JP2003213234A - Aqueous adhesive for synthetic paper and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous adhesive excellent in adhesiveness between synthetic paper and various thermoplastic resin films and capable of forming an adhesive layer having transparency as well as water-resisting properties at a low temperature. <P>SOLUTION: The aqueous adhesive for synthetic paper comprises an aqueous dispersion in which a polyolefin resin comprising an unsaturated carboxylic acid or its anhydride (A1), an ethylenic hydrocarbon (A2) and a specific compound (A3) and having ≥0.01 mass% to <5 mass% ingredient (A1) and a mass ratio of (A2)/(A3)=55/45-99/1 is dispersed in ≤1 μm number average particle size. The laminate is provided by using the aqueous adhesive and laminating the synthetic paper with the thermoplastic films. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-based adhesive having excellent adhesiveness to synthetic paper.

[0002]

2. Description of the Related Art In the adhesive industry that uses a large amount of organic solvents, the use of organic solvents has tended to be restricted in recent years from the standpoints of environmental protection, resource conservation, regulation of dangerous substances by the Fire Service Act, and improvement of the work environment. , Water-based adhesives of various resins are being developed.

Acrylic emulsions and ethylene-vinyl acetate copolymer emulsions are often used as adhesives for polyolefin synthetic papers.

Generally, it is known that an acrylic emulsion or an ethylene-vinyl acetate copolymer emulsion having a low ethylene content can be obtained by emulsion polymerization or suspension polymerization in the presence of an emulsifier or a compound having a protective colloid action. Has been. However, as the ethylene content in the ethylene-vinyl acetate copolymer becomes higher, the reaction pressure at the time of polymerization becomes higher. Therefore, in consideration of equipment and safety, it is possible to obtain a stable emulsion (aqueous dispersion). It will be difficult. The ethylene-vinyl acetate copolymer having a high ethylene content is generally obtained by high-pressure radical polymerization in a high-pressure ethylene plant or the like, and usually cannot be obtained in the state of an aqueous dispersion.

As a method for obtaining an aqueous dispersion of an ethylene-vinyl acetate copolymer having a high ethylene content, there is disclosed in Japanese Patent Laid-Open No. Hei 9-1999
As described in JP-A-296081, a method of emulsifying a resin at high temperature by adding an emulsifier to the system is described.

However, the aqueous dispersion prepared by the above method contains a non-volatile aqueous auxiliary agent such as a highly hydrophilic emulsifier and a compound having a protective colloid action in the system, and these are coated even after drying. Since it remains inside, there is a problem that the water resistance of the formed film is significantly reduced. Further, when the coating contains a non-volatile aqueous auxiliary agent such as a highly hydrophilic emulsifier or a compound having a protective colloid action, the adhesiveness to the hydrophobic substrate is deteriorated. Further, a coating film containing an emulsifier or a compound having a protective colloid action is not preferable in terms of environment and hygiene because they may bleed out.

To solve the above problems, it is known to increase the copolymerization rate of the unsaturated carboxylic acid component to obtain a polyolefin resin aqueous dispersion without adding an emulsifier or a compound having a protective colloid action. . For example, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer resin such as an ethylene-acrylic acid copolymer resin or an ethylene-methacrylic acid copolymer resin having an unsaturated carboxylic acid content of about 20% by mass is conventionally known. In particular, when an alkali metal compound or ammonia is used, an aqueous dispersion of the resin is easy to produce and is widely used. However, when a resin having a high content of unsaturated carboxylic acid is used, there is a problem that the adhesiveness to a resin having low polarity such as polypropylene is significantly reduced.

[0008]

With respect to the above problems, the present inventors can form a resin layer having excellent adhesiveness with synthetic paper and excellent transparency and water resistance at low temperature. The aim is to provide a possible water-based adhesive.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that an aqueous dispersion made of a polyolefin resin having a specific composition has excellent adhesiveness to synthetic paper. Has reached the present invention. That is,
The gist of the present invention is, firstly, a water-based adhesive for synthetic paper containing the following polyolefin resin having a number average particle size of 1 μm or less. Polyolefin resin: (A1) unsaturated carboxylic acid or anhydride thereof, (A2) ethylene hydrocarbon, (A3) at least one compound represented by any of the following formulas (I) to (IV) A polyolefin resin which is a copolymer having the following formulas (1) and (2) in which the mass ratio of each of the constituent components (A1) to (A3) is satisfied. 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 <5 (1) (A2) / (A3) = 55/45 to 99/1 (2)

[Chemical 2] Secondly, it is characterized in that it is composed of at least three layers, and that the three layers are a synthetic paper, an adhesive layer formed by applying the above-mentioned aqueous adhesive and drying, and a thermoplastic resin molding or synthetic paper. It is a laminated body.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The water-based adhesive for synthetic paper in the present invention is one in which a specific polyolefin resin having a number average particle diameter of 1 μm or less is dispersed in an aqueous medium. It is possible to obtain a polyolefin resin aqueous dispersion having a number average particle diameter of 1 μm or less without using a non-volatile aqueous solubilizing agent such as a compound having an emulsifying agent or a protective colloid action by using a specific polyolefin resin. It is possible to provide an adhesive having excellent adhesiveness with synthetic paper.

The polyolefin resin used in the present invention contains an unsaturated carboxylic acid or its anhydride (A1) component in an amount of 0.01% by mass based on the whole resin [(A1) + (A2) + (A3)].
Or more, less than 5 mass%, more preferably 0.1 mass% or more, 5
Less than mass%, more preferably 0.5 mass% or more, 5 mass%
It is necessary to contain less than 1% by mass, most preferably 1% by mass or more and 4% by mass or less. When the content of the component (A1) is less than 0.01% by mass, it becomes difficult to liquefy (liquefy) the resin, and it is difficult to obtain a good water-based adhesive. On the other hand, when the content of the unsaturated carboxylic acid or its anhydride exceeds 5% by mass, it becomes easy to make it aqueous, but the adhesiveness with the hydrophobic substrate is lowered, or the mixture with the cross-linking agent is mixed. Stability may be reduced.

The unsaturated carboxylic acid or its anhydride that can be used as the component (A1) of the polyolefin resin is a compound having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit), Specific examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid and crotonic acid, as well as half esters and half amides of unsaturated dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
The unsaturated carboxylic acid may be copolymerized in the polyolefin resin, and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.

The polyolefin resin used in the present invention requires the component (A3) represented by any of the following formulas (I) to (IV) as a constituent component, and this component imparts hydrophilicity to the polyolefin resin. Therefore, the (A1) component is
Even if it is less than 5% by mass, it can be hydrated without adding a non-volatile hydration aid such as an emulsifier or a protective colloid. The mass ratio (A2) / (A3) of the ethylene hydrocarbon (A2) component and the (A3) component needs to be in the range of 55/45 to 99/1, and 60/40 to 98/2. Is preferred, 65/35 to 97/3 is more preferred, 70/30
˜97 / 3 is more preferred, and 75/25 to 97/3 is particularly preferred. When the ratio of the component (A3) to [(A2) + (A3)] is less than 1% by mass, it becomes difficult to make the polyolefin resin water-based and it is difficult to obtain a good water-based adhesive. On the other hand, the content ratio of the compound (A3) is 45% by mass.
If it exceeds, the properties of the component (A2) as a polyolefin resin may be lost, and performance such as water resistance and adhesiveness to various substrates may deteriorate.

[0014]

[Chemical 3]

The ethylene hydrocarbon (A2) component constituting the polyolefin resin of the present invention includes ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1
-Alkenes having 2 to 6 carbon atoms such as hexene are mentioned, and a mixture thereof can also be used. Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene is particularly preferable.

Examples of the component (A3) represented by any of the above formulas (I) to (IV) constituting the polyolefin resin of the present invention include, for example, methyl (meth) acrylate represented by the formula (I), (Meth) acrylic acid esters such as ethyl (meth) acrylate and butyl (meth) acrylate, maleic acid esters such as dimethyl maleate represented by the formula (II), diethyl maleate and dibutyl maleate, and formulas (Meth) acrylic acid amides represented by (III), alkyl vinyl ethers represented by formula (IV) such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, versatic Vinyl alcohols such as vinyl acetate and vinyl alcohol obtained by saponifying vinyl esters with a basic compound, And the like, and a mixture thereof can also be used. Among these, the (meth) acrylic acid ester represented by the formula (I) is more preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is particularly preferable.

The polyolefin resin used in the present invention is most preferably a terpolymer composed of ethylene, methyl acrylate or ethyl acrylate, and maleic anhydride. Here, the acrylic acid ester unit may hydrolyze a small part of the ester bond to be converted to an acrylic acid unit when the resin is made water-based, which will be described later. It suffices that the ratio of each constituent component in consideration of the change is within the specified range.

The unsaturated carboxylic acid anhydride units such as maleic acid anhydride units constituting the polyolefin resin in the present invention form an acid anhydride structure in which adjacent carboxyl groups are dehydrated and cyclized in the dry state of the resin. However, particularly in an aqueous medium containing a basic compound, a part or all of the ring is opened to facilitate the structure of the carboxylic acid or a salt thereof. In addition, in the present invention, when the amount is defined based on the amount of the carboxyl group of the resin, it is calculated by assuming that all the acid anhydride groups in the resin are ring-opened to form the carboxyl group.

The polyolefin resin used in the present invention may be copolymerized with a small amount of other monomers. Examples thereof include dienes, (meth) acrylonitrile, vinyl halides, vinylidene halides, carbon monoxide, sulfur disulfide and the like.

The polyolefin resin used in the present invention has a melt flow rate of 0.1 to 500 g / 10 minutes, preferably 0.1 to 300, at 190 ° C. and a load of 2160 g, which is an index of molecular weight.
g / 10 minutes, more preferably 0.1 to 250 g / 10 minutes, still more preferably 0.5 to 200 g / 10 minutes, and most preferably 1 to 100 g / 10 minutes. If the melt flow rate of the polyolefin resin is less than 0.1 g / 10 minutes, it becomes difficult to make the resin water-soluble, and it is difficult to obtain a good aqueous dispersion.
On the other hand, the melt flow rate of polyolefin resin is 500
When it exceeds g / 10 minutes, the coating film obtained from the aqueous dispersion becomes hard and brittle, and the adhesiveness and mechanical strength deteriorate.

The method for synthesizing the polyolefin resin used in the present invention is not particularly limited, but it is preferable not to use an emulsifier or a compound having a protective colloid action. Generally, it is obtained by high-pressure radical copolymerization of a monomer constituting a polyolefin resin in the presence of a radical generator. Further, the unsaturated carboxylic acid or its anhydride may be graft-copolymerized (graft-modified).

In the aqueous dispersion of the present invention, the above polyolefin resin is dispersed or dissolved in an aqueous medium. Here, the aqueous medium is a medium composed of a liquid containing water as a main component, and may contain a water-soluble organic solvent described later. Moreover, you may contain the basic compound mentioned later.

Further, the number average particle size of the polyolefin resin particles dispersed in the aqueous dispersion of the polyolefin resin which is the aqueous adhesive of the present invention needs to be 1 μm or less, and the storage stability of the aqueous dispersion is high. From the viewpoint of improvement and the improvement of film-forming property at low temperature, 0.5 μm or less is preferable, 0.3 μm or less is more preferable, 0.2 μm or less is further preferable, and less than 0.1 μm is most preferable.

The content of the polyolefin resin in the water-based adhesive of the present invention can be appropriately selected depending on the film forming conditions, the thickness and performance of the intended resin coating, and is not particularly limited, but the viscosity of the coating composition is not limited. Is appropriately maintained, and in order to develop a good film-forming ability, 1 to 60 mass% is preferable, 3 to 55 mass% is more preferable, 5 to 50 mass% is further preferable, and 10 to 45 mass% is particularly preferable. preferable.

It is particularly preferred that the aqueous dispersion of the present invention contains substantially no non-volatile hydration aid. The non-volatile water-solubilizing agent remains in the polyolefin resin even after the film is formed and plasticizes the film, so that the properties of the polyolefin resin, such as water resistance and adhesiveness, are deteriorated. In the present invention, it is not necessary to add a non-volatile water-solubilizing agent, and when it is not added, the properties such as water resistance and adhesiveness are particularly excellent.

The term "aqueous solubilizer" as used herein refers to a drug or compound added for the purpose of promoting aqueous solubilization or stabilizing the aqueous dispersion in the production of the aqueous dispersion, and is "nonvolatile".
The term "has no boiling point under normal pressure" or "has a high boiling point under normal pressure (for example, 300 ° C or higher)". The phrase "substantially free of non-volatile aqueous auxiliaries" means that non-volatile aqueous auxiliaries are not positively added to the system, resulting in the absence of these. It is particularly preferable that the content of such a non-volatile aqueous solubilizing agent is zero, but it may be contained in an amount of less than 0.1% by mass with respect to the polyolefin resin component as long as the effect of the present invention is not impaired.

Examples of the non-volatile aqueous auxiliaries referred to in the present invention include emulsifiers, compounds having a protective colloid action, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers described below. Examples of emulsifiers include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, as the anionic emulsifier, sulfate ester salt of higher alcohol, higher alkyl sulfonate, higher carboxylate,
Examples thereof include alkylbenzene sulfonate, polyoxyethylene alkyl sulphate salt, polyoxyethylene alkyl phenyl ether sulphate salt, vinyl sulfosuccinate, and the like. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyethylene. Glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide,
Examples thereof include compounds having a polyoxyethylene structure such as ethylene oxide-propylene oxide copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters, and examples of amphoteric emulsifiers include lauryl betaine and lauryl dimethylamine oxide.

Compounds having a protective colloid action, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch. , Polyvinylpyrrolidone, polyacrylic acid and its salts, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax,
Number-average molecular weight of carboxyl group-containing polyethylene-propylene wax or the like is usually 5000 or less, acid-modified polyolefin waxes and salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, styrene- (meth) acrylic acid copolymers , Ethylene- (meth) acrylic acid copolymer,
Isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid-unsaturated carboxylic acid content such as (meth) acrylic acid ester copolymer 10 mass% or more carboxyl group-containing polymer and salts thereof, polyitaconic acid and Examples thereof include salts, water-soluble acrylic copolymers having an amino group, gelatin, gum arabic, casein and the like, which are generally used as dispersion stabilizers for fine particles.

In the water-based adhesive of the present invention, the carboxyl group in the polyolefin resin is preferably neutralized with a basic compound. The electric repulsive force between the carboxyl anions generated by the neutralization prevents aggregation among the fine particles and imparts stability to the aqueous dispersion. The basic compound used for making the aqueous solution may be one that can neutralize the carboxyl group. Therefore, the basic compound added for such a purpose can be said to be an hydration aid, but a volatile basic compound is used in order not to impair the effects of the present invention.

As such a basic compound, ammonia or an organic amine compound which volatilizes at the time of forming a film is preferable from the viewpoint of the water resistance of the film, and among them, an organic amine compound having a boiling point of 30 to 250 ° C., more preferably 50 to 200 ° C. preferable. When the boiling point is less than 30 ° C., the ratio of volatilization at the time of water-solubilization of the resin, which will be described later, increases, and water-hydration may not be completely progressed. When the boiling point exceeds 250 ° C, it becomes difficult to scatter the organic amine compound from the resin film by drying, and the water resistance of the 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, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine,
Examples thereof include N-ethylmorpholine. The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent to the carboxyl group in the polyolefin resin, 0.8
˜2.5 times equivalents are more preferable, and 1.01 to 2.0 times equivalents are particularly preferable. If it is less than 0.5 times the equivalent, the effect of adding the basic compound is not observed, and if it exceeds 3.0 times the drying time during the formation of the resin layer may be prolonged or the aqueous dispersion may be colored.

In the present invention, in order to accelerate the hydration of the polyolefin resin and reduce the dispersed particle size, it is preferable to add an organic solvent during the hydration. The amount of the organic solvent used is preferably 40% by mass or less in the aqueous medium,
It is more preferably 1 to 40% by mass, further preferably 2 to 35% by mass, and particularly preferably 3 to 30% by mass. When the amount of the organic solvent exceeds 40% by mass, it cannot be regarded as an aqueous medium substantially, which is one of the purposes of the present invention (environmental protection).
In addition to deviating from the above, the stability of the aqueous dispersion may decrease depending on the organic solvent used.

In general, a part of the organic solvent contained in the water-based adhesive can be distilled out of the system by an operation called stripping, but in the water-based dispersion of the present invention, this operation also results in The amount of the organic solvent in the aqueous dispersion may be appropriately reduced within the above range and can be 10% by mass or less, and 3% by mass or less is environmentally preferable. To remove the organic solvent by stripping,
Since it is necessary to take measures in the production process such as increasing the degree of depressurization of the device or prolonging the operating time, the lower limit of the amount of organic solvent in consideration of such productivity is about 0.01% by mass (the analysis used in the measurement of the present invention. Detection limit of equipment). However, even if it is less than 0.01% by mass, the performance as an aqueous dispersion does not cause any particular problem. Even if the amount of the organic solvent is reduced by stripping, the aqueous dispersion of the present invention has no particular effect on the performance and can be favorably used for various applications.

Examples of the stripping method include a method in which the aqueous adhesive is heated with stirring under normal pressure or reduced pressure, and the organic solvent is distilled off. The content of the organic solvent can be quantified by gas chromatography.
Further, by distilling off the aqueous medium, the solid content concentration increases, and for example, when the viscosity increases and workability deteriorates, water should be added to the aqueous dispersion in advance. You can also

As the organic solvent, from the viewpoint of obtaining a good aqueous dispersion, an atom having a Pauling electronegativity of 3.0 or more (specifically, oxygen, nitrogen, fluorine, chlorine) is used in the molecule. It is preferable to use one having more than one. Among them, those having a solubility in water at 20 ° C. of 5 g / L or more are preferably used, and more preferably 10 g / L or more.

Specific examples of the organic solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-butanol.
Amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols, methyl ethyl ketone, methyl isobutyl ketone, ethyl Butyl ketone, cyclohexanone, isophorone and other ketones, tetrahydrofuran, dioxane and other ethers, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, acetic acid-3- Esters such as methoxybutyl, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, glycol derivatives such as propylene glycol methyl ether acetate,
Furthermore, 3-methoxy-3-methylbutanol, 3-
Methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like, among them, the boiling point is 30 ~
A temperature of 250 ° C is preferable, and a temperature of 50 to 200 ° C is particularly preferable. You may use these organic solvents in mixture of 2 or more types. When the boiling point of the organic solvent is lower than 30 ° C., the rate of volatilization at the time of hydration of the resin increases, and the hydration efficiency may not be sufficiently increased. An organic solvent having a boiling point of higher than 250 ° C. is difficult to be scattered from the resin coating by drying, and the water resistance of the coating may be deteriorated.

Among the above-mentioned organic solvents, ethanol, n-propanol, and n-propanol are highly effective in promoting hydration of the resin and can easily remove the organic solvent from the aqueous medium.
Isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether are preferable, and ethanol, n-propanol and isopropanol are particularly preferable from the viewpoint of low temperature drying property.

The water-based adhesive prepared by the method of the present invention is 25
A resin layer having high transparency can be formed even at a temperature of not higher than ° C. Here, as a measure of transparency, the "haze" of a coated film coated with an aqueous dispersion of a polyolefin resin at room temperature is used. Haze 2.0 ~ 5.0 as base material
(%) PET film is used, and this is dried with a polyolefin resin aqueous dispersion at 25 ° C., coated with a coating film thickness of 2 μm, and dried at 25 ° C. The haze of the entire coated film thus obtained is 10.0 (%) or less. In the present invention, the haze becomes 10.0 (%) or less even if the same operation is performed at 5 ° C.

Next, a method for producing an aqueous adhesive in which a polyolefin resin is dispersed in an aqueous medium will be described. The method for obtaining the water-based adhesive of the present invention is not particularly limited, but for example, each component described above, that is, a polyolefin resin of a specific composition, a basic compound, an organic solvent, and water is preferably in a container that can be sealed. The method of heating and stirring can be adopted, and this method is the most preferable. According to this method, a polyolefin resin having a specific composition can be satisfactorily made into an aqueous dispersion without substantially adding a non-volatile hydration aid such as an emulsifier component or a compound having a protective colloid action.

As the container, any container may be used so long as it can be charged with a liquid and can appropriately stir the mixture of the aqueous medium and the resin powder or granules charged in the liquid. As such a device, a device widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier can be used,
It is preferable to use a device capable of applying a pressure of 0.1 MPa or more. The stirring method in the present invention, the rotation speed of the stirring is not particularly limited, sufficient waterification is achieved even at low speed stirring such that the resin becomes a floating state in the aqueous medium, high speed stirring (for example 1000 rpm or more) is not essential. Absent. Therefore, it is possible to manufacture the aqueous dispersion with a simple apparatus.

The shape of the polyolefin resin used for hydration is not particularly limited, but from the viewpoint of increasing the hydration rate, it is preferable to use a granular or powdery one having a particle diameter of 1 cm or less, preferably 0.8 cm or less.

An aqueous medium consisting of water, a basic compound and an organic solvent, and a granular or powdered polyolefin resin are put into the tank of this apparatus, and the mixture is preferably stirred and mixed at a temperature of 40 ° C. or lower. Then, increase the temperature in the bath to 80-20.
0 ℃, preferably 90 ~ 200 ℃, more preferably 100 ~ 200
While maintaining the temperature of ° C., to make the polyolefin resin sufficiently aqueous, preferably by continuing stirring for 5 to 120 minutes,
Thereafter, the aqueous dispersion can be obtained by preferably cooling to 40 ° C. or lower with stirring. The temperature in the tank is 80
When the temperature is lower than 0 ° C, it becomes difficult to make the polyolefin resin aqueous. If the temperature in the tank exceeds 200 ° C, the molecular weight of the polyolefin resin may decrease. As a method for heating the inside of the tank, heating from the outside of the tank is preferable, and for example, the tank can be heated using oil or water, or a heater can be attached to the tank for heating. Examples of the method for cooling the inside of the tank include a method of naturally cooling at room temperature and a method of cooling using oil or water at 0 to 40 ° C.

After this, a jet crushing treatment may be further performed if necessary. The jet pulverization treatment here means that a fluid such as an aqueous dispersion of polyolefin resin is ejected from a fine hole such as a nozzle or a slit under high pressure, and the resin particles are collided with each other or with the collision plate and the like. , Is to further refine the resin particles by mechanical energy, and a specific example of a device therefor is,
APVGAULIN's homogenizer, Mizuho Kogyo's microfluidizer M-110E / H, etc. are mentioned.

As a method for adjusting the solid content concentration of the thus obtained aqueous dispersion, for example, a method of distilling off the aqueous medium or diluting it with water so that the desired solid content concentration is obtained. Can be mentioned.

As described above, the aqueous dispersion of the present invention is obtained by dispersing or dissolving a polyolefin resin in an aqueous medium to prepare a uniform liquid form. Here, a uniform liquid state means that, in appearance, a part where the solid content concentration is locally different from other parts such as precipitation, phase separation or skinning in the aqueous dispersion is not found. Say.

The water-based yield in the production of the aqueous adhesive can be known from the amount of coarse particles remaining in the obtained aqueous adhesive. Specifically, the aqueous dispersion is subjected to pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the amount of resin remaining on the filter is measured. Even when the amount of residual resin is large and the yield is low, if the above-mentioned filtration is performed during the production process to remove such coarse particles, it can be used as an aqueous dispersion in the subsequent steps. The hydration yield in the present invention may be slightly lowered depending on the conditions, but is generally very good, and the hydration is achieved with few coarse particles remaining.

The water-based adhesive of the present invention has a low unsaturated carboxylic acid content, and therefore has excellent mixing stability with various additives. For example, aqueous dispersions of other polymers, metal ions,
Inorganic particles, a crosslinking agent or the like can be added.

The aqueous dispersion of another polymer is not particularly limited. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene- (meth) acrylic acid copolymer, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene Aqueous dispersions of resins, poly (meth) acrylonitrile resins, (meth) acrylamide resins, chlorinated polyethylene resins, chlorinated polypropylene resins, polyester resins, modified nylon resins, urethane resins, phenol resins, silicone resins, epoxy resins, etc. be able to. These are 2
You may use it in mixture of 2 or more types.

In order to further improve various coating film performances such as blocking resistance and water resistance, a crosslinking agent is added in an amount of 0.01 to 100 parts by mass, preferably 0.1 to 60 parts by mass, based on 100 parts by mass of the resin in the aqueous adhesive. Parts can be added. When the amount of the cross-linking agent added is less than 0.01 parts by mass, the degree of improvement in coating film performance is small, and when it exceeds 100 parts by mass, the performance such as workability deteriorates. As the cross-linking agent, a cross-linking agent having a self-crosslinking property, a compound having a plurality of functional groups capable of reacting with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, or the like can be used. Preferred are melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like. Further, these cross-linking agents may be used in combination.

Further, if necessary, a tackifier, a leveling agent, an antifoaming agent, an anti-armpitting agent,
The aqueous dispersion of the present invention can be used as a coating agent or paint by adding various agents such as a pigment dispersant and an ultraviolet absorber, and pigments or dyes such as titanium oxide, zinc white and carbon black. It is also possible to add an organic or inorganic compound other than the above to the aqueous dispersion within a range that does not impair the stability of the aqueous adhesive.

Additives such as the above-mentioned aqueous dispersions of other polymers, crosslinking agents, tackifiers, leveling agents, defoamers, anti-armpit agents, pigment dispersants, ultraviolet absorbers, pigments or dyes are used. You may use it in combination of 2 or more types.

The water-based adhesive of the present invention is preferably used as an adhesive for synthetic paper, particularly polyolefin synthetic paper. Here, the term “polyolefin” means that the main component is, for example, a polyethylene resin such as high-density polyethylene or medium-density polyethylene, or a polyolefin resin such as polypropylene. These resins may be used alone or in combination of two or more. Among these, it is most preferable to use polypropylene in terms of chemical resistance, heat resistance, cost and the like.

The three-dimensional structure of polypropylene is not particularly limited. For example, propylene homopolymer having isotactic or syndiotactic and various degrees of stereoregularity, propylene as a main component, and ethylene,
Examples thereof include copolymers with α-olefins such as 1-butene, 2-butene, 1-hexene, 1-heptene and 4-methyl-1-pentene. These copolymers have 2
It may be a multi-component copolymer of one or more elements, a random copolymer or a block copolymer.

Even if the synthetic paper contains a filler (generally 75% by mass or less), it can be suitably used as an adherend of the present water-based adhesive. As the filler used in the synthetic paper, examples of inorganic fillers include calcium carbonate, clay, silica, diatomaceous earth, talc, titanium oxide, barium titanate, barium sulfate, and alumina.
The average particle size of the filler is preferably 0.01 to 15 μm. In organic systems, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 6,6,
Polymers such as nylon 4,6, nylon and cyclic polyolefins having a melting point or glass transition temperature higher than that of the polyolefin resin can be used.

The structure of the polyolefin-based synthetic paper as the adherend of the adhesive of the present invention is not particularly limited. Therefore, it may have a single-layer structure or a multi-layer structure. Examples of the multilayer structure include a two-layer structure including a base layer and a surface layer, a three-layer structure in which the base layer and the front and back surfaces have a surface layer, and another resin film layer between the base layer and the surface layer. A multilayer structure can be illustrated. Each layer may or may not contain an inorganic or organic filler.

As the polyolefin synthetic paper,
A microporous synthetic paper having a large number of fine voids can be used. Among them, the porosity is 5 to 60%, preferably 8 to 40
% Is preferably used.

The polypropylene synthetic paper used in the present invention is, for example, YUPO FP manufactured by Oji Yuka Synthetic Paper Co., Ltd.
G, Yupo FGS, Yupo GFG, Yupo KPK and the like can be mentioned.

The thickness of the polyolefin synthetic paper is not particularly limited. The thickness of such synthetic paper is about 20 to 400 μm.

The water-based adhesive of the present invention has excellent adhesiveness not only to synthetic paper but also to a thermoplastic resin, and therefore its usage is not limited to the bonding of synthetic paper and synthetic paper. It can also be suitably used for bonding synthetic paper and thermoplastic resin film.

As the thermoplastic resin film to be attached to the synthetic paper, nylon 6 (hereinafter, Ny6), nylon 6
6, polyamide resin such as nylon 46, polyethylene terephthalate (hereinafter PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc. polyester resin, polypropylene (hereinafter PP ), Polyethylene (hereinafter PE), a polyolefin resin such as ethylene-vinyl acetate copolymer, a polyimide resin, a polycarbonate resin, a polyarylate resin, or a film made of a mixture thereof, or a laminate of these films. Above all, a film made of PP or PE is preferably used, and particularly a PP film is preferably used. The polyolefin resin may be copolymerized with a small amount of an ethylenically unsaturated compound,
It may be acid-modified with maleic anhydride or the like. The thermoplastic resin film may be an unstretched film or a stretched film, and the manufacturing method is not particularly limited. The thickness of the thermoplastic resin film is not particularly limited, but is usually 1 to 1000.
It should be μm. Also, the film surface is corona treated,
Adhesion tends to be better when a surface treatment such as plasma treatment or oxidation treatment is performed.

Next, a method of using the water-based adhesive of the present invention will be described. The water-based adhesive of the present invention is excellent in the ability to form a resin layer, so known coating methods such as gravure roll coating, single-wafer gravure roll coating,
Reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. are applied to the surface of various substrates, and if necessary, set at around room temperature and then dried. Alternatively, the resin layer can be formed in close contact with the surface of various base materials by subjecting it to a heat treatment for drying and baking. As a heating device at this time, an ordinary hot air circulation type oven, an infrared heater or the like may be used. The heating temperature and heating time are appropriately selected depending on the characteristics of the substrate that is the object to be coated, but in consideration of economic efficiency and heat resistance of synthetic paper,
The heating temperature is preferably 10 to 165 ° C, more preferably 30 to 160 ° C, particularly preferably 50 to 150 ° C, and the heating time is preferably 1 second to 10 minutes, more preferably 5 seconds to 5 minutes, Particularly preferred is 10 seconds to 5 minutes.

Since the water-based adhesive of the present invention has a small number average particle diameter and is in a liquid state, it can be thinly applied to the surface of the substrate, and the application amount is appropriately selected depending on its use. However, for example, the coating amount after drying is 0.1
It is preferably about 50 g / m ² . Considering performance such as adhesiveness and transparency, 0.3 to 30 g / m ² is more preferable, 0.5 to 20
g / m ² is more preferable, and 1 to 10 g / m ² is particularly preferable. If the coating amount is less than 0.1 g / m ² , the adhesiveness will be insufficient.

In order to control the thickness of the resin coating, in addition to appropriately selecting the apparatus used for coating and the operating conditions thereof, the aqueous dispersion having a concentration suitable for the intended thickness of the resin coating is obtained. Is preferably used. The concentration at this time can be adjusted by the composition charged at the time of preparation. Further, the water-based adhesive once prepared may be adjusted by appropriately diluting or concentrating it.

When the synthetic paper and the thermoplastic resin film are laminated using the water-based adhesive of the present invention, the water-based adhesive may be applied to the surface of either the synthetic paper or the thermoplastic resin film. From the viewpoint of improving the adhesiveness between the two, it is preferable to apply it to the surface of the synthetic paper. Next, the base material having the adhesive layer thus produced and various base materials are adhered under pressure. At this time, it is preferable to pressurize under heating to ensure adhesiveness, and the temperature is 60 to 16
5 ℃ is preferable, 80 ~ 150 ℃ is more preferable, 90 ~ 140 ℃
Is particularly preferable. If it is less than 60 ° C, sufficient adhesiveness cannot be obtained, and if it exceeds 165 ° C, it is more than the heat resistance of the synthetic paper, which is not preferable. The apparatus used at this time is not particularly limited, and examples thereof include a heat press machine and a roll laminator that sandwiches both base materials with two roll bars and supplies both base materials while applying pressure. The pressure at that time is
It is preferable that sufficient adhesiveness can be secured and the characteristics of the substrate are not impaired, 0.01 to 5 MPa is preferable, and 0.05 to
3 MPa is more preferable.

[0065]

EXAMPLES The present invention will now be described in detail with reference to Examples, but the present invention is not limited thereto. Various properties were measured or evaluated by the following methods. (1) Constitution of polyolefin resin ¹ H-NMR analysis (manufactured by Varian Co., Ltd., 300 MHz) was carried out in orthodichlorobenzene (d ₄ ) at 120 ° C. for determination. (2) Residual amount of ester group after hydration After drying the aqueous dispersion of the polyolefin resin after hydration at 150 ° C., 120% in orthodichlorobenzene (d ₄ ).
¹ H-NMR analysis (manufactured by Varian Co., Ltd., 300 MHz) was performed at ⁰ ° C., and the residual rate (%) of the ester group was determined with the amount of the ester group of the acrylic acid ester before hydration as 100. (3) Solid Content Concentration of Aqueous Adhesive An appropriate amount of the aqueous adhesive was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant amount, and the concentration of the non-volatile component was determined. (4) Viscosity of aqueous adhesive The rotational viscosity of the aqueous dispersion at a temperature of 20 ° C was measured using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec. (5) Average particle size of polyolefin resin particles in the aqueous dispersion Microtrack particle size analyzer UPA150 (MODE, manufactured by Nikkiso Co., Ltd.)
L No. 9340) was used to determine the number average particle size. (6) Aqueousification yield The aqueous dispersion after hydration is pressurized and filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) (air pressure 0.2
(MPa), the mass of the resin remaining on the filter was measured, and the yield was calculated from the mass of the charged resin. (7) Appearance of water-based adhesive The color tone of the water-based adhesive was evaluated by visual observation. (8) Water-resistant adhesive for coating film was coated on a biaxially stretched PET film (Emblet PET12 manufactured by Unitika Ltd., thickness 12 μm) with a Mayer bar so that the thickness of the coating film after drying was about 2 μm. 1 at ℃
Dry for minutes. The coated film thus prepared was immersed in tap water for 1 day, and then the presence or absence of dissolution or peeling of the coating layer was visually evaluated. ○: No change in appearance. X: The coat layer is dissolved or peeled off. (9) The pot life water-based adhesive was left at room temperature for 90 days.
The grade was evaluated. ○: No change in appearance. Δ: Viscosity increased. X: Solidification, aggregation and generation of precipitates are observed. (10) Content of organic solvent in water-based adhesive Shimadzu Corporation gas chromatograph GC-8A [using FID detector, carrier gas: nitrogen, column packing material (manufactured by GL Sciences Inc.): PEG-HT (5%) -Uniport HP (60/8
0 mesh), column size: diameter 3 mm x 3 m, sample input temperature (injection temperature): 150 ° C, column temperature: 60
C., internal standard substance: n-butanol], an aqueous adhesive or a water-based adhesive diluted with water was directly put into the apparatus to determine the content rate of isopropanol as an organic solvent. The detection limit was 0.01% by mass. (11) Haze (haze value) According to JIS K7105, "Haze (%)" was measured using NDH2000 "turbidity, haze meter" manufactured by Nippon Denshoku Industries Co., Ltd. PET film with a haze of 2.8% (Emblet PET12 manufactured by Unitika Ltd., thickness 12 μm) was coated with a water-based adhesive using a Meyer bar so that the coating film thickness after drying was 2 μm, and then in an atmosphere of 25 ° C. It was left standing for 3 days and dried to prepare a coated film. The haze of the entire coated film thus produced was measured. (12) Blocking resistance of resin coating YUPO paper (FGS-9 manufactured by YUPO Co., Ltd.) which is a polypropylene-based synthetic paper
A water-based adhesive was applied to 5) so that the coating amount after drying was 4 g / m ² , and then dried at 100 ° C. for 1 minute to form a resin film. After leaving at room temperature for 1 day, PP film (Pure Softy H-R111 made by Idemitsu Unitech Co., double-sided corona product,
(Thickness: 300 μm) were superposed, a load of 200 g / cm ² was applied, the mixture was allowed to stand in an atmosphere of 25 ° C. and 65% RH for 24 hours, and its blocking resistance was evaluated according to the following three grades. ◯: The film is peeled off by slightly lifting it. Δ: The film is peeled off by pulling. X: Does not peel even when the film is pulled. (13) Adhesiveness evaluation method A sample produced by the method described in the examples is cut out with a width of 15 mm, and one day later, a tensile tester (Intesco Precision Universal Material Testing Machine 2020, manufactured by Intesco Corporation) is used to measure the pulling speed. The peel strength (N / 15 mm) of the adhesive layer was measured at 200 mm / min and a pulling angle of 180 degrees. The average value of 5 measurements was used.

The composition of the resin used is shown in Table 1. In addition,
The melting points of the resins listed in Table 1 are the values measured by DSC (measurement device: Perkin-Elmer DSC-7),
The melt flow rate is the method described in JIS 6730 (190 ℃, 216
It is a value measured with 0 g load).

[0067]

[Table 1]

Example 1 Using a stirrer equipped with a pressure-tight 1 L glass container with a heater and which can be closed, 60.0 g of a polyolefin resin [Bondayne HX-8290 (A), manufactured by Sumitomo Chemical Co., Ltd.], 60.0 g of isopropanol ( Hereinafter, IPA), 4.5 g (1.8 times equivalent to the carboxyl group of maleic anhydride in the resin) triethylamine (hereinafter, TEA) and 175.5 g of distilled water were charged in a glass container, and the rotation speed of the stirring blade was adjusted. Upon stirring 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 temperature in the system was kept at 140 to 145 ° C., and the mixture was further stirred for 20 minutes. After that, put it in a water bath and cool it to room temperature (about 25 ° C) while stirring at a rotation speed of 300 rpm, and then press-filter (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). A uniform milky white polyolefin resin aqueous dispersion was obtained. Various properties of the aqueous dispersion and coating properties are shown in Table 2. The number average particle size is 0.
The distribution was 071 μm, the distribution was one peak, and the polyolefin resin was dispersed in the aqueous medium in a good state. Furthermore, the pot life of the aqueous dispersion was 90 days or more. The residual ester group of the resin after hydration was 100%, and ethyl acrylate was not hydrolyzed. This ester group residual ratio does not change after 90 days at room temperature
It was 100%. The haze of the coated film coated with this aqueous dispersion by the method described above was 2.8%, and the transparency was good. The water resistance and blocking resistance were also good. The aqueous dispersion obtained here was treated with an aqueous adhesive E-
A polypropylene-based synthetic paper, YUPO paper (FGS-95, manufactured by YUPO Co., Ltd.) was applied with a Meyer bar so that the application amount after drying was 4 g / m ^2, and the product was dried at 100 ° C. for 1 minute. A thermoplastic film [biaxially stretched PET film (Emblet PET12 manufactured by Unitika Ltd., thickness 12 μm)] biaxially stretched on the coated surface
Ny6 film (Unitika Emblem, thickness 15μ
m), PP film (Pure Softy H-R111 manufactured by Idemitsu Unitech Co., double-sided corona product, thickness 300 μm), PE film (V-50 manufactured by Tama Poly Co., thickness 40 μm)], and using PE by hot pressing Is 100 ℃, PP is 110 ℃, PE
In the case of T and Ny6, a tensile test sample was prepared by pressing at 120 ° C. and 0.2 MPa for 1 second. The results of measuring the adhesiveness are shown in Table 2.

Example 2 An aqueous solution was prepared in the same manner as in Example 1 except that a polyolefin resin [Bondaine HX-8210 (B), manufactured by Sumitomo Chemical Co., Ltd.] was used and the amount of TEA added was changed as shown in Table 2. A dispersion was obtained and designated as a water-based adhesive E-2. Table 2 shows various properties, coating properties, and adhesive properties of the aqueous dispersion.

Example 3 An aqueous solution was prepared in the same manner as in Example 1 except that a polyolefin resin [Bondaine HX-8140 (C), manufactured by Sumitomo Chemical Co., Ltd.] was used and the amount of IPA added was changed as shown in Table 2. A dispersion was obtained and designated as a water-based adhesive E-3. Table 2 shows various properties, coating properties, and adhesive properties of the aqueous dispersion.

Example 4 A method similar to that of Example 1 except that a polyolefin resin [Bondayne TX-8030 (D), manufactured by Sumitomo Chemical Co., Ltd.] was used and the amounts of TEA and IPA added were changed as shown in Table 2. To obtain an aqueous dispersion, which was used as an aqueous adhesive E-4. Table 2 shows various properties, coating properties, and adhesive properties of the aqueous dispersion.

Example 5 E-1 (250 g) and distilled water (10 g) were charged into a 1 L 2-neck round bottom flask, a mechanical stirrer and a Liebig type condenser were installed, and the flask was heated with an oil bath to distill the aqueous medium. I left. When about 100 g of the aqueous medium was distilled off, heating was stopped and the mixture was cooled to room temperature. After cooling, the liquid component in the flask was subjected to pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the solid content concentration of the filtrate was measured to be 31.3% by mass. . Distilled water was added to this filtrate with stirring to adjust the solid content concentration to 30.0% by mass to obtain an aqueous dispersion. Various properties of the aqueous dispersion and coating properties are shown in Table 2. The aqueous dispersion obtained here as an aqueous adhesive E-5,
A tensile test sample was prepared in the same manner as in Example 1. The results of measuring the adhesiveness are shown in Table 2.

Examples 6 to 8 The aqueous adhesive E-1 which is the polyolefin resin aqueous dispersion obtained in Example 1 was mixed with the crosslinking agent. As the cross-linking agent, a melamine compound (Cymel 327, manufactured by Mitsui Cytec, Example 6), a carbodiimide compound (Carbodilite E-01, manufactured by Nisshinbo, Example 7), an oxazoline group-containing compound (Epocros K-2010, Nippon Shokubai) Manufactured by Example 8)
Was used. E-1 is stirred, 10 parts by mass of the cross-linking agent in terms of solid content, relative to 100 parts by mass of solid content of E-1, is added,
Stir for 30 minutes at room temperature. The obtained liquids were used as water-based adhesives E-6 to E-8, respectively. Table 2 shows various properties of the water-based adhesive and coating properties. Samples for tensile test were prepared in the same manner as in Example 1 using the water-based adhesives E-6 to E-8. The results of measuring the adhesiveness are shown in Table 2.

Comparative Example 1 60.0 g of an ethylene-acrylic acid copolymer resin [Primacol 5980I, acrylic acid 20% by mass copolymer, Dow Chemical, P (E-AA)], 16.8g
TEA (1.0 times equivalent to the carboxyl group of acrylic acid in the resin) and 223.2 g of distilled water were charged into a glass container and stirred at a rotation speed of a stirring blade of 300 rpm. No sedimentation of the product was observed and it was confirmed that the product was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature in the system was kept at 100 to 105 ° C., and the mixture was further stirred for 20 minutes. After that, put it in a water bath and cool it to room temperature (about 25 ° C) while stirring at a rotation speed of 300 rpm, and then press-filter (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). A slightly cloudy aqueous dispersion was obtained.
Various properties of the aqueous dispersion and coating properties are shown in Table 2.
The aqueous dispersion thus obtained was used as an aqueous adhesive H-1 to prepare a sample for tensile test in the same manner as in Example 1.
The results of measuring the adhesiveness are shown in Table 2. When the polyolefin resin aqueous dispersion containing a large amount of acrylic acid, which is an unsaturated carboxylic acid, as high as 20% by mass was used as the adhesive, the adhesiveness to the polypropylene resin film and the PET film was significantly reduced as compared with the examples.

[0075]

[Table 2]

[0076]

EFFECT OF THE INVENTION The water-based adhesive of the present invention has excellent adhesiveness to synthetic paper and a thermoplastic resin film, and a laminated body can be obtained by laminating these.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 133/00 C09J 133/00 133/04 133/04 133/24 133/24 135/00 135/00 / / (C08F 210/00 C08F 220: 10 220: 10 222: 04 222: 04) C08F 222: 10 (C08F 210/00 220: 56 222: 10 C08F 218: 02 222: 04) (C08F 210/00 220: 56 222: 04) (C08F 210/00 218: 02 222: 04) F-term (reference) 4F100 AK01B AK03A AK04B AK07A AK07B AK42B AK48B AK71 AS00A AT00B BA02 BA07 CB10 GB90 JB07 J001 DD06091DF001 DD061 MA11 4J100 AA01P AA02P AA03P AA04P AA06P AA07P AA16P AD01Q AD02Q AE02Q AE03Q AE04Q AG02Q AG03Q AG04Q AJ02R AJ08R AJ09R AK31R AK32R AL03Q AL34Q AL36R AM14Q DA15Q CA15Q

Claims (12)

[Claims] 1. The following polyolefin resin has a number average particle diameter.
Aqueous adhesive for synthetic paper consisting of an aqueous dispersion dispersed at 1 μm or less. Polyolefin resin: (A1) unsaturated carboxylic acid or anhydride thereof, (A2) ethylene hydrocarbon, (A3) at least one compound represented by any of the following formulas (I) to (IV) A polyolefin resin which is a copolymer having the following formulas (1) and (2) in which the mass ratio of each of the constituent components (A1) to (A3) is satisfied. 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 <5 (1) (A2) / (A3) = 55/45 to 99/1 (2) [Chemical formula 1] 2. The aqueous adhesive for synthetic paper according to claim 1, wherein the aqueous polyolefin resin dispersion contains substantially no non-volatile aqueous auxiliaries. 3. The water-based adhesive for synthetic paper according to claim 1, wherein the melt flow rate of the polyolefin resin at 190 ° C. under a load of 2160 g is 0.1 to 500 g / 10 minutes. 4. The polyolefin resin according to claim 1, wherein the polyolefin resin is an ethylene-acrylic acid ester-maleic anhydride terpolymer or an ethylene-methacrylic acid ester-maleic anhydride terpolymer. Water-based adhesive for synthetic paper. 5. A polyolefin resin 100 in an aqueous adhesive.
The water-based adhesive for synthetic paper according to claim 1, which contains 0.01 to 100 parts by mass of a crosslinking agent with respect to parts by mass. 6. The water-based adhesive for synthetic paper according to claim 1, wherein the synthetic paper is a polyolefin-based synthetic paper. 7. The water-based adhesive for synthetic paper according to claim 6, wherein the polyolefin-based synthetic paper is polypropylene-based synthetic paper. 8. A laminate comprising at least three layers,
A laminate in which the three layers are synthetic paper, an adhesive layer obtained by applying the water-based adhesive according to any one of claims 1 to 7 and drying, and a thermoplastic resin molded body in this order. 9. The laminate according to claim 8, wherein the thermoplastic resin molding is a thermoplastic resin film. 10. The laminate according to claim 8, wherein the thermoplastic resin molded body is a molded body made of polypropylene or polyethylene. 11. A laminate comprising at least three layers, the three layers of which are synthetic paper, an adhesive layer formed by applying the aqueous adhesive according to any one of claims 1 to 7 and drying, and a synthetic paper. A laminate obtained by laminating in this order. 12. The coating amount of the water-based adhesive for synthetic paper after drying is 0.1 to 50 g / m ^2.
The laminated body according to.