KR102302377B1 - Aqueous dispersion, and laminate - Google Patents

Abstract

As an aqueous dispersion containing an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium, the resin (A) contains an ethylene-containing olefin component and an unsaturated carboxylic acid component as a copolymerization component and the content of the unsaturated carboxylic acid component is 0.1 to 15% by mass, the resin (B) contains an olefin component and an unsaturated carboxylic acid component composed of propylene and butene as a copolymerization component, and the resin (A) and the resin (B) ) of an aqueous dispersion, characterized in that the mass ratio (A/B) is 95/5 to 50/50.

Description

Aqueous dispersions and laminates {AQUEOUS DISPERSION, AND LAMINATE}

[0001] The present invention relates to an aqueous dispersion having excellent adhesion to various substrates and, in particular, to a laminate in which a polyolefin substrate and other substrates are adhered.

Polyolefin resins such as polypropylene resins have excellent electrical properties, mechanical properties, chemical properties, shapeability, hygiene, and recyclability, and are mainly used in automobiles, electricity, packaging, and daily necessities. However, since polyolefin resins generally do not have polar groups in their molecular chains, there is a problem in that adhesion with an adhesive is difficult.

For this reason, when bonding with respect to polyolefin resins, such as a polypropylene resin, using a chlorinated polyolefin resin as an adhesive agent component is proposed. However, since chlorinated polyolefin resins generate harmful substances, such as acid gas, when discarded by incineration, as interest in the environment increases in recent years, the transition to non-chlorine-based binder resins is strongly desired.

In addition, in the field such as a conventional touch panel, a laminated configuration of a touch panel has been produced by attaching an optical polyethylene terephthalate film, a polycarbonate film, and a triacetyl cellulose (TAC) film. However, the optical polyethylene terephthalate film had problems, such as a durability fall and hydrolysis, by the bleeding of an oligomer component. Therefore, recently, a cycloolefin polymer film having high transparency has been widely used instead of the optical polyethylene terephthalate film. Cycloolefin polymer (COP) is a material having excellent properties such as high heat resistance, low dielectric constant and low dielectric loss tangent in addition to high transparency, and is used in various fields such as optical applications, medical applications, automobile applications, packaging applications, and electronic component applications. It's getting a lot of attention. However, since the cycloolefin polymer is also a resin having poor adhesion, an adhesive having good adhesion is desired.

From the background described above, development of an acid-modified polyolefin resin obtained by modifying a polyolefin resin with an acid as a non-chlorine-based binder resin has been carried out, and further studies have been made to water-base acid-modified polyolefin resin without substantially using a surfactant. . For example, Patent Documents 1 and 2 disclose a technique for obtaining an aqueous acid-modified polyolefin resin dispersion without substantially using a surfactant. In addition, Patent Document 3 discloses an aqueous dispersion containing an acid-modified polyolefin resin and a polyester resin, and Patent Document 4 discloses an aqueous dispersion containing two types of acid-modified polyolefin resins having different carbon numbers of olefin components.

International Publication No. 2002/055598 International Publication No. 2004/104090 Japanese Patent Laid-Open No. 2003-327756 Japanese Patent Laid-Open No. 2007-177148

However, the coating films obtained from the aqueous dispersions disclosed in Patent Documents 1 to 3 have room for improvement in adhesion to polyolefin resins such as cycloolefin polymers, and are also inferior in water resistance, alkali resistance and chemical resistance in some cases. Moreover, when the aqueous dispersion containing the acid-modified polyolefin resin and polyester resin disclosed in patent document 3 was stored over a long period of time, a viscosity may raise or gelatinize.

On the other hand, the coating film obtained from the aqueous dispersion containing two types of acid-modified polyolefin resins disclosed in Patent Document 4 has improved adhesion to polyolefin resins such as cycloolefin polymers. It was necessary to press at the bottom, and the adhesion at low temperature was inferior. Further, in the laminate obtained by adhering polyolefin resin, when a bag was prepared and the contents were stored for a long period of time, the interlayer adhesiveness of the laminate was lowered and the content resistance was inferior.

The present invention solves the drawbacks of the prior art, and is an aqueous dispersion comprising an aqueous dispersion of acid-modified polyolefin resin with excellent liquid stability. An object of the present invention is to provide an aqueous dispersion that can be formed by pressing and can produce a laminate excellent in content resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject could be solved by the aqueous dispersion containing specific acid-modified polyethylene resin and specific acid-modified polypropylene resin, and reached this invention.

That is, the summary of this invention is as follows.

(1) an aqueous dispersion comprising an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium,

The acid-modified polyethylene resin (A) contains an ethylene-containing olefin component and an unsaturated carboxylic acid component as a copolymerization component, and the content of the unsaturated carboxylic acid component is 0.1 to 15 mass%,

The acid-modified polypropylene resin (B) contains an olefin component composed of propylene and butene and an unsaturated carboxylic acid component as a copolymerization component,

An aqueous dispersion characterized in that the mass ratio (A/B) of the acid-modified polyethylene resin (A) to the acid-modified polypropylene resin (B) is 95/5 to 50/50.

(2) The aqueous dispersion according to (1), wherein the mass ratio of propylene and butene (propylene/butene) is 60/40 to 95/5.

(3) The aqueous dispersion according to (1) or (2), wherein the acid-modified polyethylene resin (A) further contains a (meth)acrylic acid ester component as a copolymerization component.

(4) The aqueous solution according to any one of (1) to (3), wherein the number average particle diameter of each of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) has a difference of 20 nm or more. dispersion.

(5) A laminate characterized in that a layer formed from the aqueous dispersion according to any one of (1) to (4) is laminated on a substrate.

(6) The laminate according to (5), wherein a substrate of the same type or of a different type is further laminated on the layer laminated on the substrate.

(7) The laminate according to (6), wherein at least one of the substrates is a polypropylene substrate or a cycloolefin polymer substrate.

(Effects of the Invention)

According to the aqueous dispersion of the present invention, by containing a specific acid-modified polyethylene resin (A) and a specific acid-modified polypropylene resin (B), a coating film having good water resistance, alkali resistance and chemical resistance can be obtained, and further, a cycloolefin polymer, etc. A laminate having excellent adhesive strength with a polyolefin resin substrate or various substrates can be obtained by low-temperature pressing, and the bag produced from this laminate has excellent resistance to contents. Moreover, the aqueous dispersion of this invention is excellent in liquid stability. Therefore, the aqueous dispersion of the present invention can be suitably used for various applications including optical films requiring chemical resistance.

Hereinafter, the present invention will be described in detail.

The aqueous dispersion of the present invention contains an acid-modified polyethylene resin (A) and an acid-modified polypropylene resin (B) in a specific ratio in an aqueous medium.

<Acid-modified polyethylene resin (A)>

In the present invention, the acid-modified polyethylene resin (A) contains an ethylene-containing olefin component and an unsaturated carboxylic acid component as a copolymerization component.

It is preferable that it is 50 mass % or more, and, as for content of ethylene in an olefin component, it is more preferable that it is 70 mass % or more. When content of ethylene in an olefin component is less than 50 mass %, characteristics, such as base material adhesiveness derived from a polyethylene resin, may be lost.

Examples of the olefin component other than ethylene include alkenes such as propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and cycloalkenes such as norbornene, and mixtures thereof can also be used. Among them, alkenes having 3 to 6 carbon atoms, such as propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene, are preferable, and alkenes having 3 to 4 carbon atoms, such as propylene, isobutylene, and 1-butene, are more preferable. desirable.

Content of the unsaturated carboxylic acid component as a copolymerization component in acid-modified polyethylene resin (A) needs to be 0.1-15 mass %, It is preferable from an adhesive point that it is 0.1-10 mass %, It is 0.1-5 mass % It is more preferable that it is 0.5-4 mass %, It is still more preferable, It is especially preferable that it is 1-4 mass %. Aqueous dispersion|dispersion of acid-modified polyethylene resin (A) becomes difficult that content of an unsaturated carboxylic acid component is less than 0.1 mass %. On the other hand, when content of an unsaturated carboxylic component exceeds 15 mass %, water resistance, alkali resistance, and chemical-resistance may fall as for the coating film obtained.

The unsaturated carboxylic acid component is an unsaturated carboxylic acid or anhydride thereof. Specifically, unsaturated dicarboxylic acid other than acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc. half esters and half amides of Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are mentioned, and acrylic acid and maleic anhydride are preferable.

The unsaturated carboxylic acid component should just be copolymerized in the acid-modified polyethylene resin (A), and the form is not limited. For example, random copolymerization, block copolymerization, graft copolymerization, etc. are mentioned.

In addition, the acid anhydride component introduced into the acid-modified polyethylene resin (A) tends to take an acid anhydride structure in a dry state, and part or all of it is ring-opened in an aqueous medium containing a basic compound described later, and carboxylic acid or its tends to become salty.

The method for introducing the unsaturated carboxylic acid component into the unmodified polyethylene resin is not particularly limited, and for example, the unmodified polyethylene resin and the unsaturated carboxylic acid component are heated and melted above the melting point of the unmodified polyethylene resin in the presence of a radical generator. Graft copolymerization of an unsaturated carboxylic acid component to an unmodified polyethylene resin by a reaction method or by dissolving an unmodified polyethylene resin and an unsaturated carboxylic acid component in an organic solvent and then heating and stirring in the presence of a radical generator to react how to do it

Examples of the radical generator used for graft copolymerization include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, and di-tert-butyl diperphthalate; and azo compounds such as azobisisobutyronitrile. These may be appropriately selected and used according to the reaction temperature.

Usually, when an unsaturated carboxylic acid component is introduce|transduced into unmodified polyethylene resin by the above method, an unreacted unsaturated carboxylic acid monomer remains in acid-modified polyethylene resin (A). Moreover, when there is much content of the unsaturated carboxylic acid component as a copolymerization component in acid-modified polyethylene resin (A), there exists a tendency for many unreacted unsaturated carboxylic acid monomers to remain|survive.

It is preferable that the acid-modified polyethylene resin (A) contains a (meth)acrylic acid ester component from the reason of improving adhesiveness with various thermoplastic resin base materials including polyolefin resin base materials, such as a polypropylene resin.

It is preferable that content of the (meth)acrylic acid ester component in acid-modified polyethylene resin (A) is 0.5-40 mass %, It is more preferable that it is 1-35 mass %, It is more preferable that it is 3-30 mass % , It is especially preferable that it is 5-25 mass %, and it is most preferable that it is 10-25 mass %. If the content of the (meth)acrylic acid ester component is less than 0.5% by mass, the adhesion to the substrate may decrease, and if it exceeds 40% by mass, the properties derived from the polyethylene resin may be lost and the adhesion to the substrate may decrease. .

Examples of the (meth)acrylic acid ester component include an esterified product of (meth)acrylic acid and an alcohol having 1 to 30 carbon atoms. Among them, an ester product of (meth)acrylic acid and an alcohol having 1 to 20 carbon atoms is preferred from the viewpoint of availability. do. Specific examples of such compounds include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid propyl, (meth) acrylate butyl, (meth) acrylic acid hexyl, (meth) acrylate octyl, (meth) acrylate decyl, ( Lauryl (meth)acrylic acid, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are mentioned. A mixture of these may be used. Among these, (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesion to the substrate, ethyl acrylate and butyl acrylate are more preferable, and ethyl acrylate is Especially preferred. In addition, "(meth)acrylic acid -" means "acrylic acid - or methacrylic acid -".

Moreover, the acid-modified polyethylene resin (A) may contain other components other than the said component in 10 mass % or less of the whole acid-modified polyethylene resin. As other components, maleic acid esters such as dienes, dimethyl maleate, diethyl maleate, and dibutyl maleate, (meth)acrylic acid amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, Vinyl alcohol, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate obtained by saponifying vinyl esters and vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versate with a basic compound, etc. , (meth)acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like, and mixtures thereof can also be used.

Examples of the acid-modified polyethylene resin (A) include an ethylene-(meth)acrylic acid copolymer, an ethylene-(meth)acrylic acid ester-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-propylene-maleic anhydride copolymer. copolymers, ethylene-butene-maleic anhydride copolymers, ethylene-propylene-butene-maleic anhydride copolymers, or those obtained by acrylic modification of acid-modified resins thereof with acrylic acid ester or the like. The polyethylene resin may be chlorinated in the range of 5-40 mass %.

The acid-modified polyethylene resin (A) in the present invention preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 10,000 to 80,000, still more preferably 20,000 to 70,000, and most preferably 30,000 to 60,000. do. When the weight average molecular weight of the acid-modified polyethylene resin (A) is less than 5,000, the adhesion to the substrate decreases or the resulting coating film tends to be hard and brittle. There is this. In addition, the weight average molecular weight of resin can be calculated|required using gel permeation chromatography (GPC) using polystyrene resin as a standard.

In the present invention, a commercially available one may be used as the acid-modified polyethylene resin (A). For example, Du Pont-Mitsui Fluorochemicals Co., Ltd. NUCREL series, Sumitomo Chemical Company, Limited BONDFAST series, Sumitomo Chemical Industry Company Limited BONDINE series, The Dow Chemical Company PRIMACOR series, etc. are mentioned. As the acid-modified polyethylene resin (A), an unsaturated carboxylic acid component introduced into an unmodified polyethylene resin such as NOVATEC series manufactured by Japan Polyethylene Corporation or ZEONEX series manufactured by Prime Polymer Co., Ltd. by a known method may be used as the acid-modified polyethylene resin (A). .

<Acid-modified polypropylene resin (B)>

Next, an acid-modified polypropylene resin (B) is demonstrated.

In the present invention, the acid-modified polypropylene resin (B) contains an olefin component composed of propylene and butene and an unsaturated carboxylic acid component as a copolymerization component.

The olefin component of the acid-modified polypropylene resin (B) must consist of propylene and butene (1-butene, isobutene, etc.) Moreover, the coating film may be inferior in chemical resistance, and the bag produced from a laminated body may become inferior in content resistance.

The mass ratio of propylene and butene in the olefin component (propylene/butene) is 60/40 to from the viewpoint of reducing the dispersed particle diameter of the acid-modified polypropylene resin (B) and improving the adhesion to the polypropylene resin substrate. It is preferable that it is 95/5, and it is more preferable that it is 60/40 - 80/20. When the proportion of propylene is less than 60% by mass or exceeds 95% by mass, the dispersed particle diameter of the acid-modified polypropylene resin (B) becomes large, and aqueous dispersion of the resin may become difficult, and the aqueous dispersion obtained is a polypropylene resin There exists a tendency for adhesiveness to a base material or a cycloolefin polymer base material to fall easily. In addition, since the aqueous dispersion of the present invention is an aqueous dispersion with a small difference in the number average particle diameter of the resin particles of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B), as will be described later, the low-temperature adhesiveness is also may be lowered.

In addition, in this invention, you may mix and use multiple types of acid-modified polypropylene resin (B) as needed.

The content of the unsaturated carboxylic acid component as a copolymerization component in the acid-modified polypropylene resin (B) is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the olefin component composed of propylene and butene from the viewpoint of dispersibility in an aqueous medium. , It is more preferable that it is 0.5-10 mass parts, It is still more preferable that it is 0.5-8 mass parts, It is especially preferable that it is 1-7 mass parts, It is most preferable that it is 1.5-7 mass parts. If the content of the unsaturated carboxylic acid component is less than 0.5 parts by mass, it may be difficult to make the acid-modified polypropylene resin (B) into water. Adhesiveness to a propylene resin base material may fall.

As the unsaturated carboxylic acid component, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, allylsuccinic acid In addition to these, compounds having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit), such as half esters and half amides of unsaturated dicarboxylic acids, can also be used. Among them, maleic anhydride, acrylic acid, and methacrylic acid are preferable, and maleic anhydride is more preferable from the viewpoint of ease of introduction into a polypropylene resin containing propylene and butene (hereinafter referred to as unmodified polypropylene resin).

Accordingly, in the present invention, it is preferable to use a propylene/butene/maleic anhydride terpolymer as the acid-modified polypropylene resin (B).

The unsaturated carboxylic acid component should just be copolymerized in acid-modified polypropylene resin, and the form is not limited. For example, random copolymerization, block copolymerization, graft copolymerization, etc. are mentioned.

In addition, the acid anhydride component introduced into the acid-modified polypropylene resin (B) tends to take an acid anhydride structure in a dry state, and in an aqueous medium containing a basic compound described later, a part or all of it is ring-opened to form a carboxylic acid or its tends to become salty.

The method for introducing the unsaturated carboxylic acid component into the unmodified polypropylene resin is not particularly limited, and for example, the unmodified polypropylene resin and the unsaturated carboxylic acid component are mixed with the unmodified polypropylene resin at a melting point or higher in the presence of a radical generator. Unmodified polypropylene resin with unsaturated carboxylic acid by heating and melting to react, or by dissolving unmodified polypropylene resin and unsaturated carboxylic acid component in an organic solvent and then heating and stirring in the presence of a radical generator to react The method of graft copolymerizing a component is mentioned.

Examples of the radical generator used for graft copolymerization include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide and di-tert-butyl diperphthalate; and azo compounds such as azobisisobutyronitrile. These may be appropriately selected and used according to the reaction temperature.

Usually, when an unsaturated carboxylic acid component is introduce|transduced into an unmodified polypropylene resin by the above method, an unreacted unsaturated carboxylic acid monomer remains in the acid-modified polypropylene resin (B). Moreover, when there is much content of the unsaturated carboxylic acid component as a copolymerization component in acid-modified polypropylene resin (B), there exists a tendency for many unreacted unsaturated carboxylic acid monomers to remain|survive.

The acid-modified polypropylene resin (B) in the present invention may contain components other than the above as needed. Other components include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, maleic acid esters such as dimethyl maleate, diethyl maleate, and dibutyl maleate, ( Alkyl vinyl ethers such as meth)acrylic acid amides, methyl vinyl ether, and ethyl vinyl ether; Vinyl alcohol obtained by saponification with and mixtures thereof may be used.

Generally, it is preferable that content of these other components is 10 mass % or less of acid-modified polypropylene resin (B).

In the present invention, a commercially available one may be used as the acid-modified polypropylene resin (B). For example, TAFTHREN series manufactured by Sumitomo Chemical Company, Limited, TAFMER series manufactured by Mitsui Chemicals, Inc., APAO series (amorphous polyalphaolefin) manufactured by Rextac LLC, Licocene PP series manufactured by Clariant International Ltd., Evonik Degussa VESTOPLAST manufactured by GmbH, etc. are mentioned. Moreover, you may use what introduce|transduced the unsaturated carboxylic component by a well-known method to the unmodified polypropylene resin marketed as an acid-modified polypropylene resin (B).

The acid-modified polypropylene resin (B) in the present invention preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 150,000, still more preferably 20,000 to 120,000, and particularly preferably 30,000 to 100,000. Preferably, it is most preferred that it is 35,000-80,000. If the weight average molecular weight of the acid-modified polypropylene resin (B) is less than 5,000, the adhesion to the substrate decreases or the resulting coating film tends to be hard and brittle. On the other hand, if the weight average molecular weight exceeds 200,000, the resin becomes difficult to water tends to In addition, the weight average molecular weight of resin can be calculated|required using gel permeation chromatography (GPC) using polystyrene resin as a standard.

<Aqueous medium>

The aqueous dispersion of the present invention contains an aqueous medium together with the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B), and the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) are Dispersed or dissolved in an aqueous medium. In this invention, an aqueous medium is a liquid which has water as a main component, and may contain the basic compound and organic solvent mentioned later.

As a basic compound, ammonia or organic amine compound which volatilizes at the time of coating film formation is preferable from the point of water resistance of a coating film, and especially, an organic amine compound with a boiling point of 30-250 degreeC and 50-200 degreeC is preferable. When a boiling point is less than 30 degreeC, the rate of volatilization at the time of aqueous-ization of resin mentioned later increases, and aqueous-ization may not progress completely. When a boiling point exceeds 250 degreeC, it may become difficult to scatter an organic amine compound by drying from a resin coating film, and the water resistance of a coating film may fall.

Specific examples of the organic amine compound include triethylamine, N,N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3 -ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, Monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole, pyridine, etc. are mentioned.

It is preferable that the compounding quantity of a basic compound is 0.5-10 times equivalent with respect to the carboxyl group in acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B), 0.8-5 times equivalent is more preferable, 0.9-3.0 times equivalent This is particularly preferred. When the amount is less than 0.5 equivalents, the effect of adding the basic compound is not observed, and when the amount exceeds 10 equivalents, the drying time at the time of coating film formation may be prolonged or the stability of the aqueous dispersion may be reduced.

In this invention, in order to accelerate|stimulate aqueous-ization of an acid-modified polyethylene resin (A) or an acid-modified polypropylene resin (B), and to make a dispersed particle diameter small, it is preferable to mix|blend a hydrophilic organic solvent at the time of aqueousification. As content of the hydrophilic organic solvent, 50 mass % or less is preferable with respect to the whole aqueous medium, It is more preferable that it is 1-45 mass %, 2-40 mass % is still more preferable, 3-35 mass % is especially preferable. When the content of the hydrophilic organic solvent exceeds 50 mass %, it cannot be regarded as an aqueous medium substantially, and it not only deviates from one of the objectives of the present invention (environmental protection), but also aqueous dispersion depending on the hydrophilic organic solvent used. The stability of the body may be lowered.

As the hydrophilic organic solvent, from the viewpoint of obtaining an aqueous dispersion having good dispersion stability, the solubility in water at 20°C is preferably 10 g/L or more, more preferably 20 g/L or more, and still more preferably 50 g/L or more.

It is preferable that a boiling point is 150 degrees C or less from a viewpoint of efficiently removing from a coating film in the process of film forming as a hydrophilic organic solvent. The hydrophilic organic solvent having a boiling point of more than 150° C. tends to be difficult to scatter from the coating film by drying, and in particular, the water resistance of the coating film during low-temperature drying, adhesion to the substrate, and the like may decrease.

Preferred hydrophilic organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert- alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol; methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone ketones, ethers such as tetrahydrofuran, dioxane, ethyl acetate, acetate-n-propyl, isopropyl acetate, acetate-n-butyl, isobutyl acetate, acetate-sec-butyl, acetate-3-methoxybutyl, Esters such as methyl propionate, ethyl propionate, diethyl carbonate, and dimethyl carbonate; glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol ethyl ether acetate or 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone Alcohol, ethyl acetoacetate, 1, 2- dimethyl glycerol, 1, 3- dimethyl glycerol, trimethyl glycerol, etc. are mentioned.

Among them, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether is preferable because it is more effective in accelerating the aqueous conversion of the acid-modified polyolefin resin.

In the present invention, a plurality of these hydrophilic organic solvents may be mixed and used.

In order to further accelerate|stimulate aqueous-ization of an acid-modified polyethylene resin (A) or an acid-modified polypropylene resin (B), you may further add a hydrophobic organic solvent. As a hydrophobic organic solvent, the solubility with respect to 20 degreeC water is less than 10 g/L, and it is preferable that a boiling point is 150 degrees C or less for the above reasons. Examples of such a hydrophobic organic solvent include olefin solvents such as n-pentane, n-hexane, n-heptane, cycloheptane, cyclohexane and petroleum ether, aromatic solvents such as benzene, toluene and xylene, carbon tetrachloride and halogen-based solvents such as 1,2-dichloroethane, 1,1-dichloroethylene, trichloroethylene, 1,1,1-trichloroethane and chloroform. It is preferable that it is 15 mass % or less with respect to an aqueous dispersion, and, as for the addition amount of these hydrophobic organic solvents, it is more preferable that it is 10 mass % or less, It is more preferable that it is 5 mass % or less. When the addition amount exceeds 15 mass %, gelation etc. may be caused.

<Aqueous Dispersion>

The aqueous dispersion of the present invention contains an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium, and the mass ratio of the acid-modified polyethylene resin (A) to the acid-modified polypropylene resin (B) ( A/B) needs to be 95/5-50/50, and it is preferable that it is 90/10-70/30 from the point of adhesiveness and heat-sealing property. When the content of the acid-modified polypropylene resin (B) is less than 5% by mass, adhesion to a polyolefin resin substrate such as a polypropylene resin or a cycloolefin polymer decreases, and conversely, when it exceeds 50% by mass, adhesion to a substrate other than the polyolefin resin is reduced. Adhesiveness may be impaired.

In the aqueous dispersion containing the acid-modified polyethylene resin (A), the acid-modified polypropylene resin (B) and the aqueous medium of the present invention, the amount of the unsaturated carboxylic acid monomer in the dry residue of the aqueous dispersion is preferably 10,000 ppm or less. and more preferably 5,000 ppm or less, more preferably 3,000 ppm or less, particularly preferably 1,000 ppm or less, and most preferably 300 ppm or less. When an additive described below is included, the dry residue refers to the dried residue of the aqueous dispersion after the addition of the additive.

Usually, when the unsaturated carboxylic acid component is introduced into the unmodified polyethylene resin or unmodified polypropylene resin by the method as described above, the unreacted unsaturated carboxylic acid monomer is the acid-modified polyethylene resin (A) or acid-modified polypropylene. It remains in the resin (B).

When the amount of the unsaturated carboxylic acid monomer contained in the dry residue of the aqueous dispersion exceeds 10,000 ppm, the resulting coating film may be inferior in water resistance, chemical resistance, and adhesiveness. When it exceeds 5,000 ppm especially, adhesiveness and chemical-resistance may be inferior.

According to the present inventors, the amount of unsaturated carboxylic acid monomers in the dry residue of an aqueous dispersion containing only acid-modified polyolefin resin as a solid component is an unsaturated carboxylic acid monomer measured by each acid-modified polyolefin resin raw material before aqueous-conversion. It has been confirmed that it is consistent with the total amount of the amount.

Therefore, it is preferable to use the raw materials of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) constituting the aqueous dispersion so that the total amount of the unsaturated carboxylic acid monomer is 10,000 ppm or less, and 5,000 ppm or less It is more preferable to use it as much as possible.

Although the method for reducing the amount of unsaturated carboxylic acid monomers in the acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B) is not particularly limited, for example, an acid-modified polyethylene resin (A) or an acid-modified polypropylene resin ( A method of depressurizing distillation from B), a method of dissolving an acid-modified polyethylene resin (A) or an acid-modified polypropylene resin (B) in a solvent and reprecipitating to separate them, and an acid-modified polyethylene resin (A) in powder or pellet form Or the method of washing|cleaning the acid-modified polypropylene resin (B) in water or an organic solvent, the method of reducing by the Soxhlet extraction method, etc. are mentioned. Among them, from the viewpoint of operability and reduction efficiency, a method of distillation under reduced pressure, a method of dissolving in a solvent and reprecipitating to separate, and a method of washing in water or an organic solvent in the form of powder or pellets are preferable.

The amount of the unsaturated carboxylic acid monomer in the dry residue of the aqueous dispersion and the amount of the unsaturated carboxylic acid monomer in the acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B) are determined by high-performance liquid chromatography described later. so it can be quantified.

In the aqueous dispersion of the present invention, from the viewpoint of adhesion to the substrate, the difference in the number average particle diameter of the resin particles of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is preferably 20 nm or more, and 50 nm or more. More preferably. When the difference between the number average particle diameters of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is less than 20 nm, the adhesiveness to a polyolefin resin substrate or the like and low-temperature adhesiveness tend to decrease.

Moreover, it is preferable that the aqueous dispersion in this invention does not contain a non-volatile aqueous-forming adjuvant substantially. Although the present invention does not exclude the use of a non-volatile aqueous-forming aid, the acid-modified polyolefin resin can be stably dispersed in an aqueous medium within a weight average particle diameter of 0.15 µm or less even without the use of an aqueous-based aid.

Here, "aqueous-forming aid" is a drug or compound added for the purpose of accelerating aqueousification or stabilizing an aqueous dispersion in the production of an aqueous dispersion, and "non-volatile" means having no boiling point at normal pressure or at normal pressure. It points out that it has a high boiling point (for example, 300 degreeC or more). "Substantially free of a non-volatile aqueous-forming aid" means that such an auxiliary is not used in the production (when aqueous-forming of the resin), and the resulting aqueous dispersion is consequently free of this auxiliary. Therefore, although it is especially preferable that content of this water-based auxiliary agent is zero, it does not interfere even if it contains less than 0.5 mass % with respect to an acid-modified polyolefin resin component in the range which does not impair the effect of this invention.

Examples of the nonvolatile water-based auxiliary in the present invention include an emulsifier, a compound having a protective colloidal action, modified waxes, an acid-modified compound having a high acid value, and a water-soluble polymer, which will be described later.

Examples of the emulsifier include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers, and surfactants are also included in addition to those generally used for emulsion polymerization. Examples of the anionic emulsifier include sulfuric acid ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, and vinyl sulfonates. and phosuccinate, and examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, and ethylene oxide. - A compound having a polyoxyethylene structure, such as a propylene oxide copolymer, or a sorbitan derivative such as polyoxyethylene sorbitan fatty acid ester, etc. are mentioned. Examples of the amphoteric emulsifier include lauryl betaine and lauryl dimethylamine oxide. can be heard

Compounds having a protective colloidal action, modified waxes, acid-modified compounds with high acid values, and water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl skin. Acid-modified polyolefin waxes and their salts having a number average molecular weight of usually 5000 or less, such as rollidone, polyacrylic acid and its salts, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, and carboxyl group-containing polyethylene-propylene wax, and acrylic acid-maleic anhydride copolymer Unsaturated carboxylic acids such as copolymers and salts thereof, styrene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, etc. Carboxyl group-containing polymers having an acid content of 10% by mass or more and their salts, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having an amino group, gelatin, gum arabic, casein, etc. compounds generally used as dispersion stabilizers for fine particles, etc. can be heard

<Method for Producing Aqueous Dispersion>

Next, a method for producing the aqueous dispersion of the present invention will be described.

The method for producing the aqueous dispersion of the present invention is not limited as long as it is a method in which the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) are uniformly mixed and dispersed in an aqueous medium. For example, the aqueous dispersion of the acid-modified polyethylene resin (A) prepared in advance and the aqueous dispersion of the acid-modified polypropylene resin (B) are mixed, and water or a hydrophilic organic solvent is further added as necessary. A method and the method of mixing an acid-modified polyethylene resin (A) and an acid-modified polypropylene resin (B), and performing stirring and heating with water and a solvent are mentioned. In all of the above methods, an aqueous dispersion having a desired component ratio can be easily prepared, but the former method is preferable because it is simpler.

Although the method for producing the aqueous dispersion of the acid-modified polyethylene resin (A) or the aqueous dispersion of the acid-modified polypropylene resin (B) in the present invention is not particularly limited, for example, an acid-modified polyethylene resin (A) in a sealable container ) or acid-modified polypropylene resin (B), the hydrophilic organic solvent, the basic compound, and water, etc. are added, and stirred while maintaining the temperature in the tank at a temperature of about 40 to 150 ° C. to form an aqueous dispersion method and the like.

As the aqueous dispersion of the acid-modified polyethylene resin (A), commercially available ones can be used, and ZAIKTHENE series (ZAIKTHENE A, ZAIKTHENE L) manufactured by SUMITOMO SEIKA CHEMICALS CO., LTD., CHEMIPEARL series (S) manufactured by Mitsui Chemicals, Inc. -100, S-75N, etc.).

The content of the resin comprising the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) in the aqueous dispersion of the present invention is appropriately adjusted depending on the film formation conditions, the target adhesive layer thickness or performance, etc., and is particularly limited Although it does not become necessary, in order to maintain the viscosity of an aqueous dispersion moderately and to obtain a favorable coating film and adhesive layer, it is preferable that it is 1-50 mass %, and it is more preferable that it is 5-40 mass %.

<Additives>

A crosslinking agent can be added to the aqueous dispersion of the present invention in order to further improve various coating film performances such as water resistance, chemical resistance, and adhesiveness. Although it does not specifically limit as a crosslinking agent, A crosslinking agent which has self-crosslinking property, a compound which has a plurality of functional groups reacting with a carboxyl group in a molecule|numerator, a metal complex which has a polyvalent coordination site, etc. can be used, Among these, an oxazoline group containing compound, carbodie A mid group-containing compound, an isocyanate group-containing compound, an epoxy group-containing compound, a melamine compound, a urea compound, an aziridine compound, a zirconium salt compound, a silane coupling agent, etc. are mentioned. Moreover, you may use combining these crosslinking agents.

Although the addition amount of a crosslinking agent is not specifically limited, It is preferable that it is 0.01-80 mass parts with respect to a total of 100 mass parts of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B).

To the aqueous dispersion of the present invention, other polymers, aqueous dispersions thereof, tackifying components, antiblocking agents and the like can be further added.

The aqueous dispersion of other polymers is not particularly limited, but polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinidene chloride, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile- Butadiene resin, polyurethane resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin, phenol resin, silicone resin, epoxy resin, etc. Aqueous dispersion etc. are mentioned. These may be used in mixture of 2 or more types. It is especially preferable to add a polyurethane resin from a viewpoint of adhesiveness with a base material.

Although the content is not specifically limited when using a polyurethane resin as an additive, It is preferable that it is 1-300 mass parts with respect to a total of 100 mass parts of an acid-modified polyethylene resin (A) and an acid-modified polypropylene resin (B).

Although it does not specifically limit as a tackifying component, Rosin, terpenes, petroleum resin, coumarone resin, indene resin, etc. are mentioned.

A pigment or dye may be added to the aqueous dispersion of the present invention depending on the intended use, or the aqueous dispersion of the present invention may be added to a paint or ink. The pigment or dye to be used is not particularly limited, and examples of the pigment include inorganic materials such as titanium dioxide, zinc oxide, chronium oxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, iron oxide, and carbon black. Pigment, azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzoimidazole, perylene, perinone, phthalocyanine, halogenated phthalocyanine, anthrapyridine, Organic pigments, such as a dioxadine type, are mentioned. Examples of the dye include direct dyes, reactive dyes, acid dyes, cationic dyes, butt dyes, mordant dyes, and the like. The said pigment or dye may be contained individually or 2 or more types may be contained.

Moreover, you may add various additives, such as a leveling agent, an antifoamer, an anti-boiling agent, a pigment dispersant, and a ultraviolet absorber, to the aqueous dispersion of this invention as needed. Moreover, you may add organic or inorganic compounds other than the above in the range which does not impair the storage stability of an aqueous dispersion.

<How to use the aqueous dispersion>

Since the aqueous dispersion of the present invention has good adhesion and adhesion to various substrates, a good coating film and adhesive layer can be formed by removing the aqueous medium from the aqueous dispersion.

Since the aqueous dispersion of the present invention has excellent film-forming ability, known film formation methods, for example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush A uniform resin coating film can be formed by adhering to the surfaces of various substrates by uniformly coating the surfaces of various substrates by a coating method or the like, setting at room temperature if necessary, and then subjecting them to drying or heat treatment for drying and baking. As the heating device at this time, a general hot air circulation type oven, infrared heater, or the like may be used. In addition, the heating temperature and heating time are suitably selected depending on the characteristics of the base material, the kind of the crosslinking agent, the compounding amount, etc., and are not particularly limited, and can be used at a heating temperature of about 50 to 250°C, for example. Moreover, in order to advance a crosslinking reaction, you may perform an aging process at about 20-60 degreeC.

Although the thickness of the coating film formed by removing the aqueous medium from the aqueous dispersion of this invention is not specifically limited, It is preferable that it is 0.5-20 micrometers, It is more preferable that it is 3-15 micrometers, It is still more preferable that it is 5-13 micrometers, , it is especially preferable that it is 8-10 micrometers. When the thickness is less than 0.5 µm, the laminate strength is low and the effect as an adhesive is small, and when it exceeds 20 µm, the drying time becomes long.

A layer formed from an aqueous dispersion by the above method can be laminated on a substrate to obtain the laminate of the present invention.

In addition, a coating film formed by removing the aqueous medium from the aqueous dispersion can be laminated by bonding substrates of different types or the same type as an adhesive layer.

Although the bonding conditions are not specifically limited, It is preferable that it is 60 degreeC or more and the temperature is below melting|fusing point of a thermoplastic resin when using a thermoplastic resin film as a base material. As a lamination method, the method of laminating, applying pressure with a hot roll, is mentioned, for example.

<Reference>

The aqueous dispersion of the present invention has excellent adhesion to a polyolefin resin, and as a substrate to which the aqueous dispersion of the present invention is applied, a polyolefin resin substrate such as polyethylene, polypropylene, or cycloolefin polymer is preferable. In addition, the aqueous dispersion of the present invention can be applied to a resin having a relatively low heat resistance, for example, a polyolefin resin substrate having a melting point of 180° C. or less, such as polyethylene or polypropylene, because excellent adhesion is obtained even in heat treatment at a relatively low temperature condition.

As the cycloolefin polymer, for example, in the main chain described in Japanese Patent Application Laid-Open No. 10-120768, JP-A-11-43566, JP 2004-51949 , JP 2004-156048 , etc. and thermoplastic olefin resins having a cyclic olefin skeleton. As a commercial item of a cycloolefin polymer, ARTON by JSR Corporation, ZEONOR by Zeon Corporation, ZEONEX, TOPAS by POLYPLASTICS CO., LTD., APEL by Mitsui Chemicals, Inc., etc. are mentioned.

Examples of the substrate to which the aqueous dispersion of the present invention is applied include, in addition to the polyolefin resin substrate, a film made of a thermoplastic resin, a molded article, paper, synthetic paper, glass, or metal such as aluminum foil.

Examples of the thermoplastic resin other than the polyolefin resin include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene and polyester resins such as phthalate polyethylene succinate, polyglycolic acid, polylactic acid, polycarbonate, and polyarylate, polyurethane resins, polyimide resins, ABS resins, acrylic resins, or mixtures thereof.

As for the shape of the thermoplastic resin constituting the base material, a laminate thereof other than a film or a molded body is exemplified.

The thermoplastic resin film may be an unstretched film or a stretched film, and a manufacturing method is not limited, either. Although the thickness of a thermoplastic resin film is not specifically limited, either, Usually, the range of 5-500 micrometers is used.

The thermoplastic resin film may contain a filler. Although it does not specifically limit as a filler, Calcium carbonate, clay, silica, diatomaceous earth, talc, titanium oxide, barium titanate, barium sulfate, alumina, etc. are mentioned.

The thermoplastic resin film may be subjected to various kinds of functional treatment such as barrier coating, easily adhesive coating, antistatic coating, and ultraviolet shielding coating, and various vapor deposition treatments such as silica, alumina, and aluminum.

Although the combination of the base material to be adhered using the aqueous dispersion of the present invention is not particularly limited, polyolefin resin and metal such as aluminum, polyolefin resin and polyester resin, polyolefin resin and polycarbonate resin, polyolefin resin and acrylic resin, polyolefin resin and a combination of dissimilar materials such as polyamide resin, polyolefin resin and triacetyl cellulose, and a combination of polyolefin resins such as polypropylene, and the aqueous dispersion of the present invention has particularly good adhesion to these substrates.

The use of the aqueous dispersion of the present invention as an adhesive is not particularly limited, but an adhesive for an optical film such as a touch panel, an anchor coating agent, an adhesive for a solar cell back sheet, a vapor deposition film subjected to various deposition treatments such as silica, alumina, aluminum, etc. Adhesive for the deposition surface of the surface, building material such as wall materials, packaging material adhesive, paper container adhesive, cover material adhesive, in-mold transfer foil adhesive, PP steel sheet adhesive, hair transplantation adhesive, secondary battery electrode binder adhesive, Adhesives for secondary battery exteriors, adhesives for belt moles for automobiles, adhesives for automobile members, adhesives for different types of substrates, and the like are exemplified.

Moreover, the aqueous dispersion of this invention can be used suitably also as a coating agent, a primer, a paint, an ink, etc. other than the said adhesive agent. Specific examples include anchor coating agents for PP extrusion lamina, coating agents for secondary battery separators, primers for UV curable coating agents, primers for shoes, primers for automobile bumpers, primers for clear boxes, paints for PP substrates, and fiber bundling agents.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these.

In addition, about various characteristics, the following method measured or evaluated.

1. Characteristics of resin

(1) Composition of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B)

^It calculated|required from 1 H-NMR analysis (made by Varian Medical Systems, Inc., 300 MHz). Resins (A) and (B) were measured at 120°C using _{orthodichlorobenzene (d 4 ) as a solvent.}

(2) Copolymerization amount of unsaturated carboxylic acid component of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B)

The copolymerization amount of the unsaturated carboxylic acid component in the acid-modified polyethylene resin (A) and the copolymerization amount of the unsaturated carboxylic acid component with respect to a total of 100 parts by mass of propylene and butene in the acid-modified polypropylene resin (B) are each infrared absorption spectrum analysis (Perkin Elmer System 2000 Fourier-transform infrared spectrophotometer, the resolution 4㎝ ^{- 1)} was determined by.

(3) Melt index (MFR) of acid-modified polyethylene resin (A)

It measured by the method of JIS 6730 base material (190 degreeC, 2160 g load).

(4) Melting point of acid-modified polyethylene resin (A)

The measurement was performed at a temperature increase rate of 10°C/min using DSC (DSC-7 manufactured by PerkinElmer Co., Ltd.).

(5) Weight average molecular weight of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B)

For the weight average molecular weight, GPC analysis (HLC-8020 manufactured by TOSOH CORPORATION, the column was used by connecting two KF-804L and one KF805L manufactured by Showa Denko KK) was used, and tetrahydrofuran was used as the eluent, flow rate 1 It measured under the conditions of ml/min and 40 degreeC. About 10 mg of resin was dissolved in 5.5 ml of tetrahydrofuran, and what was filtered through a PTFE thin film filter was used as a measurement sample. The weight average molecular weight was calculated|required from the calibration curve created with the polystyrene standard sample. When it was difficult to melt|dissolve in tetrahydrofuran, it melt|dissolved with orthodichlorobenzene.

(6) Amount of unsaturated carboxylic acid monomer of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B)

About 0.05 g of resin pellets refined by freeze grinding were precisely weighed, 20 ml of methanol was used as an extraction solvent, and extraction was performed at room temperature by continuous inversion mixing for 21 hours. High-performance liquid chromatography (HP1100 manufactured by Hewlett-Packard Company, column: Puresil 5 μm C18 120 Å φ 4.6 mm×250 mm (40° C.) )) was quantified.

When the amount of unsaturated carboxylic acid monomer was less than 1000 ppm, the amount of resin pellets was changed to 0.5 g, and it quantified similarly.

The calibration curve was created using a standard sample of an unsaturated carboxylic acid monomer of known concentration.

2. Characteristics of aqueous dispersion of acid-modified polyethylene resin (A) and aqueous dispersion of acid-modified polypropylene resin (B)

(1) solid content concentration

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 determine the solid content concentration.

(2) Number average particle diameter, weight average particle diameter and dispersion degree of resin (A) particles and resin (B) particles

The number average particle diameter (mn) and the weight average particle diameter (mw) were measured using the NIKKISO CO., LTD. product, Nanotrac Wave-UZ152 particle size distribution analyzer. In addition, the refractive index of resin was made into 1.5.

The dispersion degree was calculated based on the following formula.

Dispersity = weight average particle diameter (mw) / number average particle diameter (mn)

(3) Viscosity of acid-modified polypropylene resin (B) aqueous dispersion

The rotational viscosity (mPa*s) in the temperature of 20 degreeC was measured for the aqueous dispersion after 300-mesh filtration using the B-type viscometer (TOKIMEC INC. make, DVL-BII-type digital viscometer).

3. Characteristics of aqueous dispersions

When the base material was used in the evaluation of the following aqueous dispersions, the following were used.

COP-1: Cycloolefin polymer film (ZEONOR ZF-14-100 manufactured by Zeon Corporation, 100 μm thick)

COP-2: cycloolefin copolymer plate (manufactured by POLYPLASTICS CO., LTD., molded product of TOPAS 5013L-10, 10 cm × 5 cm × thickness 2 mm)

CPP: Unstretched polypropylene film (manufactured by Mitsui Chemicals Tohcello. Inc., thickness 50 µm)

PE: unstretched polyethylene film (manufactured by TAMAPOLY CO., LTD., thickness 40㎛)

PET: Biaxially stretched polyethylene terephthalate film (EMBLET PET manufactured by UNITIKA LTD., thickness 50㎛)

PC: polycarbonate plate (manufactured by Nippon Testpanel Co., Ltd., 10 cm × 2 cm × thickness 2 mm)

Ac: Acrylic plate (manufactured by Nippon Testpanel Co., Ltd., 10 cm × 5 cm × thickness 2 mm)

Ny: nylon 6 film (manufactured by UNITIKA LTD., thickness 15㎛)

Al: Aluminum foil (manufactured by Mitsubishi Aluminum Company, Ltd., thickness 25㎛)

(1) Amount of unsaturated carboxylic acid monomer

Except for using about 0.05 g of fine powder obtained by freeze-pulverizing the dry residue obtained by drying the aqueous dispersions prepared in Examples and Comparative Examples, and using the above "1. The amount of the unsaturated carboxylic acid monomer in the aqueous dispersion was measured in the same manner as in the method for measuring the amount of the unsaturated carboxylic acid monomer in the resin pellet described in (6) of "Characteristics of the resin".

(2) liquid stability

The aqueous dispersions prepared in the Examples and Comparative Examples were stored at 50°C for 3 months, and the liquid state was visually evaluated for liquid stability.

○: No change from immediately after production

×: There is thickening or gelation

(3) water resistance

The aqueous dispersion was applied on COP-1 using a Mayer bar so that the thickness after drying might be 2 µm, and dried at 90°C for 1 minute. After leaving the obtained laminated body at 40 degreeC for 1 day, it was immersed in 60 degreeC warm water for 24 hours, and the state of the coating film after air drying was visually evaluated for water resistance.

○: No change in the coating film

△: Cloudy coating

x: The coating film is peeling off

(4) alkali resistance

The aqueous dispersion was apply|coated so that the thickness after drying might be set to 1 micrometer on PET, and it dried at 100 degreeC for 2 minutes. After leaving the obtained laminated body for 1 day, it was immersed in 30 degreeC and the sodium hydroxide aqueous solution of pH 12.0 for 1 day, and the state of the coating film was visually evaluated for alkali resistance.

○: No change in the coating film

×: The coating film is completely dissolved or peeled off

(5) Chemical resistance

The aqueous dispersion was applied on COP-1 using a Mayer bar to have a thickness of about 2 µm after drying, followed by drying at 130°C for 10 minutes. The resulting laminate was immersed in simulated gasoline at 20°C (an isovolume mixture of toluene and isooctane (both manufactured by Wako Pure Chemical Industries, Ltd.) for 24 hours), and then dried. The state of the coating film on COP-1 was visually evaluated for chemical resistance.

○: No change in the coating film

(triangle|delta): Although the coating film did not peel, whitening and blistering were confirmed

x: The coating film is peeling off

(6) Adhesion

The aqueous dispersion was applied on PET using a Mayer bar so as to have a thickness of 2 µm after drying, followed by drying at 120°C for 1 minute. The coated surface of the obtained laminate was divided into 100 pieces in a checkerboard shape. Cellophane Tape (manufactured by Nichiban Co., Ltd.) was attached to 100 divisional surfaces, and peeled off rapidly from the divided coating film was counted and adhesiveness was evaluated.

○: 0 to 5 peels off

△: 6 to 10 peels off

×: 11 or more peels

(7) Peel strength

A measurement sample having a width of 15 mm was cut out from each laminate created by the following method, and a tensile rate of 200 mm/min and a tensile angle of 180° using a tensile tester (Precision Universal Material Testing Machine 2020 Model manufactured by INTESCO Co., Ltd.) The peel strength between the substrates was measured. In addition, peeling strength was set as the pass if it was the following numerical values.

(7.1) Bonding of PET and COP-1

The aqueous dispersion was coated on the corona surface of PET with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. COP-1 was bonded to the adhesive-coated surface of PET, and it pressed at 125 degreeC with a heat press machine (60 second at 0.5 MPa of sealing pressure). If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(7.2) Conjugation of PC and COP-1

The aqueous dispersion was coated on PC with a Mayer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. COP-1 was bonded to the adhesive-coated surface of a PC, and it pressed at 125 degreeC with a heat press machine (60 second at 0.5 MPa of sealing pressure). If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(7.3) Conjugation of Ac and COP-1

The aqueous dispersion was coated on Ac with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 90°C for 1 minute. COP-1 was joined to the adhesive-coated surface of Ac, and it pressed at 90 degreeC with a heat press machine (60 second at 0.5 MPa of sealing pressure). If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(7.4) Bonding of PET and COP-2

The aqueous dispersion was coated on the corona surface of PET with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. COP-2 was bonded to the adhesive-coated surface of PET, and it pressed at 125 degreeC with the heat press machine (60 second at 0.5 MPa of sealing pressure). If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(7.5) Bonding of PE and CPP

The aqueous dispersion was coated on PE with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 90°C for 1 minute. CPP was joined to the adhesive-coated surface of PE, and it pressed at 90 degreeC with a heat press machine (60 second at 0.5 MPa sealing pressure). If the peeling strength was 20 N/15 mm or more, it was set as the pass.

(7.6) Bonding of PET and CPP

The aqueous dispersion was coated on the corona surface of PET with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. CPP was bonded to the adhesive-coated surface of PET, and it pressed at 125 degreeC with a heat press machine (60 second at 0.5 MPa of sealing pressure). If the peeling strength was 15 N/15 mm or more, it was set as the pass.

(7.7) Conjugation of Ny and CPP

The aqueous dispersion was coated with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm on the glossy surface of Ny, and dried at 120°C for 1 minute. CPP was adhere|attached to the adhesive-coated surface of Ny, and it pressed at 125 degreeC with a heat press machine (60 second with a sealing pressure of 0.5 MPa). If the peeling strength was 20 N/15 mm or more, it was set as the pass.

(7.8) bonding of Al and CPP

The aqueous dispersion was coated with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm on the glossy surface of Al, and dried at 120°C for 1 minute. CPP was joined to the adhesive-coated surface of Al, and it pressed at 125 degreeC with a heat press machine (60 second with a sealing pressure of 0.5 MPa). If the peeling strength was 20 N/15 mm or more, it was set as the pass.

(7.9) Bonding of PET and PE

The aqueous dispersion was coated on the corona surface of PET with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. PE was joined to the adhesive-coated surface of PET, and it pressed at 90 degreeC with a heat press machine (60 second with a sealing pressure of 0.5 MPa). If the peeling strength was 20 N/15 mm or more, it was set as the pass.

(7.10) PET and PET bonding

The aqueous dispersion was coated on the corona surface of PET with a Meyer bar so that the thickness of the adhesive layer after drying was 10 µm, and dried at 120°C for 1 minute. PET was bonded to the adhesive-coated surface of PET, and it pressed at 120 degreeC with a heat press machine (60 second at 0.5 MPa sealing pressure). If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(8) Peel strength after content test

Using the laminated body composed of CPP/adhesive layer/PET obtained by the method described in (7.6) above, a bag of 5×10 cm was produced so that the CPP surface was the inner surface. 5 g of Tabasco (registered trademark) was put in the bag as the contents and sealed. After the bag was stored at 50°C for 2 months, it was opened, and the peel strength of the laminate constituting the bag was measured by the method described in (7) to evaluate the content resistance. If the peeling strength was 10 N/15 mm or more, it was set as the pass.

(9) low temperature adhesive

In the bonding method as described in said (7.6), except having changed the press temperature of 125 degreeC by a heat press machine to 70 degreeC, it carried out similarly, and produced the laminated body. The peeling strength of the obtained laminated body was measured by the method as described in (7), and the following reference|standard evaluated low-temperature adhesiveness.

○: 7N/15mm or more

△: 4N/15mm or more, less than 7N/15mm

×: less than 4N/15mm

The aqueous dispersion of the acid-modified polyethylene resin (A) used for preparation of the aqueous dispersion was prepared by the following method.

(Preparation of acid-modified polyethylene resin aqueous dispersion A-1)

60.0 g of acid-modified polyethylene resin (manufactured by Sumitomo Chemical Industry Company Limited, BONDINE HX-8290), 60.0 g of isopropanol, 2.2 g of tree Ethylamine and 177.8 g of distilled water were poured into a glass container, sealed, and stirred with the rotation speed of the stirring blade at 300 rpm. As a result, it was confirmed that the resin granular material was not precipitated at the bottom of the container and was in a floating state. . So, while maintaining this state, after 10 minutes, the heater was turned on and heated. And the system internal temperature was maintained at 120 degreeC, and it stirred for 20 minutes further. After that, it is cooled to room temperature (about 25°C) while stirring with air cooling at a rotation speed of 300 rpm, and then filtered under pressure (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to uniformly acid-modify milky white. A polyethylene resin aqueous dispersion A-1 was obtained.

(Preparation of acid-modified polyethylene resin aqueous dispersion A-2)

In the production of the acid-modified polyethylene resin aqueous dispersion A-1, the same operation was performed except that BONDINE TX-8030 manufactured by Sumitomo Chemical Industry Company Limited was used instead of BONDINE HX-8290 manufactured by Sumitomo Chemical Industry Company Limited as the acid-modified polyethylene resin. A uniform acid-modified polyethylene resin aqueous dispersion A-2 was obtained.

(Preparation of acid-modified polyethylene resin aqueous dispersion A-3)

60.0 g of acid-modified polyethylene resin (PRIMACOR 5980I, manufactured by The Dow Chemical Company), 16.8 g of triethylamine, and 223.2 g of distilled water were mixed with a stirrer equipped with a sealable pressure-resistant 1 liter capacity glass container equipped with a heater. As a result of pouring into the glass container and stirring the stirring blade at a rotational speed of 300 rpm, it was confirmed that the resin granular material was not precipitated at the bottom of the container but was in a floating state. So, while maintaining this state, after 10 minutes, the heater was turned on and heated. And the system internal temperature was maintained at 130 degreeC, and it stirred for further 30 minutes. After that, it was cooled to room temperature (about 25°C) while stirring with air cooling at a rotation speed of 300 rpm, and then filtered under pressure (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and white, acid-modified polyethylene resin An aqueous dispersion A-3 was obtained.

Table 1 shows the composition of the acid-modified polyethylene resin used for production of the acid-modified polyethylene resin aqueous dispersions A-1 to A-3 and the various characteristics of the aqueous dispersions A-1 to A-3.

The acid-modified polypropylene resin (B) used for production of the aqueous dispersion was produced by the following method.

Preparation Example 1: Acid-modified polypropylene resin P-1

280 g of a propylene-butene copolymer (mass ratio: propylene/1-butene = 80/20) was heated and dissolved in 470 g of xylene in a nitrogen atmosphere in a four-necked flask, and then anhydrous as an unsaturated carboxylic acid under stirring while maintaining the system temperature at 140 ° C. 40.0 g of maleic acid and 28.0 g of dicumyl peroxide as a radical generator were added over 2 hours, respectively, and it was made to react for 6 hours after that. After completion of the reaction, the obtained reactant was poured into a large amount of acetone to precipitate a resin.

This precipitated resin was washed once with a triethylamine acetone solution (mass ratio: triethylamine/acetone = 1/4), and then washed with acetone to reduce unreacted maleic anhydride, and then dried in a vacuum dryer. Thus, acid-modified polypropylene resin P-1 was obtained.

Preparation Example 2: Acid-modified polypropylene resin P-2

In Production Example 1, the same operation was performed except that the acetone solution of triethylamine was changed to acetone, and subsequent acetone washing was changed to methanol washing to obtain acid-modified polypropylene resin P-2.

Preparation Example 3: Acid-modified polypropylene resin P-3

In Production Example 1, the same operation was performed except that the addition amount of maleic anhydride was 60.0 g instead of 40.0 g, and the washing step of triethylamine acetone solution and the washing step of acetone were omitted. got

Preparation Example 4: Acid-modified polypropylene resin P-4

In Production Example 1, the same operation was performed to obtain an acid-modified polypropylene resin P-4, except that the addition amount of maleic anhydride was 24.0 g and the addition amount of dicumyl peroxide was 18.5 g.

Preparation Example 5: Acid-modified polypropylene resin P-5

Acid-modified polypropylene resin P-5 was obtained in the same manner as in Production Example 1, except that a propylene-butene copolymer having a mass ratio (propylene/1-butene) of 97/3 was used.

Preparation Example 6: Acid-modified polypropylene resin P-6

Acid-modified polypropylene resin P-6 was obtained in the same manner as in Production Example 1, except that a propylene-butene copolymer having a mass ratio (propylene/1-butene) of 65/35 was used.

Preparation Example 7: Acid-modified polypropylene resin P-7

Acid-modified polypropylene resin P-7 was obtained in the same manner as in Production Example 1, except that a propylene-butene copolymer having a mass ratio (propylene/1-butene) of 50/50 was used.

Preparation 8: Acid-modified polypropylene resin P-8

Acid-modified polypropylene resin P-8 was obtained in the same manner as in Production Example 1 except that a propylene-ethylene copolymer (mass ratio: propylene/ethylene = 92/8) was used instead of the propylene-butene copolymer.

Preparation Example 9: Acid-modified polypropylene resin P-9

Acid-modified polypropylene resin P was performed in the same manner as in Production Example 1 except that a propylene-butene-ethylene copolymer (mass ratio: propylene/1-butene/ethylene = 65/24/11) was used instead of the propylene-butene copolymer. -9 was obtained.

Table 2 shows the properties of the acid-modified polypropylene resin (B) obtained in Production Examples 1 to 9.

An aqueous dispersion of the acid-modified polypropylene resin (B) used for production of the aqueous dispersion was prepared by the following method.

(Preparation of acid-modified polypropylene resin aqueous dispersion B-1)

60.0 g of acid-modified polypropylene resin P-1, 99.0 g of tetrahydrofuran, 11.6 g of N,N-dimethylethanolamine ( DMEA) and 159.4 g of distilled water were poured into a glass container, and as a result of stirring with the rotation speed of the stirring blade set to 300 rpm, precipitation of resin was not confirmed at the bottom of the container, but it was confirmed that it was in a floating state. So, while maintaining this state, after 10 minutes, the heater was turned on and heated. And the system internal temperature was maintained at 130 degreeC, and it stirred for further 60 minutes.

Then, after cooling to room temperature (about 25° C.) while stirring with air cooling at a rotation 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) was performed to produce a whitening turbid acid-modified poly A propylene resin aqueous dispersion B-1 was obtained. At this time, almost no resin remained on the filter.

(Preparation of acid-modified polypropylene resin aqueous dispersion B-2)

60.0 g of acid-modified polypropylene resin P-1, 45.0 g of ethylene glycol-n-butyl ether, 8.0 g of DMEA, and 137.0 g using a stirrer equipped with a sealed, pressure-resistant 1 liter capacity glass container with a heater attached. of distilled water was poured into the glass container, and as a result of stirring with the rotation speed of the stirring blade set to 300 rpm, it was confirmed that the resin was not precipitated at the bottom of the container, but was in a floating state. So, while maintaining this state, after 10 minutes, the heater was turned on and heated. And the system internal temperature was maintained at 160 degreeC, and it stirred for 60 minutes further.

Then, it cooled by air cooling until the internal temperature became 80 degreeC, it opened, and 45.0 g of tetrahydrofuran, 5.0 g of DMEA, and 30.0 g of distilled water were added. It sealed after that, the rotation speed of a stirring blade was made into 300 rpm, the system internal temperature was maintained at 140 degreeC, and it stirred for further 60 minutes.

Then, after cooling to room temperature (about 25° C.) while stirring with air cooling at a rotation 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) was performed, and acid denaturation of whitening turbidity A polypropylene resin aqueous dispersion B-2 was obtained. At this time, almost no resin remained on the filter.

(Preparation of acid-modified polypropylene resin aqueous dispersion B-3)

250 g of aqueous dispersion B-2 and 120 g of distilled water were poured into a 0.5 L two-necked round bottom flask, a mechanical stirrer and a Liebig type cooler were installed, and the flask was heated in an oil bath to distill off the aqueous medium. . As a result of distilling off about 120 g of the aqueous medium, heating was completed and the mixture was cooled to room temperature. After cooling, the liquid component in the flask was filtered under pressure (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polypropylene resin aqueous dispersion B-3.

(Preparation of acid-modified polypropylene resin aqueous dispersion B-4 to 10)

In the method for producing the aqueous dispersion B-2, in place of the acid-modified polypropylene resin P-1, P-2 in B-4, P-3 in B-5, P-4 in B-6, and B- The same operation was performed except that P-5 was used in 7, P-6 was used in B-8, P-7 was used in B-9, and P-8 was used in B-10 to obtain aqueous dispersions B-4 to 10. . In addition, in B-5, the addition amount of the first DMEA was changed from 8.0 g to 12.0 g, and the addition amount of DMEA of the 2nd time was 5.0 g similarly to the manufacturing method of B-2.

(Preparation of acid-modified polypropylene resin aqueous dispersion B-11)

In the method for producing the aqueous dispersion B-1, the same operation was performed except that P-9 was used instead of the acid-modified polypropylene resin P-1 to obtain an aqueous dispersion B-11.

Table 2 shows the various properties of the aqueous dispersions B-1 to B-11.

In the preparation of the aqueous dispersion, the following were used as additives.

-Polyurethane resin: Polyether type polyurethane resin aqueous dispersion (Kusumoto Chemicals, Ltd. make, NeoRez R-600, solid content concentration 33 mass %)

Crosslinking agent: aqueous solution of an oxazoline group-containing compound (manufactured by NIPPON SHOKUBAI CO., LTD., EPOCROS WS-700, solid content concentration of 25% by mass)

Crosslinking agent: aqueous dispersion of epoxy group-containing compound (made by Adeka Corporation, ADEKA RESIN EM-0517, solid content concentration of 51% by mass)

・Aqueous polyester dispersion (U-1): ELITEL KA-3556 manufactured by UNITIKA LTD. (solid content concentration: 30%, number average particle diameter: 11 nm)

Aqueous acrylic dispersion (N-1): NeoCryl A-6045 (manufactured by Kusumoto Chemicals, Ltd., solid content concentration: 40%, number average particle diameter: 120 nm)

Example 1

The acid-modified polyethylene resin aqueous dispersion A-1 and the acid-modified polypropylene resin aqueous dispersion B-1 are blended so that the solid content mass ratio of the acid-modified polyolefin resin aqueous dispersion and the acid-modified polypropylene resin aqueous dispersion is 95/5; , and stirred for 5 minutes at room temperature to obtain an aqueous dispersion. Various performance evaluations were performed using the obtained aqueous dispersion.

Examples 2 to 20, Comparative Examples 1 to 17

As shown in Tables 3 and 4, the type and solid content mass ratio of the acid-modified polyethylene resin (A) aqueous dispersion and the acid-modified polypropylene resin (B) aqueous dispersion were changed, and in Examples 18 to 20, additives were added. and in Comparative Examples 12 to 17, the same operation as in Example 1 was performed except that an aqueous polyester dispersion or an aqueous acrylic dispersion was used instead of the aqueous dispersion of the acid-modified polypropylene resin (B) to obtain an aqueous dispersion.

The results of Examples 1 to 20 and Comparative Examples 1 to 17 are shown in Tables 3 and 4.

The aqueous dispersions of Examples 1 to 20 were excellent in liquid stability, and the obtained coating film was excellent in water resistance, alkali resistance, and chemical resistance, and was excellent in adhesiveness with a large peeling strength with various base materials. Moreover, a laminated body was obtained by low-temperature pressing, and the bag produced from this laminated body was excellent in content resistance. Among them, the coating film obtained from the aqueous dispersion to which a polyurethane resin or a crosslinking agent such as an oxazoline group-containing compound or an epoxy group-containing compound was added further improved the peel strength with respect to various substrates and was more excellent in adhesiveness.

On the other hand, in the aqueous dispersions of Comparative Examples 1 to 7, since the mass ratio of the acid-modified polyethylene resin (A) to the acid-modified polypropylene resin (B) is outside the range stipulated in the present invention, the coating film has a low peel strength from the substrate, , and also the low-temperature adhesiveness may be inferior.

In Comparative Examples 8 to 9, the peel strength from the substrate was good, but the olefin component of the acid-modified polypropylene resin (B) did not consist of propylene and butene as stipulated in the present invention. .

In Comparative Examples 10 to 11, the acid-modified polyethylene resin (A) has a lower peel strength from the substrate because the content of the unsaturated carboxylic acid component is higher than the prescribed amount of the present invention, and the coating film is inferior in water resistance, alkali resistance, and chemical resistance. it was

In the aqueous dispersions of Comparative Examples 12 to 17, since an aqueous polyester dispersion or an aqueous acrylic dispersion was used instead of the aqueous dispersion of the acid-modified polypropylene resin (B), the liquid stability may be poor, and the coating film has alkali resistance. , was inferior in chemical resistance, and the peeling strength with a base material was low, and it was inferior to adhesiveness.

Claims (7)

An aqueous dispersion comprising an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium,
The acid-modified polyethylene resin (A) contains an ethylene-containing olefin component and an unsaturated carboxylic acid component as a copolymerization component, and the content of the unsaturated carboxylic acid component is 0.1 to 15% by mass,
The acid-modified polypropylene resin (B) contains an olefin component composed of propylene and butene and an unsaturated carboxylic acid component as a copolymerization component, and the unsaturated carboxylic acid component is graft copolymerized;
An aqueous dispersion characterized in that the mass ratio (A/B) of the acid-modified polyethylene resin (A) to the acid-modified polypropylene resin (B) is 95/5 to 50/50. The method of claim 1,
An aqueous dispersion, characterized in that the mass ratio of propylene and butene (propylene/butene) is 60/40 to 95/5. 3. The method according to claim 1 or 2,
The acid-modified polyethylene resin (A) further contains a (meth)acrylic acid ester component as a copolymerization component, The aqueous dispersion characterized by the above-mentioned. 3. The method according to claim 1 or 2,
An aqueous dispersion characterized in that the number average particle diameter of each of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) has a difference of 20 nm or more. A laminate characterized in that a layer formed of the aqueous dispersion according to claim 1 or 2 is laminated on a substrate. 6. The method of claim 5,
A laminate, characterized in that the same or different substrates are further laminated on the layer laminated on the substrate. 7. The method of claim 6,
A laminate, wherein at least one of the substrates is a polypropylene substrate or a cycloolefin polymer substrate.