JP2006348078A - Aqueous adhesive and laminated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous adhesive having high adhesive strength compared with conventional adhesive in the case of laminating vinyl chloride resins or vinyl chloride resin and other material (especially a polyolefin resin) by heat-sealing method. <P>SOLUTION: The aqueous adhesive for vinyl chloride substrate contains (A) a polyolefin resin, (B) a polyester resin having an acid value of 2-40 mgKOH/g and an aqueous medium wherein the mass ratio of (A)/(B) is 100/(2-50). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a water-based adhesive for a vinyl chloride substrate containing a polyolefin resin and a polyester resin in a specific ratio.

  Vinyl chloride resin-based materials are used as building materials such as flooring materials and baseboards because they are easy to construct and have excellent design properties such as patterns and colors. However, in recent years, due to diversification and sophistication of required performance, a technique for bonding with other materials, particularly polyolefin resin materials, has begun to be studied.

  Solvent-based vinyl acetate copolymer resin-based adhesives, latex-type SBR-based adhesives, acrylic resin-based adhesives, and the like have been used as adhesives for bonding vinyl chloride resin-based materials to other materials. It was. Recently, water-based adhesives have attracted attention from the viewpoint of environmental problems (indoor pollution and environmental pollution) and safety. For example, Patent Document 1 discloses a water-based adhesive using an ethylene-vinyl acetate resin. ing.

  Further, Patent Document 2 discloses an aqueous dispersion comprising a polyolefin resin and a polyester resin as an aqueous dispersion having good adhesion to various thermoplastic resin films and good heat sealability. This document does not describe the adhesiveness of the aqueous dispersion to the vinyl chloride resin.

JP 2003-277706 A JP 2003-327756 A

  When a water-based ethylene-vinyl acetate resin adhesive as in Patent Document 1 uses a heat seal method that is generally used to bond a vinyl chloride resin and another material using this adhesive. There was a problem that sufficient strength (heat seal strength) could not be obtained.

  As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous adhesive containing a polyolefin resin and a polyester resin having a specific composition in a specific ratio is excellent in heat seal strength. Reached.

That is, the gist of the present invention is as follows.
(1) Polyolefin resin (A), polyester resin (B) having an acid value of 2 to 40 mgKOH / g, and an aqueous medium are contained, and the mass ratio of (A) and (B) is in the range of 100/2 to 100/50. A water-based adhesive for a vinyl chloride substrate, characterized in that:
(2) The water-based adhesive according to (1), wherein the content of the nonvolatile water-based auxiliary is 5% by mass or less.
(3) An adhesive layer (b) formed by removing the aqueous medium from the aqueous adhesive described in the vinyl chloride resin (a), (1) or (2), and another substrate (c) are laminated in this order. A laminated body.
(4) The laminate according to (3), wherein the other substrate (c) is a vinyl chloride resin.
(5) The laminate according to (3), wherein the other substrate (c) is a resin other than vinyl chloride resin.
(6) The laminate according to (5), wherein the resin other than the vinyl chloride resin is a polyolefin resin.
(7) The laminate according to (3), wherein the other substrate (c) is a metal.
(8) The laminate according to (7), wherein the metal is aluminum.

  The water-based adhesive for vinyl chloride resin of the present invention exhibits good adhesion to various materials including vinyl chloride resin. In particular, when laminating vinyl chloride resin materials or vinyl chloride resin and other materials (especially polyolefin resin, aluminum) by the heat seal method, it is possible to obtain higher adhesive strength than conventional adhesives. .

  The present invention will be described in detail below.

  The polyolefin resin (A) is a resin mainly composed of an olefin component (A2) such as olefins having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. A mixture of these monomers may be used. Among these, olefins having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene is particularly preferable.

  The polyolefin resin (A) preferably contains an unsaturated carboxylic acid (A1) for making the resin aqueous (liquefied). The unsaturated carboxylic acid (A1) is preferably contained in an amount of 0.01% by mass or more and less than 10% by mass, more preferably 0.1% by mass or more and less than 8% by mass, and still more preferably, of the total resin. It is 0.5 mass% or more and less than 5 mass%, and 1-4 mass% is the most preferable. When the content of the component (A1) is less than 0.01% by mass, it tends to be difficult to make the resin aqueous (liquefied). On the other hand, when the content of the component (A1) is 10% by mass or more, the aqueous solution can be easily formed, but the water resistance may be deteriorated.

  Examples of such unsaturated carboxylic acid (A1) include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, and crotonic acid. The unsaturated carboxylic acid (A1) may be a derivative such as a salt, an acid anhydride, a half ester, and a half amide. Among these, acrylic acid, methacrylic acid, and (anhydrous) maleic acid are preferable, and acrylic acid and maleic anhydride are particularly preferable. Moreover, the copolymerization form of this component is not specifically limited, Any of random copolymerization, block copolymerization, graft copolymerization, etc. may be sufficient. Note that the acid anhydride forms an acid anhydride structure in which the adjacent carboxyl group is dehydrated and cyclized in the dry state of the resin, but in an aqueous medium containing a basic compound, part or all of the acid anhydride is ring-opened. As a result, the structure of the carboxylic acid or its salt is easily taken.

  Furthermore, it is preferable that the polyolefin resin (A) contains a (meth) acrylic acid ester component (A3) from the viewpoint of adhesion to a vinyl chloride substrate and heat sealability. Regarding the content of (A3), the mass ratio (A2) / (A3) between the olefin component (A2) and the (meth) acrylic acid ester (A3) component is the total amount of these two components being 100% by mass. It is preferably 55/45 to 99/1, and most preferably 75/25 to 90/10 in order to improve the adhesion to the vinyl chloride substrate. When the ratio of the component (A3) is less than 1% by mass, the adhesion to the vinyl chloride base material and the heat sealability tend to decrease. On the other hand, when the content of the compound (A3) exceeds 45% by mass, the properties of the resin derived from the olefin component are lost, and performances such as water resistance and heat sealability are deteriorated.

  Examples of the (meth) acrylic acid ester (A3) component include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Examples include lauryl (meth) acrylate. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are particularly preferable. In addition, the (meth) acrylic acid ester component may be converted to a (meth) acrylic acid component by hydrolyzing a part of the ester bond when the aqueous resin is made. In such a case, The component ratio after the change may be within a specified range.

  Specific examples of the polyolefin resin (A) include ethylene-acrylic acid ester-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, propylene-butene- Maleic anhydride copolymer, ethylene-propylene-butene-maleic anhydride copolymer, ethylene-propylene-acrylic ester-maleic anhydride copolymer, ethylene-butene-acrylic ester-maleic anhydride copolymer, Propylene-butene-acrylic acid ester-maleic anhydride copolymer, ethylene-propylene-butene-acrylic acid ester-maleic anhydride copolymer, and the like. Among them, ethylene-acrylic acid ester-maleic anhydride copolymer is exemplified. Most preferred.

  In the polyolefin resin (A), monomers other than those described above may be copolymerized at 20% by mass or less of the entire resin. Examples thereof include alkyl vinyl ethers having 3 to 30 carbon atoms such as methyl vinyl ether and ethyl vinyl ether, dienes, (meth) acrylonitrile, halogenated vinyls, halogenated vinylidenes, carbon monoxide, and sulfur dioxide.

  The polyolefin resin (A) preferably has a melt flow rate of 0.01 to 500 g / 10 min at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, more preferably 0.1 to 400 g / 10 min, and 1 to 300 g. / 10 minutes is more preferable, and 5-200 g / 10 minutes is more preferable. When the melt flow rate of the polyolefin resin (A) is less than 0.01 g / 10 min, it may be difficult to make the resin water-based or heat sealability may be deteriorated. On the other hand, when the melt flow rate of the polyolefin resin (A) exceeds 500 g / 10 minutes, the resulting coating film tends to be hard and brittle, and the heat sealability tends to be lowered.

  The polyester resin (B) is a polymer mainly composed of a polybasic acid component and a polyhydric alcohol component.

  Polybasic acid components constituting the polyester resin (B) include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, biphenyldicarboxylic acid; oxalic acid, succinic acid, succinic anhydride Saturated aliphatic dicarboxylic acids such as acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, hydrogenated dimer acid; fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid , Unsaturated aliphatic dicarboxylic acids such as citraconic anhydride and dimer acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornene dicarboxylic acid and its anhydride Products, tetrahydrophthalic acid and anhydrides, etc. It is phosphate and the like.

  Trifunctional or higher acid components may be used in small amounts, such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, trimesic acid, Ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2,3,4-butanetetracarboxylic acid, etc. can be used. From the viewpoint of suppression, it is preferable to keep it at 5 mol% or less of the total acid component.

  Among the acid components described above, aromatic polybasic acids are preferred, particularly industrially, because the proportion of aromatic ester bonds that are difficult to hydrolyze in the resin skeleton increases and the water resistance of the adhesive layer is improved. Terephthalic acid and isophthalic acid are preferred because they are produced in large quantities and are inexpensive. In the total acid component, the aromatic polybasic acid is preferably 50 mol% or more, particularly preferably 50 to 100%, more preferably 60 to 100 mol%, and most preferably 70 to 100 mol%. It is.

  Examples of the polyhydric alcohol component constituting the polyester resin include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5 -Aliphatic glycols such as pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol; Alicyclic glycols such as 4-cyclohexanedimethanol; ether-bond-containing glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol; 2,2-bis [4- (hydroxyethoxy ) Fe Le] bisphenols such as propane (bisphenol A) and its ethylene oxide adduct, bis [4- (hydroxyethoxy) phenyl] bisphenols such as sulfone (bisphenol S, etc.) and its ethylene oxide adduct, and the like. In addition, since the water resistance of a polyester resin, blocking resistance, and heat-sealability may be reduced when an ether bond increases, the ratio of the ether bond containing glycol to the polyhydric alcohol component of a polyester resin is 10 mol% or less. It is preferable that it is 5 mol% or less.

  As the polyhydric alcohol, ethylene glycol and neopentyl glycol are preferably used because they are inexpensive because they are industrially produced in large quantities. The total proportion of ethylene glycol and neopentyl glycol in the polyhydric alcohol component of the polyester resin is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, and more preferably 80 to 100 mol% is most preferred. Ethylene glycol has the advantage of improving heat sealability and neopentyl glycol having improved water resistance.

  Furthermore, a polyhydric alcohol having three or more functional groups such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like may be contained as the polyhydric alcohol component, but in order to suppress gelation during the production of the polyester resin. In addition, the proportion of the trifunctional or higher polyhydric alcohol in the polyhydric alcohol component of the polyester resin is preferably limited to 5 mol% or less.

  The polyester resin (B) may be copolymerized with a monocarboxylic acid, monoalcohol, or hydroxycarboxylic acid, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, Use of benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, stearyl alcohol, 2-phenoxyethanol, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxyethoxybenzoic acid, etc. it can. These compounds are preferably 4 mol% or less, particularly preferably 2 mol% or less, based on all monomer components constituting the polyester resin.

  The polyester resin (B) can be produced by polycondensing the above-described components by a known method. For example, all monomer components and / or low polymers thereof are reacted at 180 to 260 ° C. for about 2.5 to 10 hours in an inert atmosphere to carry out an esterification reaction, and subsequently 130 Pa or less in the presence of a polycondensation catalyst. And a method of obtaining a polyester resin by advancing a polycondensation reaction at a temperature of 220 to 280 ° C. until the desired molecular weight is reached.

  In order to control the acid value and hydroxyl value of the polyester resin (B), a method in which a polybasic acid component or a polyhydric alcohol component is further added to the polycondensation reaction, followed by depolymerization in an inert atmosphere, etc. Can be adopted. In particular, when a polybasic acid having 3 or more functional groups such as trimellitic acid or trimellitic anhydride is used during depolymerization, an aqueous dispersion with more excellent heat sealability while suppressing a decrease in the molecular weight of the polyester resin due to depolymerization. Since a body can be obtained, it is preferable.

  The acid value of the polyester resin (B) is required to be 2 to 40 mgKOH / g, preferably 2 to 30 mgKOH / g, and more preferably 2 to 20 mgKOH / g. When the acid value exceeds 40 mgKOH / g, the water resistance may be insufficient. Moreover, when the acid value is less than 2 mgKOH / g, it tends to be difficult to obtain an aqueous dispersion having good blocking resistance and heat sealability.

  Further, the polyester resin (B) may contain a hydroxyl group as long as the water resistance of the resin film is not impaired, and the hydroxyl value is preferably 30 mgKOH / g or less, and preferably 20 mgKOH / g or less. More preferably, it is 10 mgKOH / g or less.

  The number average molecular weight of the polyester resin (B) is preferably 4,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more. If the number average molecular weight is less than 4,000, the heat sealability of the resin film tends to be insufficient. The upper limit of the number average molecular weight is not particularly limited, but the number average molecular weight of the polyester resin is preferably 50,000 or less from the viewpoint that an adhesive having good blocking resistance can be easily obtained.

  Although the glass transition temperature of a polyester resin (B) is not specifically limited, -40-60 degreeC is preferable from the viewpoint with a favorable heat seal property of an adhesive agent, and 0-40 degreeC is more preferable from the point of an improvement in blocking resistance.

  The mass ratio (A) / (B) of the polyolefin resin (A) to the polyester resin (B) needs to be 100/2 to 100/50. From the viewpoint of blocking resistance, adhesiveness, and heat sealability. 100/2 to 100/40 is preferable, 100/5 to 100/30 is more preferable, 100/5 to 100/25 is more preferable, and 100/5 to 100/20 is particularly preferable. (A) When the content of (B) with respect to 100 parts by mass is less than 2 parts by mass, the adhesiveness with the vinyl chloride substrate decreases, and when it exceeds 50 parts by mass, the vinyl chloride substrate and the ionomer There exists a tendency for the adhesiveness at the time of bonding of a resin film to fall.

  As an aqueous medium in the present invention, from the viewpoint of safety to workers and working environment, it is most preferable that all of it is originally water, but the polyolefin resin (A) and the polyester resin (B) are made water-based, For the purpose of reducing the drying load, a hydrophilic organic solvent may be contained in addition to water as long as it does not depart from the characteristics of “aqueous”. Examples of such an organic solvent include ketones such as methyl ethyl ketone, acetone and diethyl ketone, alcohols such as phenol, butanol, methanol and ethanol, cyclic ethers such as tetrahydrofuran and dioxane, and ethylene glycol monobutyl ether. And glycol derivatives. The amount of these organic solvents in the total amount of the aqueous dispersion is preferably 40% by mass or less, more preferably 20% by mass or less, and further preferably 5% by mass or less. Further, the aqueous medium may contain a basic compound that is added when the polyolefin resin (A) is made aqueous as described later.

  The method for producing the aqueous adhesive of the present invention will be described.

  The method for producing the aqueous adhesive of the present invention is particularly limited as long as the polyolefin resin (A) and the polyester resin (B) are uniformly mixed in an aqueous medium and can be dispersed or dissolved. Although not, there are the following two examples: (a) A method of mixing an aqueous dispersion of a polyolefin resin (A) and an aqueous dispersion of a polyester resin (B), each prepared in advance; ) A method in which the polyolefin resin (A) and the polyester resin (B) are simultaneously dispersed in water. Among these, the method (a) is preferable because an aqueous dispersion comprising a combination of various polyester resins and polyolefin resins can be prepared more easily.

  First, the manufacturing method of the aqueous dispersion of polyolefin resin (A) is demonstrated.

  Although the method for obtaining the aqueous dispersion of polyolefin resin (A) is not specifically limited, For example, the method of heating and stirring a polyolefin resin and an aqueous medium in the container which can be sealed can be employ | adopted. At this time, the shape of the resin used for the aqueous treatment is not particularly limited, but it is preferable to use a granular or powdery material having a particle diameter of 1 cm or less, preferably 0.8 cm or less, from the viewpoint of increasing the aqueousization rate.

  Any container may be used as long as it is equipped with a tank into which liquid can be charged and can appropriately stir the mixture of the aqueous medium and resin charged into the tank. As such an apparatus, a known solid / liquid stirring apparatus or emulsifier can be used, and an apparatus capable of pressurization of 0.1 MPa or more is preferable. The stirring method and the rotation speed of stirring are not particularly limited.

  After each raw material is put into the tank of this apparatus, it is preferably stirred and mixed at a temperature of 40 ° C. or lower. Next, while maintaining the temperature in the tank at 50 to 200 ° C., preferably 60 to 200 ° C., the resin is sufficiently made aqueous by continuing stirring for 5 to 120 minutes, and then the temperature is lowered to 40 ° C. or less under stirring. An aqueous dispersion can be obtained by cooling. When the temperature in the tank is less than 50 ° C., it becomes difficult to make the resin water-based. When the temperature in a tank exceeds 200 degreeC, there exists a possibility that the molecular weight of resin may fall.

  When the polyolefin resin (A) has an unsaturated carboxylic acid component, it is preferable to add a basic compound at the time of aqueous formation. The unsaturated carboxylic acid component is anionized by the basic compound, and aggregation between the fine particles is prevented by electrical repulsion and stability is imparted to the aqueous dispersion. The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent to the carboxyl group in the polyolefin resin (1 mol of acid anhydride group is regarded as 2 mol of carboxyl group), 0.8 -2.5 times equivalent is more preferable and 1.0-2.0 times equivalent is especially preferable. If it is less than 0.5 times equivalent, the addition effect of a basic compound is not recognized, and if it exceeds 3.0 times equivalent, the drying time at the time of coating film formation may become long or the aqueous dispersion may be colored.

  As a basic compound added here, the compound which volatilizes at the time of coating-film formation is preferable from the surface of the water resistance of a coating film, and ammonia or various organic amine compounds are preferable. The boiling point of the organic amine compound is preferably 250 ° C. or lower. If it exceeds 250 ° C., it becomes difficult to scatter the organic amine compound from the resin coating film by drying, and the water resistance of the coating film may deteriorate. Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N- Examples thereof include ethyl morpholine.

  In addition, when making the polyolefin resin (A) aqueous, it is preferable to add an organic solvent from the viewpoints of improving the aqueous conversion rate and reducing the particle size of the resin particles. The addition amount of the organic solvent is preferably 1 to 40% by mass in the aqueous dispersion of polyolefin resin, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass. The organic solvent can be removed (stripped) partly from the system by heating the aqueous dispersion with stirring under normal pressure or reduced pressure. It can also be 1 mass% or less in a dispersion. Specific examples of the organic solvent used include ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. From the viewpoint of drying at a lower temperature, ethanol, isopropanol, and n-propanol are particularly preferable.

  The number average particle diameter of the polyolefin resin (A) particles in the aqueous dispersion is the stability of the aqueous dispersion, the surface smoothness when applied, the transparency of the coating film obtained by mixing with the polyester resin (B), From the viewpoint of performance (adhesiveness, heat sealability), it is preferably 0.5 μm or less, more preferably 0.3 μm or less, further preferably 0.2 μm or less, and particularly preferably 0.15 μm or less. The weight average particle diameter is also preferably 0.5 μm or less, and more preferably 0.3 μm or less.

  As a method for producing an aqueous dispersion of the polyester resin (B), 1) a method in which the polyester resin is dissolved in an organic solvent, and water is added to the polyester resin solution to obtain an aqueous dispersion. Similarly to the method for producing an aqueous dispersion, there may be mentioned a method in which a polyester resin, a basic compound, an organic solvent and water are charged all at once in a container and heated while stirring the system. For example, when the acid value of the polyester resin is 10 mgKOH / g or less, the method 1) is preferable, and when the acid value exceeds 10 mgKOH / g, the method 2) is preferable.

  Commercially available products can be used as the aqueous dispersion of the polyolefin resin (A), and examples thereof include “Arrow Base” series manufactured by Unitika Ltd.

  The polyester resin (B) can be prepared by the same method as the method for preparing the aqueous dispersion of the polyolefin resin (A) described above. Moreover, a commercially available polyester resin aqueous dispersion can also be used, and examples thereof include “Elitel” KT series and KZ series manufactured by Unitika Ltd.

  As a manufacturing method (A) of the aqueous adhesive, each aqueous dispersion of the polyolefin resin (A) and the polyester resin (B) obtained by the above-described method may be mixed. In mixing, a known liquid / liquid mixing apparatus may be used as appropriate. Since the dispersion and mixing properties of the aqueous polyolefin resin dispersion and the polyester resin are good, a simple mixing operation can be performed in a very short time. Moreover, after mixing, solid content concentration can also be adjusted by the method of distilling an aqueous medium or diluting with water so that it may become desired solid content concentration.

  As the production method (A) of the water-based adhesive, for example, the above-mentioned method of heating and stirring a polyolefin resin and a polyester resin, a basic compound, and an aqueous medium in a container can be employed, and the above raw materials are charged into the apparatus. Then, the polyolefin resin and the polyester resin are sufficiently dispersed by heating (for example, 45 to 200 ° C.) and continuing to stir until coarse particles disappear (for example, 5 to 120 minutes). An aqueous coating agent can be obtained by cooling to below ℃. Moreover, solid content concentration can be adjusted with methods, such as distilling an aqueous medium or diluting with water similarly to a manufacturing method (a).

  The aqueous adhesive of the present invention may use a non-volatile aqueous auxiliary agent such as an emulsifier, but from the viewpoint of water resistance and heat sealability, 5% by mass or less of the final aqueous adhesive. And most preferably not used. In addition, if the said manufacturing method is used, a fine and stable aqueous dispersion can be obtained without adding a non-volatile aqueous | water-based auxiliary agent, and using this, the aqueous adhesive of this invention is prepared. Can do. Examples of the non-volatile aqueous auxiliary agent include emulsifiers described later, compounds having a protective colloid action, modified waxes, high acid value acid-modified compounds, water-soluble polymers, and the like.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like. Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid values, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, etc., and acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid- Maleic anhydride copolymer and its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating Polymers, carboxyl group-containing polymers having an unsaturated carboxylic acid content of 10% by mass or more, such as (meth) acrylic acid- (meth) acrylic acid ester copolymers, and salts thereof, polyitaconic acid and salts thereof, and amino groups Examples thereof include water-soluble acrylic copolymers, gelatin, gum arabic, and casein, which are generally used as fine particle dispersion stabilizers.

  The aqueous adhesive of the present invention can form a good adhesive layer on a vinyl chloride resin substrate by removing the liquid medium after being applied to the vinyl chloride resin substrate. At this time, since the surface of the formed adhesive layer is excellent in blocking resistance, handling is easy. Moreover, since the formed contact bonding layer is excellent in heat-sealability, a laminated body can be obtained by heat-pressing another base material on the contact bonding layer. Examples of the base material to be laminated include vinyl chloride resin, other resins, paper, synthetic paper, wood, woven fabric, knitted fabric, non-woven fabric, and metal. Particularly, it is suitable for lamination of vinyl chloride resins, lamination of vinyl chloride resin and polyolefin resin, lamination of vinyl chloride resin and metal, and the like. As the polyolefin resin, an ionomer resin obtained by allowing a metal cation such as sodium or zinc to act on a copolymer of ethylene and acrylic acid or methacrylic acid is particularly preferable. Moreover, as a metal, aluminum is preferable.

  The vinyl chloride resin to which the water-based adhesive of the present invention can be applied is prepared by, for example, emulsion polymerization or the like with a vinyl chloride monomer as a main component. In addition, the vinyl chloride resin may contain a plasticizer such as dinormal octyl phthalate and diisononyl phthalate.

  The shape of the vinyl chloride resin substrate is not particularly limited, such as a film or a sheet. The film may be an unstretched film or a stretched film, and its production method is not limited. Moreover, although the thickness of a base film is not specifically limited, Usually, what is necessary is just to be the range of 1-500 micrometers. Furthermore, you may perform what is called in-line coating which apply | coats the water-based adhesive of this invention to an unstretched film, and extends | stretches the coat film.

  The method of applying the aqueous adhesive of the present invention to a substrate is not particularly limited, but gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dipping Coating, brushing, etc. can be employed. What is necessary is just to determine suitably the application quantity of a water-based adhesive with a base material. In the case where the substrate is a thermoplastic resin film, the thickness of the coating film is preferably at least 0.1 μm, more preferably 0.1 to 10 μm, in order to sufficiently enhance the heat sealability. 2-8 micrometers is further more preferable and 0.3-7 micrometers is especially preferable.

  The drying temperature of the aqueous adhesive of the present invention is not particularly limited, and may be appropriately determined depending on the heat-resistant temperature of the base material, etc., but is usually 50 to 150 ° C., more preferably 60 to 100 ° C., 70-90 degreeC is further more preferable. When the drying temperature is less than 50 ° C., the aqueous medium cannot be volatilized sufficiently, or it takes time to volatilize, and it becomes difficult to develop good adhesive performance. On the other hand, when the drying temperature exceeds 150 ° C., the adhesion performance tends to be lowered.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

  Various characteristics were measured or evaluated by the following methods.

1. Resin properties

(1) Resin composition
^It calculated | required from < ¹ > H-NMR analysis (The product made by Varian, 300MHz). The polyolefin resin was measured at 120 ° C. using orthodichlorobenzene (d ₄ ) as a solvent. The polyester resin was measured at room temperature using chloroform (d) or trifluoroacetic acid (d) as a solvent. For polyester resins containing constituent monomers for which no peaks that can be assigned or quantified are observed on the ¹ H-NMR spectrum, methanol decomposition was performed at 230 ° C. for 3 hours in a sealed tube, and then subjected to gas chromatogram analysis for quantitative analysis. went.

(2) Melting point of resin, glass transition temperature ( _Tg )
Using 10 mg of the resin as a sample, a DSC (Differential Scanning Calorimetry) apparatus (DSC7 manufactured by Perkin Elmer Co., Ltd.) was used for measurement at a temperature rising rate of 10 ° C./min, and the melting point was determined from the obtained temperature rising curve. Moreover, the intermediate value of the temperature of two bending points derived from the glass transition in the obtained temperature rising curve was _{calculated |} required, and this was made into Tg.

(3) Melt flow rate of polyolefin resin It measured by the method of JIS6730 description (190 degreeC, 2160g load).

(4) Acid value of polyester resin 0.5 g of polyester resin was dissolved in 50 ml of water / dioxane = 10/1 (volume ratio), titrated with KOH using cresol red as an indicator, and the amount of KOH consumed for neutralization. The acid value (mgKOH / g) in the polyester resin was determined from the mg number.

(5) Weight average molecular weight of polyester resin The weight average molecular weight was measured by GPC analysis (liquid feeding unit LC-10ADvp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation), detection wavelength: 254 nm, solvent: tetrahydrofuran , Polystyrene conversion).

2. Characteristics of aqueous dispersions

(1) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to obtain the solid content concentration.

(2) Average particle diameter of aqueous dispersion The number average particle diameter and the weight average particle diameter were calculated | required using the Nikkiso Co., Ltd. make and Microtrac particle size distribution analyzer UPA150 (MODEL No.9340, dynamic light scattering method). Here, the refractive index of the resin used for calculating the particle diameter was set to 1.50.

(3) Organic solvent content of aqueous dispersion Shimadzu Corporation gas chromatograph GC-8A [using FID detector, carrier gas: nitrogen, column packing material (manufactured by GL Sciences): PEG-HT (5%) − Uniport HP (60/80 mesh), column size: diameter 3 mm × 3 m, sample charging temperature (injection temperature): 150 ° C., column temperature: 60 ° C., internal standard substance: n-butanol], aqueous dispersion or aqueous A dispersion diluted with water was directly charged into the apparatus, and the content of the organic solvent was determined. The detection limit was 0.01% by mass.

3. Characteristics of the coating In the following evaluation, as a substrate, a biaxially stretched polyethylene terephthalate (PET) film (Embret PET12 manufactured by Unitika, thickness 12 μm), a vinyl chloride resin film (Dragon's Belfan FE-33PHP manufactured by tatsuta, thickness 200 μm) ), An ionomer film (HM-52 manufactured by Tamapoly, thickness 0.1 μm), and a stretched polypropylene (PP) film (manufactured by Tosero Co., Ltd., thickness 20 μm) were used.

(1) Water resistance The water-based adhesive was applied to the corona-treated surface of the vinyl chloride resin film using a Mayer bar so that the film thickness after drying was 2 μm, and then dried at 100 ° C. for 2 minutes. The obtained laminated film was evaluated after standing at room temperature for 1 day. The coating film was rubbed several times with a cloth wetted with water, and the state of the coating film was visually evaluated according to the following criteria.

○: No change △: The coating film is cloudy ×: The coating film is completely dissolved

(2) Adhesiveness (tape peeling test)
After applying a water-based adhesive to the corona-treated surface of biaxially stretched PET film, stretched PP film, and vinyl chloride resin film using a Meyer bar so that the film thickness after drying becomes 1 μm, it is dried at 100 ° C. for 2 minutes. I let you. The obtained laminated film was evaluated after standing at room temperature for 1 day. A cellophane tape (TF-12 manufactured by Nichiban Co., Ltd.) was attached to the adhesive surface, and the degree of peeling when the tape was peeled at once was visually evaluated according to the following criteria.

○: No peeling at all △: Some peeling off ×: All peeling off

(3) Heat seal strength The aqueous adhesive was applied to the corona-treated surface of the vinyl chloride resin film so that the film thickness after drying was 2 μm, and dried at 100 ° C. for 2 minutes. The coating layer of the obtained laminated film and the ionomer film were bonded together and pressed at 120 ° C. with a heat press (sealing pressure of 0.3 MPa for 2 seconds). This sample was cut out at a width of 15 mm, and one day later, the peel strength of the coating film was measured at a tensile speed of 200 mm / min and a tensile angle of 180 degrees using a tensile tester (Intesco Precision Universal Material Tester Model 2020 manufactured by Intesco Corporation). Similarly, the corona-treated surface of the vinyl chloride resin film and the stretched PP film, and the heat seal strength of the vinyl chloride resin film and the aluminum foil (thickness: 12 μm) were also measured.

(4) Blocking resistance of resin coating After applying a water-based adhesive on a corona-treated surface of a vinyl chloride resin film using a Meyer bar so that the film thickness after drying becomes 2 μm, at 100 ° C. for 2 minutes, Dried. The obtained laminated film was allowed to stand at room temperature for 1 day, and then a non-corona-treated surface of a biaxially stretched PET film was superimposed on the adhesive surface, a load of 0.02 MPa was applied, and an atmosphere of 25 ° C. and 65% RH After standing for 24 hours, the blocking resistance was evaluated in the following three stages.

○: Peel off by lifting the film lightly.
(Triangle | delta): It peels by pulling a film.
X: Even if a film is pulled, it does not peel.

  Tables 1, 2 and 3 show the compositions of the polyolefin resin and the polyester resin used in the following examples and comparative examples.

(Production of aqueous polyolefin resin dispersion E-1)
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g polyolefin resin [Bondaine HX-8290 (A), manufactured by Arkema Co., Ltd.], 60.0 g isopropanol (hereinafter, iPA) , 4.5 g (1.8 times equivalent to the carboxyl group of maleic anhydride in the resin) of triethylamine (hereinafter referred to as TEA) and 175.5 g of distilled water were charged in a glass container, and the rotational speed of the stirring blade was adjusted. When stirring was performed at 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion E-1 was obtained.

(Production of aqueous polyolefin resin dispersion E-2)
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 60.0 g of propylene-butene-ethylene terpolymer (manufactured by Huls Japan, Bestplast 708 (I), propylene / butene / Ethylene / maleic anhydride = 60.7 / 22.4 / 10.6 / 6.3% by mass), 45.0 g of ethylene glycol-n-butyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 6.9 g of N, When N-dimethylethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 188.1 g of distilled water were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no resin precipitation was observed at the bottom of the container. It was confirmed that it was floating. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky-yellow uniform polyolefin resin aqueous dispersion E-2 was obtained.

  Table 4 shows the liquid characteristics of the aqueous polyolefin resin dispersion.

(Production of polyester resin P-1)
A mixture of 2492 g of terephthalic acid, 415 g of isophthalic acid, 1516 g of sebacic acid, 1210 g of ethylene glycol, and 1484 g of neopentyl glycol was heated in an autoclave at 250 ° C. for 4 hours to carry out an esterification reaction. Subsequently, after adding 3.3 g of zinc acetate dihydrate as a catalyst, the temperature of the system was raised to 270 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction is continued for another 4 hours, the system is brought to atmospheric pressure with nitrogen gas, the temperature of the system is lowered, and when the temperature reaches 265 ° C., 29 g of trimellitic anhydride is added and stirred at 265 ° C. for 2 hours. The depolymerization reaction was performed. Thereafter, the system was put under pressure with nitrogen gas, and the resin was dispensed in a sheet form. After cooling at room temperature, a sheet-like polyester resin P-1 was obtained.

(Production of polyester resin P-2)
A mixture of 2492 g of terephthalic acid, 415 g of isophthalic acid, 1516 g of sebacic acid, 1210 g of ethylene glycol, and 1484 g of neopentyl glycol was heated in an autoclave at 250 ° C. for 4 hours to carry out an esterification reaction. Subsequently, after adding 3.3 g of zinc acetate dihydrate as a catalyst, the temperature of the system was raised to 270 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction is continued for another 4 hours, the system is brought to atmospheric pressure with nitrogen gas, the temperature of the system is lowered, and when it reaches 265 ° C., 58 g of trimellitic anhydride is added and stirred at 265 ° C. for 2 hours. The depolymerization reaction was performed. Thereafter, the system was put into a pressurized state with nitrogen gas, and the resin was dispensed into a sheet shape. After cooling at room temperature, a sheet-shaped polyester resin P-2 was obtained.

(Polyester resin P-3)
A mixture of 1578 g of terephthalic acid, 83 g of isophthalic acid, 374 g of ethylene glycol and 730 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 2.5 hours to carry out an esterification reaction. Next, 0.262 g of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under this condition, the polycondensation reaction was further continued. After 1.5 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 260 ° C., 50 g of isophthalic acid and 57 g of trimellitic anhydride were added, The mixture was stirred at 255 ° C. for 30 minutes and discharged into a sheet. And after fully cooling to room temperature, this was grind | pulverized with the crusher and the polyester resin P-3 was obtained for the fraction with an opening of 1-6 mm using the sieve.

(Production of polyester resin aqueous dispersion T-1)

(1):
By adding 400 g of polyester resin P-1 and 600 g of MEK to a 3 L polyethylene container and stirring the container with hot water of about 60 ° C. using a stirrer (manufactured by Tokyo Rika Co., Ltd., MAZELA1000), The polyester resin was completely dissolved in MEK to obtain a polyester resin solution having a solid concentration of 40% by mass.

  Next, 500 g of the above-mentioned polyester resin solution was charged into a jacketed glass container (internal volume 2 L), the temperature inside the system was kept at 13 ° C. by passing cold water through the jacket, and the mixture was stirred with a stirrer (Mazela 1000, manufactured by Tokyo Rika Co., Ltd.) ). Next, 23.3 g of triethylamine was added as a basic compound while stirring, and 476.7 g of distilled water at 13 ° C. was subsequently added at a rate of 100 g / min. During addition of the whole amount of distilled water, the system temperature was always 15 ° C. or lower. After completion of the addition of distilled water, stirring was performed for 30 minutes to obtain an aqueous polyester resin dispersion having a solid content concentration of 20% by mass and an organic solvent content of 3% by mass or more.

(2):
800 g of the polyester resin aqueous dispersion obtained in (1) and 52.3 g of distilled water were placed in a 2 L flask, and the organic solvent was removed by distillation at normal pressure. Distillation was terminated when the amount of distillation reached about 360 g, and after cooling to room temperature, it was filtered through a 250 mesh (opening 0.071 mm) stainless steel filter. Subsequently, after measuring the solid content concentration of this aqueous dispersion, distilled water was added so that the solid content concentration was 30% by mass. The solid content concentration of the polyester resin aqueous dispersion thus obtained was 30.3% by mass. The content of the organic solvent was 0.01% by mass or less.

(3):
While stirring 500 g of the polyester resin aqueous dispersion obtained in (2), 2.6 g of triethylamine was added to obtain an aqueous polyester resin dispersion T-1.

  The solid content concentration of this aqueous dispersion was 30.1% by mass.

(Production of aqueous polyester resin dispersion T-2)

(1):
By adding 400 g of polyester resin P-2 and 600 g of MEK to a 3 L polyethylene container and stirring the container with hot water of about 60 ° C. using a stirrer (manufactured by Tokyo Rika Co., Ltd., MAZELA1000), The polyester resin was completely dissolved in MEK to obtain a polyester resin solution having a solid concentration of 40% by mass.

  Next, 500 g of the above-mentioned polyester resin solution was charged into a jacketed glass container (internal volume 2 L), the temperature inside the system was kept at 13 ° C. by passing cold water through the jacket, and the mixture was stirred with a stirrer (Mazela 1000, manufactured by Tokyo Rika Co., Ltd.) ). Next, 2.5 g of 28% by mass of ammonia water was added as a basic compound while stirring, and then 497.5 g of 13 ° C. distilled water was added at a rate of 100 g / min. During addition of the whole amount of distilled water, the system temperature was always 15 ° C. or lower. After completion of the addition of distilled water, stirring was performed for 30 minutes to obtain an aqueous polyester resin dispersion having a solid content concentration of 20% by mass and an organic solvent content of 3% by mass or more.

(2):
800 g of the polyester resin aqueous dispersion obtained in (1) and 52.3 g of distilled water were placed in a 2 L flask, and the organic solvent was removed by distillation at normal pressure. Distillation was terminated when the amount of distillation reached about 360 g, and after cooling to room temperature, it was filtered through a 250 mesh (opening 0.071 mm) stainless steel filter. Subsequently, after measuring the solid content concentration of this aqueous dispersion, distilled water was added so that the solid content concentration was 30% by mass. The solid content concentration of the polyester resin aqueous dispersion thus obtained was 30.2% by mass. The content of the organic solvent was 0.01% by mass or less.

(3):
While stirring 500 g of the polyester resin aqueous dispersion obtained in (2), 2.6 g of triethylamine was added to obtain an aqueous polyester resin dispersion T-2.

  The solid content concentration of this aqueous dispersion was 30.0% by mass.

(Production of aqueous polyester resin dispersion T-3)
Using a tabletop homodisper (made by TK Robotics Co., Ltd., TK Robotics) that is equipped with a 2L glass container with a jacket and that is sealed when installed, 300 g of polyester resin P-3 is placed in the glass container. , 80 g of ethylene glycol-n-butyl ether and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 times the total amount of carboxyl groups contained in the polyester resin were added and stirred at 6,000 rpm. However, no sedimentation of resin granules was observed at the bottom of the container, and it was confirmed that the container was in a completely floating state. Therefore, 10 minutes after maintaining this state, hot water was passed through the jacket and heated. When the temperature in the container reached 68 ° C., stirring was set at 7,000 rpm, the temperature in the container was maintained at 70 to 72 ° C., and the mixture was further stirred for 20 minutes to obtain a milky white uniform aqueous dispersion. Then, cold water was poured into the jacket and cooled to room temperature while stirring at 3500 rpm, followed by filtration using a stainless steel filter (635 mesh, plain weave) to obtain an aqueous polyester resin dispersion T-3. This aqueous dispersion solid content concentration was 30.0 mass%.

  Table 5 shows the liquid properties of the aqueous polyester resin dispersion.

Example 1
The aqueous polyolefin resin dispersion E-1 and the aqueous polyester resin dispersion T-1 were stirred (100 rpm) and mixed at room temperature with a mechanical stirrer so that the polyester resin was 5 parts by mass with respect to 100 parts by mass of the polyolefin resin. Aqueous adhesive J-1 was prepared.

Examples 2-9
As shown in Table 6, the same operations as in Example 1 were performed except that the types of the polyolefin resin aqueous dispersion and the polyester resin aqueous dispersion and the mixing ratio of the resin components were changed. -9 was obtained.

  Table 6 shows the evaluation results of Examples 1 to 9.

Comparative Examples 1 and 7
The polyolefin resin aqueous dispersion E-1 or E-2 was used alone without adding the polyester resin aqueous dispersion, and these were designated as H-1 and H-7, respectively.

Comparative Examples 2-6 and 8-9
As shown in Table 7, the same operations as in Example 1 were performed except that the types of the aqueous polyolefin resin dispersion and the aqueous polyester resin dispersion and the mixing ratio of the resin components were changed. 2 to H-6, H-8, and H-9 were obtained.

Comparative Example 10
Dicarboxylic acid diester (DBE manufactured by DuPont) with respect to 100 parts by mass of an ethylene-vinyl acetate copolymer emulsion (SF-467 manufactured by Sumitomo Chemical Co., Ltd., ethylene content 20% by weight, emulsifying dispersant polyvinyl alcohol). 7 parts by mass of a mixture of dimethyl succinate, dimethyl glutarate and dimethyl adipate) was added and mixed to prepare an emulsion adhesive H-10 having a viscosity of 18,000 mPa · s and a solid content of 60% by mass.

  Table 7 shows the evaluation results of Comparative Examples 1 to 10.

  In Examples 1 to 9, the coating obtained from the aqueous dispersion has good adhesion to a vinyl chloride substrate, water resistance and blocking resistance, and excellent adhesion to a different substrate and heat sealability. It was.

On the other hand, since Comparative Examples 1 and 7 did not contain a polyester resin, there were problems in adhesion with a vinyl chloride substrate, adhesion with a different substrate, and blocking resistance. Moreover, since the content of the polyester resin was outside the scope of the present invention, Comparative Examples 2, 4, and 8 were inferior in adhesion to the vinyl chloride base material and blocking resistance. Comparative Examples 3, 5, and 9 had good blocking resistance, but the polyester resin content was outside the scope of the present invention, so the heat seal strength was inferior. In particular, polyolefins as in Comparative Examples 1 and 7 The heat seal strength was lower than that of the adhesive consisting only of the resin component. In Comparative Example 6, since the acid value of the polyester resin used was outside the range of the present invention, the heat seal strength was inferior. The ethylene-vinyl acetate copolymer emulsion of Comparative Example 10 is a well-known liquid as an adhesive having good adhesion to a vinyl chloride substrate, but has poor heat seal strength.

Claims (8)

It contains a polyolefin resin (A), a polyester resin (B) having an acid value of 2 to 40 mgKOH / g, and an aqueous medium, and the mass ratio of (A) and (B) is in the range of 100/2 to 100/50. A water based adhesive for vinyl chloride base material. The water-based adhesive according to claim 1, wherein the content of the non-volatile water-based auxiliary is 5 mass% or less. A laminate obtained by laminating a vinyl chloride resin (a), an adhesive layer (b) obtained by removing an aqueous medium from the aqueous adhesive according to claim 1, and another substrate (c) in this order. The laminate according to claim 3, wherein the other substrate (c) is a vinyl chloride resin. The laminate according to claim 3, wherein the other substrate (c) is a resin other than vinyl chloride resin. The laminate according to claim 5, wherein the resin other than the vinyl chloride resin is a polyolefin resin. The laminate according to claim 3, wherein the other substrate (c) is a metal. The laminate according to claim 7, wherein the metal is aluminum.