyolefin resin to the alcohol-soluble nylon resin (acid-modified polyolefin resin / alcohol-soluble nylon resin) is 90 / 10 to 30 / 70, and the acid-modified polyolefin resin is dispersed in the alcohol solvent.

[0012] When bonding glass and polyvinyl chloride substrates, conventional adhesive compositions have been used that contain a polyamide resin and an alcohol solvent as their main components. However, when bonding glass and TPE substrates, these adhesive compositions exhibit good adhesion to glass but insufficient adhesion to TPE. On the other hand, conventional adhesive compositions containing an acid-modified polypropylene resin and an organic solvent as their main components can bond TPE but exhibit insufficient adhesion to glass. Furthermore, they have poor storage stability when the components are mixed, necessitating the use of a two- or three-component adhesive composition. In light of the above circumstances, the present inventors conducted extensive research and found that the emulsion adhesive composition of the present disclosure is a one-component adhesive composition that exhibits excellent adhesion between thermoplastic elastomers and glass. The emulsion adhesive composition is prepared by emulsifying an acid-modified polyolefin resin in an alcohol solvent to form an emulsion, which is then mixed with a polyamide.

[0013] The emulsion adhesive composition according to the present disclosure will be described in detail below.

[0014] <Acid-Modified Polyolefin Resin> The adhesive composition according to the present disclosure contains an acid-modified polyolefin resin. Examples of the acid-modified polyolefin resin include polyolefin resins modified with an α,β-unsaturated carboxylic acid or a derivative thereof.

[0015] The polyolefin resin is not particularly limited, but preferred examples include homopolymers or copolymers of olefins having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, and 4-methyl-1-pentene. Among these, from the viewpoint of adhesiveness, the polyolefin resin is preferably a propylene homopolymer or a propylene copolymer, more preferably at least one selected from the group consisting of an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer, and particularly preferably a propylene-butene copolymer. Furthermore, from the viewpoint of adhesiveness, a copolymer in which the proportion of propylene relative to all monomers constituting the copolymer is 50 mol% to 98 mol% is preferred. The acid-modified polyolefin resins may be used alone or in combination of two or more types.

[0016] Examples of α,β-unsaturated carboxylic acids or derivatives thereof include unsaturated polycarboxylic acids such as maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, aconitic acid, phthalic acid, trimellitic acid, and norbornene dicarboxylic acid, and derivatives thereof (e.g., acid anhydrides, acid halides, amides, imides, esters, etc.). Among these, itaconic anhydride and / or maleic anhydride are preferred in terms of the adhesiveness, handleability, and cost of the acid-modified polyolefin resin. That is, the acid-modified polyolefin resin is preferably an itaconic anhydride and / or maleic anhydride-modified polyolefin resin. The α,β-unsaturated carboxylic acids and derivatives thereof may be used alone or in combination of two or more.

[0017] From the viewpoint of adhesiveness, the graft mass of the α,β-unsaturated carboxylic acid and its derivative in the acid-modified polyolefin resin is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass, based on 100% by mass of the acid-modified polyolefin resin. The graft mass (mass%) of the α,β-unsaturated carboxylic acid and its derivative can be measured by a known method. For example, it can be determined by alkali titration or Fourier transform infrared spectroscopy.

[0018] Furthermore, from the viewpoints of adhesiveness and compatibility with the alcohol-soluble nylon resin, the acid-modified polyolefin resin is preferably modified with a (meth)acrylic acid ester. The (meth)acrylic acid ester is not particularly limited, but from the viewpoints of adhesiveness and compatibility with the alcohol-soluble nylon resin, a compound represented by the following formula (I) is preferred. CH ２ =CR １Ａ COOR ２Ａ ... (I) In formula (I), R １Ａ represents a hydrogen atom or a methyl group, R ２Ａ represents an alkyl group having 8 to 18 carbon atoms.

[0019] In formula (I), R １Ａ is preferably a methyl group. ２Ａ is preferably an alkyl group having 8 to 16 carbon atoms, and is preferably a linear alkyl group. The compound represented by formula (I) is preferably octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, or stearyl (meth)acrylate. In this specification, "(meth)acrylic" means acrylic and methacrylic.

[0020] The graft mass of the (meth)acrylic acid ester in the acid-modified polyolefin resin is preferably 0.1% by mass to 30% by mass, and more preferably 1% by mass to 15% by mass, based on 100% by mass of the acid-modified polyolefin resin, from the viewpoints of adhesiveness and compatibility with the alcohol-soluble nylon resin. The graft mass (mass%) of the (meth)acrylic acid ester can be measured by a known method. For example, Fourier transform infrared spectroscopy or １ It can be determined by H-NMR.

[0021] In the present disclosure, depending on the purpose, graft components other than α,β-unsaturated carboxylic acids and derivatives thereof, and (meth)acrylic acid esters can be used in combination, as long as the properties of the adhesive composition according to the present disclosure are not impaired. Usable graft components include, for example, (meth)acrylic acid, glycidyl (meth)acrylate, isocyanate-containing (meth)acrylic acid, and other copolymerizable unsaturated monomers such as styrene, cyclohexyl vinyl ether, and dicyclopentadiene. The use of these monomers in combination can further improve adhesiveness and solubility in solvents, as well as the graft rate of the α,β-unsaturated carboxylic acids and derivatives thereof, and (meth)acrylic acid esters. It is preferable that the amount of these monomers used does not exceed the total graft amount of the α,β-unsaturated carboxylic acids and derivatives thereof, and (meth)acrylic acid esters.

[0022] The weight-average molecular weight of the acid-modified polyolefin resin is not particularly limited, but is preferably 15,000 to 200,000, and more preferably 30,000 to 200,000. Within this range, the resin has excellent adhesive properties and excellent solubility in alcohol. The weight-average molecular weight of the acid-modified polyolefin resin is measured by gel permeation chromatography (hereinafter also referred to as "GPC") and converted based on the molecular weight of polystyrene.

[0023] Furthermore, the melting point of the acid-modified polyolefin resin as measured by a differential scanning calorimeter (hereinafter also referred to as "DSC") is preferably 50°C to 135°C, more preferably 50°C to 90°C, and particularly preferably 60°C to 85°C, from the viewpoints of adhesiveness and liquid stability.

[0024] The acid-modified polyolefin resin is a resin obtained by graft-modifying a polyolefin resin (A) with an α,β-unsaturated carboxylic acid or a derivative thereof (B) and a (meth)acrylic acid ester (C) represented by formula (I), wherein the graft masses of the α,β-unsaturated carboxylic acid or a derivative thereof (B) and the (meth)acrylic acid ester (C) represented by formula (I) in the acid-modified polyolefin resin are 0.3% by mass to 1.2% by mass and 0.5% by mass to 3.6% by mass, respectively, and the weight-average molecular weight of the acid-modified polyolefin resin is preferably 82,000 to 20,000. Preferred examples of the polyolefin resin (A), the α,β-unsaturated carboxylic acid or a derivative thereof (B), and the (meth)acrylic acid ester (C) represented by formula (I) include the polyolefin resin, the α,β-unsaturated carboxylic acid or a derivative thereof, and the (meth)acrylic acid ester represented by formula (I), respectively.

[0025] Acid-modified polyolefin resins can be obtained, for example, by graft polymerizing an α,β-unsaturated carboxylic acid or a derivative thereof, and a (meth)acrylic acid ester onto a polyolefin resin. The modified polyolefin resin can be synthesized by a known method, and a radical generator, as described below, may be used during production. Examples include a solution method in which a polyolefin resin is heated and dissolved in a solvent such as toluene, and an α,β-unsaturated carboxylic acid or a derivative thereof, and a (meth)acrylic acid ester are added, and a melt method in which an α,β-unsaturated carboxylic acid or a derivative thereof, a (meth)acrylic acid ester, and a radical generator are added to a molten polyolefin resin using a Banbury mixer, kneader, extruder, or the like. Each component may be added all at once or sequentially.

[0026] Depending on the purpose of use, the acid-modified polyolefin resin may further contain a reaction aid for improving the grafting efficiency of the unsaturated carboxylic acid, a stabilizer for adjusting the resin stability, a radical initiator for accelerating the reaction, etc.

[0027] Examples of the reaction aid include styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene, divinylbenzene, hexadiene, and dicyclopentadiene. Examples of the stabilizer include hydroquinone, benzoquinone, and nitrosophenylhydroxy compounds. Known radical initiators can be used, and it is preferable to use organic peroxides such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and cumene hydroperoxide.

[0028] <Alcohol-Soluble Nylon Resin> The adhesive composition according to the present disclosure contains an alcohol-soluble nylon resin. The alcohol-soluble nylon resin used in the present disclosure is a nylon resin that dissolves in an alcohol solvent and is preferably a nylon resin that is solid at 25°C. Furthermore, in the present disclosure, the alcohol-soluble nylon resin preferably dissolves in an amount of 1 g or more, more preferably 5 g or more, and particularly preferably 10 g or more in 100 g of an alcohol-based solvent (e.g., ethanol) at 25°C. The alcohol-soluble nylon resin can be synthesized by a dehydration condensation reaction between various dicarboxylic acids and diamines, self-condensation of aminocarboxylic acids, ring-opening polymerization of intramolecular cyclic compounds of aminocarboxylic acids, or a combination of these reactions.

[0029] The alcohol-soluble nylon resin used in the present disclosure preferably contains piperazine as a constituent component. By using piperazine as a constituent component, the adhesiveness is improved. The content of piperazine in the alcohol-soluble nylon resin is preferably 20 mol% or more, and more preferably 40 mol% to 100 mol%, when the total amount of the diamine components constituting the alcohol-soluble nylon resin is taken as 100 mol%.

[0030] Examples of diamine compounds other than piperazine that can be used in synthesizing the alcohol-soluble nylon resin include, but are not limited to, ethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, p-diaminomethylcyclohexane, bis(p-aminocyclohexyl)methane, m-xylenediamine, and isophoronediamine.

[0031] Dicarboxylic acids used in synthesizing the alcohol-soluble nylon resin include, but are not limited to, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, isophthalic acid, terephthalic acid, 5-sodium sulfoisophthalate, etc. From the viewpoint of solubility in alcohol, it is preferable to use all or part of dicarboxylic acids with relatively low crystallinity, such as azelaic acid, undecanedioic acid, and dimer acid.

[0032] Examples of aminocarboxylic acids used in synthesizing the alcohol-soluble nylon resin include 11-aminoundecanoic acid, 12-aminododecanoic acid, 4-aminomethylbenzoic acid, and 4-aminomethylcyclohexanecarboxylic acid. Examples of intramolecular cyclic compounds of aminocarboxylic acids include, but are not limited to, β-lactam, ε-caprolactam, laurinlactam, α-pyrrolidone, and α-piperidone.

[0033] In addition, alcohol-soluble nylon resins obtained by introducing N-alkoxymethyl groups into polyamide bonds of alcohol-soluble nylon resins can also be used. The introduction of N-alkoxymethyl groups contributes to a lower melting point, increased flexibility, and improved solubility, and the introduction rate is determined depending on the purpose.

[0034] From the viewpoints of adhesiveness and curability, the amine value of the alcohol-soluble nylon resin is preferably 1 mgKOH / g to 6 mgKOH / g. Furthermore, from the viewpoints of adhesiveness and curability, the acid value of the alcohol-soluble nylon resin is preferably 4 mgKOH / g to 10 mgKOH / g. The amine value of the alcohol-soluble nylon resin refers to the number of milligrams of KOH equivalent to the amount of hydrochloric acid required to neutralize the amine present in 1 g of resin, and the acid value refers to the number of milligrams of KOH required to neutralize the acid present in 1 g of resin.

[0035] The method for measuring the amine value of an alcohol-soluble nylon resin in the present disclosure is as follows: 3 g of alcohol-soluble nylon resin is dissolved in a mixed solution of 20 mL of 1-butanol and 20 mL of toluene, and an automatic titrator "AT-510" manufactured by Kyoto Electronics Manufacturing Co., Ltd., connected to an "APB-510-01B" manufactured by Kyoto Electronics Manufacturing Co., Ltd. as a burette, is used. Potentiometric titration is performed using a 0.1 mol / L 2-propanol hydrochloric acid solution as the titration reagent, and the number of mg of hydrochloric acid and the equivalent amount of KOH per 1 g of resin is calculated.

[0036] The method for measuring the acid value of an alcohol-soluble nylon resin in the present disclosure is as follows: 1 g of alcohol-soluble nylon resin is dissolved in 40 mL of benzyl alcohol, and an automatic titrator "AT-510" manufactured by Kyoto Electronics Manufacturing Co., Ltd., connected to an "APB-510-20B" manufactured by Kyoto Electronics Manufacturing Co., Ltd. as a burette, is used. Potentiometric titration is performed using a 0.01 mol / L benzyl alcohol-based KOH solution as the titration reagent, and the number of mg of KOH per 1 g of resin is calculated.

[0037] Alcohol-soluble nylon resins can be synthesized in a single batch without solvent through dehydration condensation, dealcoholization, ring-opening polymerization, or other reactions. In this case, water can be added in advance along with the raw material monomers, and the dehydration reaction can be carried out while distilling off the water. This reaction can be carried out either under normal pressure or under reduced pressure. The molecular weight and amine value of the nylon resin can be adjusted by adjusting the ratio of diamines and dicarboxylic acids added, the reaction time, and the degree of reduced pressure during nylon resin synthesis.

[0038] In the adhesive composition according to the present disclosure, the mass ratio of the acid-modified polyolefin resin to the alcohol-soluble nylon resin (acid-modified polyolefin resin / alcohol-soluble nylon resin) is 90 / 10 to 30 / 70, and from the viewpoint of adhesiveness, it is preferably 70 / 30 to 30 / 70, and more preferably 60 / 40 to 40 / 60.

[0039] From the viewpoint of adhesiveness, the total content of the acid-modified polyolefin resin and the alcohol-soluble nylon resin in the adhesive composition according to the present disclosure is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass to 100% by mass, based on the total solid content of the adhesive composition.

[0040] From the viewpoint of liquid stability, the resin solids content of the adhesive composition according to the present disclosure is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 1% by mass to 20% by mass, and particularly preferably 3% by mass to 15% by mass, relative to the total mass of the adhesive composition. The resin solids content includes the acid-modified polyolefin resin, the alcohol-soluble nylon resin, and the polymeric polyfunctional silane coupling agent described below.

[0041] <Alcohol Solvent> The adhesive composition according to the present disclosure contains an alcohol solvent. From the viewpoint of liquid stability, the adhesive composition according to the present disclosure is preferably a solution of the acid-modified polyolefin resin and the alcohol-soluble nylon resin in a solvent containing an alcohol solvent. From the viewpoint of solubility, the alcohol solvent is preferably an alcohol having one hydroxy group. Furthermore, from the viewpoint of solubility, the alcohol solvent is preferably an alcohol having 1 to 4 carbon atoms, and more preferably an alcohol having 1 to 3 carbon atoms. Specific examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, and 2-butanol. Among these, from the viewpoint of solubility, the alcohol solvent is preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol, and more preferably ethanol.

[0042] The alcohol solvent may be used alone or in combination of two or more. From the viewpoint of liquid stability, the solid content of the adhesive composition according to the present disclosure is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 1% by mass to 20% by mass, and particularly preferably 3% by mass to 15% by mass, relative to the total mass of the adhesive composition.

[0043] From the viewpoint of liquid stability, the content of the alcohol solvent in the adhesive composition according to the present disclosure is preferably 50% by mass or more, more preferably 60% by mass to 99% by mass, even more preferably 65% ​​by mass to 97% by mass, and particularly preferably 70% by mass to 95% by mass, relative to the total mass of the adhesive composition.

[0044] <Water> From the viewpoint of liquid stability, the adhesive composition according to the present disclosure preferably further contains water. Also, from the viewpoint of liquid stability, the adhesive composition according to the present disclosure is preferably a solution of a solvent containing an alcohol solvent and water, more preferably a solution of an alcohol solvent and water. In the method for producing an adhesive composition according to the present disclosure, it is preferable to use an emulsion in which water is used as the solvent for the acid-modified polyolefin resin as a raw material (aqueous emulsion), and therefore the adhesive composition according to the present disclosure preferably contains not only an alcohol solvent but also water. That is, the adhesive composition according to the present disclosure may contain a mixed solvent of alcohol and water.

[0045] From the viewpoint of liquid stability, the water content in the adhesive composition according to the present disclosure is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, even more preferably 3% by mass to 25% by mass, and particularly preferably 4% by mass to 20% by mass, relative to the total mass of the adhesive composition. The water content, based on the total amount of the acid-modified polyolefin and water, is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass.

[0046] By blending an alcohol into an emulsion of an acid-modified polyolefin resin (especially an aqueous emulsion) to create a mixed state, and then dissolving an alcohol-soluble nylon resin in the mixture, an emulsion can be obtained in which the solution containing the acid-modified polyolefin is dispersed in the solvent as fine droplets, thereby obtaining a one-component adhesive composition that has excellent adhesion between thermoplastic elastomers and glass.

[0047] From the viewpoint of liquid stability, the total content of the alcohol solvent and water in the adhesive composition according to the present disclosure is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 80% by mass to 99% by mass, and particularly preferably 85% by mass to 97% by mass, relative to the total mass of the adhesive composition.

[0048] <Silane Coupling Agent> From the viewpoint of adhesiveness and adhesive strength, the adhesive composition according to the present disclosure preferably further comprises a silane coupling agent, more preferably further comprises a silane coupling agent having an epoxy group, and particularly preferably further comprises a polymeric polyfunctional silane coupling agent having two or more epoxy groups. As the silane coupling agent, a known one can be used, but from the viewpoint of adhesive strength, one having an epoxy group is preferred, and one having two or more epoxy groups is more preferred.

[0049] Furthermore, from the viewpoint of adhesiveness and adhesive strength, the silane coupling agent is preferably a polymeric polyfunctional silane coupling agent. The polymeric polyfunctional silane coupling agent is a polymeric silane coupling agent having an alkoxysilyl group and two or more reactive functional groups other than the alkoxysilyl group (e.g., an epoxy group, an amino group, etc.). Among the polymeric polyfunctional silane coupling agents, from the viewpoint of adhesive strength, a polymeric polyfunctional silane coupling agent having two or more epoxy groups is preferred. Furthermore, from the viewpoint of adhesive strength, the polymeric polyfunctional silane coupling agent preferably has an alkoxysilyl group and two or more epoxy groups and has a weight average molecular weight of 200 to 10,000.

[0050] Examples of polymeric polyfunctional silane coupling agents having two or more epoxy groups include compounds represented by the following formula (1) or (2): １ ~R ３ each independently represents a hydrogen atom, a glycidyl group, or an alkoxysilyl group represented by the following formula (3), and R １ ~R ３ At least one of R is an alkoxysilyl group represented by the following formula (3): １ ~R ３ At least two of the groups represented by a are glycidyl groups. a represents an integer of 1 to 100, preferably an integer of 1 to 40, and more preferably an integer of 1 to 30. In formula (2), R ４ ~R ６each independently represents a hydrogen atom, a glycidyl group, or an alkoxysilyl group represented by the following formula (3), and R ４ ~R ６ At least one of R is an alkoxysilyl group represented by the following formula (3): ４ ~R ６ At least two of the groups are glycidyl groups. b represents an integer of 4 to 10, preferably an integer of 4 to 8, and more preferably 4 or 5. c represents an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 5. d represents an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 5. e represents an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 5. In formula (3), R ７ represents an alkyl group having 1 to 6 carbon atoms; X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and n represents an integer of 1 to 3.

[0051] In the compound represented by formula (1), the molar ratio MC / MD of the glycidyl group MC to the alkoxysilyl group MD is preferably 0.02 to 100, more preferably 0.05 to 50, and even more preferably 0.1 to 10. In the compound represented by formula (2), the molar ratio ME / MF of the glycidyl group ME to the alkoxysilyl group MF is preferably 0.1 to 9, and more preferably 0.2 to 5.

[0052]

[0053] From the viewpoint of adhesive strength, the epoxy equivalent of the polymeric polyfunctional silane coupling agent (the mass of the resin containing one equivalent of epoxy groups) is preferably 100 to 500, more preferably 100 to 400, and even more preferably 100 to 300. The epoxy equivalent can be determined in accordance with JIS K 7236:2009. The weight average molecular weight of the polymeric polyfunctional silane coupling agent is preferably 200 to 10,000, more preferably 300 to 8,000. Here, the weight average molecular weight of the polymeric polyfunctional silane coupling agent is a value measured by gel permeation chromatography (GPC) using standard polystyrene.

[0054] Specific examples of polymer-type polyfunctional silane coupling agents having two or more epoxy groups include X-12-981S and X-12-984S manufactured by Shin-Etsu Chemical Co., Ltd.

[0055] The content of the silane coupling agent in the adhesive composition according to the present disclosure, preferably the content of a polymeric polyfunctional silane coupling agent having two or more epoxy groups, is preferably 0.5% by mass to 20% by mass, more preferably 1.0% by mass to 10% by mass, and particularly preferably 1.0% by mass to 8.0% by mass, relative to the total solid content of the adhesive composition, from the viewpoints of adhesiveness and adhesive strength.

[0056] <Other Components> The adhesive composition according to the present disclosure may contain other components in addition to those described above. Examples of other components that can be used include known additives, such as extender pigments, coloring pigments, dyes, antioxidants, plasticizers, lubricants, flame retardants, antistatic agents, UV absorbers, fillers, surfactants, and thickeners. These additives can be added during or after dissolving the raw materials in alcohol.

[0057] Examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate and dimyristyl-3,3'-dithiopropionate; and phosphorus-based antioxidants such as trisnonylphenyl phosphite and tris(2,4-di-t-butylphenyl)phosphite.

[0058] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[(2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octylbenzophenone; and phenyl salicylate. Examples of the ultraviolet absorber include salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, oxalic anilide-based ultraviolet absorbers such as 2-ethoxy-2'-ethyl oxalic acid bisanilide, and hindered amine-based ultraviolet absorbers such as bis[2,2,6,6-tetramethyl-4-piperidine]sebacate and bis[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl]sebacate.

[0059] Examples of the flame retardant include bromine-based flame retardants such as tetrabromobisphenol A, hexabromobenzene, decabromodiphenyl ether, hexabromocyclododecane, bis(pentabromophenyl)ethane, and bis(tetrabromophthalimide)ethane; aromatic phosphate ester-based flame retardants such as triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and cresyl diphenyl phosphate; aromatic condensed phosphate esters such as 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl)phosphate, and bisphenol A bis(diphenyl phosphate); halogen-containing phosphate ester-based flame retardants such as tris(dichloropropyl)phosphate; red phosphorus-based flame retardants such as red phosphorus; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and antimony trioxide; silicon-based flame retardants; and boron-based flame retardants.

[0060] Examples of fillers include calcium carbonate, titanium oxide, zinc oxide, talc, calcium carbonate, carbon black, silica, copper powder, aluminum powder, and silver powder.

[0061] <Method for Producing Adhesive Composition> The method for producing the adhesive composition according to the present disclosure is not particularly limited, but from the viewpoints of ease of preparation of the adhesive composition and liquid stability, it preferably includes a step of mixing an acid-modified polyolefin resin emulsion with an alcohol solvent to obtain a mixture, and a step of adding an alcohol-soluble nylon resin to the mixture. Furthermore, from the viewpoints of ease of preparation of the adhesive composition and liquid stability, it is preferable that the acid-modified polyolefin resin emulsion is an aqueous emulsion of an acid-modified polyolefin resin. The method for producing an aqueous emulsion of an acid-modified polyolefin resin is not particularly limited, but a preferred method is to dissolve the acid-modified polyolefin resin emulsion in an organic solvent such as toluene, add a basic compound such as an amine compound and a surfactant, then add water to cause phase inversion emulsification, remove the organic solvent under reduced pressure, and adjust the solids concentration with water. Examples of materials used for preparing the aqueous emulsion of an acid-modified polyolefin resin are listed below. These materials may be contained directly in the adhesive composition.

[0062] The organic solvent is preferably one that dissolves the acid-modified polyolefin. Specific examples of the organic solvent include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as n-hexane, alicyclic organic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, ketone organic solvents such as acetone and methyl ethyl ketone, alcohol organic solvents such as methanol and ethanol, ester organic solvents such as ethyl acetate and butyl acetate, and propylene glycol ether organic solvents such as propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol t-butyl ether.

[0063] Examples of basic compounds such as amine compounds include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, isobutylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1- Examples of the surfactant include propanol, 2-aminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, piperazines, pyrrole, pyridine, and alkali metal compounds such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide. Among these, from the viewpoint of ease of emulsification and dispersion, morpholine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and 2-amino-2-methyl-1-propanol are preferred.

[0064] The boiling point of the basic compound at normal pressure is preferably not more than 200° C. If the boiling point exceeds 200° C., for example, when the modified polyolefin resin water dispersion composition is used to form a coating film, it may be difficult to remove the basic compound by drying treatment in the water removal step, and the water resistance and moisture resistance of the coating film, particularly when dried at low temperature, and the adhesion to substrates such as non-polar resin molded products may be deteriorated.

[0065] The basic compound such as an amine compound may be a single basic compound or a combination of two or more basic compounds, and in the latter case, the blending ratio of each compound is not particularly limited.

[0066] The adhesive composition may contain a basic compound, particularly an amine compound. The content of the basic compound, particularly the amine compound, is not particularly limited, but may be, for example, in the range of 0.1 to 10 parts by mass per 100 parts by mass of the acid-modified polyolefin.

[0067] Examples of the surfactant include a nonionic surfactant (emulsifier), an anionic surfactant (emulsifier), and a cationic surfactant (emulsifier), as exemplified below.

[0068] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, polyoxyalkylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth)acrylates.

[0069] Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides.

[0070] The adhesive composition according to the present disclosure may contain a surfactant. The content of the surfactant is not particularly limited, but is preferably 1 part by mass to 20 parts by mass, and more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the acid-modified polyolefin.

[0071]

[0023] <Applications> The adhesive composition according to the present disclosure has excellent adhesion between thermoplastic elastomers and glass, and can therefore be suitably used for bonding these. Because the adhesive composition according to the present disclosure has the properties described above, it can be used as an adhesive for automobiles, rolling stock (bullet trains, electric trains), ships, aircraft, architecture, civil engineering, electronics, the aerospace industry, and other industrial products.

[0072] Furthermore, the adhesive composition according to the present disclosure can be used as an adhesive composition to be applied to objects to be bonded, such as interior and exterior parts of automobiles. In particular, the adhesive properties according to the present disclosure can improve the adhesion between glass members, such as automobile window glass, and resin members, and therefore the adhesive composition according to the present disclosure can be suitably used as a window sealant. That is, the adhesive composition according to the present disclosure can be particularly suitably used as an adhesive composition for automobile window glass.

[0073] (Coating Film and Adhesive) The coating film according to the present disclosure is a coating film formed by drying the adhesive composition according to the present disclosure, or by drying and curing. The adhesive product according to the present disclosure is an adhesive product having an adhesive layer formed by drying and curing the adhesive composition according to the present disclosure. After forming a coating film using the adhesive composition according to the present disclosure, the coating film is dried to volatilize the organic solvent, thereby producing a dried coating film, i.e., an adhesive product. The drying temperature for the coating film is not particularly limited, and from the viewpoint of workability, it is preferably 30°C to 100°C. Furthermore, in order to obtain strong adhesion between the two members to be bonded, a method such as pressure bonding at a temperature of 80°C or higher can be applied.

[0074] The adhesive article according to the present disclosure preferably has the adhesive layer between a thermoplastic elastomer member and a glass member. Examples of the thermoplastic elastomer include, but are not limited to, styrene elastomers, olefin elastomers, polyester elastomers, urethane elastomers, and amide elastomers. Examples of the glass include, but are not limited to, soda glass, quartz glass, lead glass, borosilicate glass, and crystallized glass. The thickness of the adhesive layer is not particularly limited, but is preferably 0.5 μm to 20 μm, and more preferably 1 μm to 10 μm.

[0075] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. Unless otherwise specified, "%" is based on mass.

[0076] Synthesis Example 1 Preparation of Acid-Modified Polyolefin Resin Emulsion Into a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a funnel, 100 g of maleic anhydride [MAH]-modified polyolefin resin (weight average molecular weight 150,000, melting point (Tm) = 70 ° C., MAH graft amount = 2% to 5%) of propylene-butene random copolymer [P-B] (propylene component 70 mol%, butene component 30 mol%), 80 g of toluene, and 4 g of morpholine were added, and 10 g of Emulgen 109P (nonionic surfactant, manufactured by Kao Corporation) was added, and the mixture was kneaded for 60 minutes at an internal temperature of 95 ° C. Thereafter, 290 g of deionized water at 90 ° C. was added over 60 minutes. Subsequently, a portion of the toluene was removed under reduced pressure, and the mixture was cooled to room temperature with stirring, and an acid-modified polyolefin resin emulsion was obtained in which the solid content was adjusted to 30% by mass with deionized water.

[0077] Synthesis Example 2: Preparation of alcohol-soluble nylon resin A flask equipped with a stirrer, a reflux dehydration apparatus, and a distillation column was charged with 47 parts by mass of azelaic acid, 215 parts by mass of dodecanedioic acid, 100 parts by mass of piperazine, 63 parts by mass of 11-aminoundecanoic acid, and 120 parts by mass of distilled water. The temperature was raised to 120°C to distill off water, and then the temperature was raised to 240°C at a rate of 20°C / hour. The reaction was continued for 3 hours, and it was confirmed that the amine value had reached the target range, yielding an alcohol-soluble nylon resin. The amine value at this time was 2.5 mgKOH / g, and the acid value was 7.2 mgKOH / g.

[0078] Synthesis Example 3 An alcohol-soluble nylon resin was obtained by charging each component in the amounts shown in Table 1 and reacting them in the same manner as in Synthesis Example 2. The amine value and acid value of the resulting alcohol-soluble nylon resin are shown in Table 1.

[0079]

[0080] Synthesis Example 4: Preparation of non-emulsion acid-modified polyolefin resin Into a twin-screw extruder having a screw length L / diameter D ratio of 42 (L / D) and a screw diameter φ of 58 mm, 100 parts by mass of a propylene-ethylene-α-olefin copolymer (72 mol% propylene, 7 mol% ethylene, 21 mol% butene, weight average molecular weight 120,000, Tm=100°C), 1.5 parts by mass of maleic anhydride, 4 parts by mass of lauryl methacrylate, and 1.5 parts by mass of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane were added. The mixture was reacted for a residence time of 10 minutes at a barrel temperature of 180°C (first to seventh barrels), and degassed in the seventh barrel to remove any remaining unreacted material. The weight average molecular weight of the obtained acid-modified polyolefin resin was 92,000, Tm=90°C, the graft mass of maleic anhydride was 1.1 mass%, and the graft mass of lauryl methacrylate was 3.6 mass%. The carboxy group content was 22.4 mmol / 100 g. The graft mass of unsaturated polycarboxylic acids such as maleic anhydride and their derivatives was measured by alkali titration, and the graft mass of lauryl methacrylate was １ Measured by H-NMR.

[0081] Example 1 A flask equipped with a stirrer, a condenser, and a thermometer was charged with 100 g of the acid-modified polyolefin resin emulsion obtained in Synthesis Example 1 and 476.9 g of ethanol, and then 30.36 g of the alcohol-soluble nylon resin obtained in Synthesis Example 2 was added thereto. The flask temperature was raised to 30°C to 50°C, and the mixture was stirred for 90 minutes to dissolve the alcohol-soluble nylon resin, thereby obtaining an emulsion adhesive composition with a mass ratio of acid-modified polyolefin resin / alcohol-soluble nylon resin = 5 / 5.

[0082] Example 2 An emulsion adhesive composition was obtained by adding 1.2 g of a silane coupling agent X-12-984S (a polymer-type multifunctional silane coupling agent having two or more epoxy groups, manufactured by Shin-Etsu Chemical Co., Ltd.) to 607.3 g of the acid-modified polyolefin resin / alcohol-soluble nylon resin solution obtained in Example 1.

[0083] (Examples 3 to 14 and Comparative Examples 1 to 7) Each component was charged so as to have the ratio shown in Table 2 or Table 3, and an (emulsion) adhesive composition was obtained in the same manner as in Example 1 or 2.

[0084] The resulting (emulsion) adhesive composition was subjected to various tests using the methods described below.

[0085] <Preparation of Glass Plates (Test Specimens) with Thermoplastic Elastomer Molding (TPV)> A glass plate measuring 25 mm long, 150 mm wide, and 5 mm thick was prepared, and the (emulsion) adhesive composition was applied to the glass plate so that the adhesive layer would have a dry thickness of approximately 1 μm to 10 μm. The glass plate was then air-dried to prepare a glass plate with an adhesive layer formed thereon. An olefin-based thermoplastic elastomer material (Santoprene 121-58W175, manufactured by ExxonMobil Corporation) was insert-molded onto the glass plate with the adhesive layer formed thereon to obtain a glass plate with a thermoplastic elastomer molding. The molding temperature was 210°C. Using each of the glass plates (test specimens) with thermoplastic elastomer molding obtained above, an initial peel strength test and a humidity resistance test were performed to measure the adhesive strength. The results are shown in Tables 2 and 3.

[0086] Each test piece was left at room temperature (25°C, hereinafter the same) for 24 hours, and then subjected to a 90-degree peel test at room temperature at a crosshead moving speed of 50 mm / min in accordance with the floating roller peel test specified in JIS K 6854. The initial peel strength (N / mm) was measured and the fracture morphology after the measurement was confirmed. In addition, the fracture morphology of the test piece after the test was confirmed visually.

[0087] 2. Moisture Resistance Test Each test piece was left at room temperature for 24 hours, then left at 80°C and 80% RH for 24 hours, and then left at room temperature for another 24 hours, and then subjected to a 90-degree peel test in accordance with JIS K 6854. The peel strength after moisture resistance (moisture resistance test, N / mm) was measured and the fracture morphology after measurement was confirmed. In addition, the fracture morphology of the test piece after the test was confirmed visually.

[0088] 3. Liquid Stability Test The prepared (emulsion) adhesive composition was left at room temperature for two weeks, and then the appearance of the liquid was visually inspected. The presence or absence of liquid separation or resin sedimentation was evaluated as A, B, or C. A: No liquid separation or resin sedimentation was observed. B: Slight liquid separation or resin sedimentation was observed. C: Liquid separation and / or resin sedimentation was observed.

[0089]

[0090]

[0091] In Tables 2 and 3, Synthesis Example 1 represents the resin solid content in the emulsion obtained in Synthesis Example 1, and Synthesis Examples 2 to 4 represent the resins obtained in Synthesis Examples 2 to 4, respectively. In Tables 2 and 3, CF represents cohesive failure, which is failure within the adhesive layer, and AF represents interfacial failure, which is failure at the bonding interface between the adhesive layer and the adherend. Cohesive failure indicates excellent adhesion, and interfacial failure indicates insufficient adhesion.

[0092] Details of the abbreviations used in Table 2 are as follows: X-12-981S: Polymer-type multifunctional silane coupling agent having two or more epoxy groups (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0093] As shown in Tables 2 and 3, the emulsion adhesive compositions of Examples 1 to 14 had superior adhesion between thermoplastic elastomer and glass compared to the adhesive compositions of Comparative Examples 1 to 6. Comparative Example 7 could not be evaluated because it was unable to maintain a homogeneous state as a solution. Furthermore, as shown in Tables 2 and 3, the emulsion adhesive compositions of Examples 1 to 13 also had excellent liquid stability.

[0094] The disclosure of Japanese Patent Application No. 2024-6299, filed on January 18, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An emulsion adhesive composition comprising an acid-modified polyolefin resin, an alcohol-soluble nylon resin, and an alcohol solvent, wherein the mass ratio of the acid-modified polyolefin resin to the alcohol-soluble nylon resin (acid-modified polyolefin resin / alcohol-soluble nylon resin) is 90 / 10 to 30 / 70, and the acid-modified polyolefin resin is dispersed in the alcohol solvent.

2. The emulsion adhesive composition according to claim 1, wherein the resin solid content is 20% by mass or less.

3. The emulsion adhesive composition according to claim 1, further comprising water.

4. The emulsion adhesive composition according to claim 1, further comprising a polymer type polyfunctional silane coupling agent having two or more epoxy groups.

5. The emulsion adhesive composition according to claim 4, wherein the mass ratio of the total mass of the resin solids of the acid-modified polyolefin resin and the alcohol-soluble nylon resin to the polymer type polyfunctional silane coupling agent having two or more epoxy groups (acid-modified polyolefin resin + solvent-soluble nylon resin / polymer type polyfunctional silane coupling agent having two or more epoxy groups) is 100 / 0.5 to 100 / 10.

6. The emulsion adhesive composition according to claim 1, wherein the acid-modified polyolefin resin is an acid-modified product of at least one resin selected from the group consisting of ethylene-propylene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers.

7. The emulsion adhesive composition according to claim 1, wherein the acid-modified polyolefin resin is an itaconic anhydride and / or maleic anhydride-modified polyolefin resin.

8. The emulsion adhesive composition according to claim 1, wherein the melting point of the acid-modified polyolefin resin is 50°C to 135°C.

9. The emulsion adhesive composition according to claim 1, wherein the alcohol-soluble nylon resin contains 20 mol% or more of piperazine and has an amine value of 1 mgKOH / g to 6 mgKOH / g and an acid value of 4 mgKOH / g to 10 mgKOH / g when the total amount of the diamine components constituting the alcohol-soluble nylon resin is 100 mol%.

10. The emulsion adhesive composition according to claim 4, wherein the polymer type polyfunctional silane coupling agent has an alkoxysilyl group and two or more epoxy groups and a weight average molecular weight of 200 to 10,000.

11. The emulsion adhesive composition according to claim 1, which is for automotive window glass.

12. A coating film obtained by drying, or drying and curing, the emulsion adhesive composition according to any one of claims 1 to 11.

13. An adherend having an adhesive layer obtained by drying and curing the emulsion adhesive composition according to any one of claims 1 to 11.

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