TW201940578A - Aqueous dispersion composition - Google Patents

Abstract

To provide an aqueous dispersion composition which exhibits excellent adhesion not only to polyolefin base materials but also to other plastic base materials, and which is thus useful in applications such as coating materials, inks, coating agents, adhesives, and primers that are used for coating, printing, bonding and coating. An aqueous dispersion composition which contains a modified polyolefin (A), a polyolefin (B) which is different from the modified polyolefin (A), a tackifying agent (C) and an epoxy resin (D).

Description

Aqueous dispersion composition

The present invention relates to an aqueous dispersion composition that exhibits good adhesion to any plastic substrate such as polyolefin, ABS, polycarbonate, polyamide, and FRP.

Polyolefin and ABS are representative of plastic substrates. In addition to their excellent performance, they are lightweight materials. Therefore, they are often used in various molded products such as automotive parts. They are coated for the purpose of surface protection, decoration, and touch improvement. Cloth plastic coating. In the past, this plastic coating is generally an organic solvent-based coating obtained by dissolving a resin in an organic solvent. However, due to the toxicity from organic solvents, flammability and other dangers, and concerns about air pollution, it has gradually been replaced by water-based coatings ( See, for example, Patent Document 1).
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-298932

[Questions to be Solved by the Invention]

However, compared with organic solvent-based coatings, water-based coatings generally have poorer adhesion to plastic substrates, and have particularly poor water resistance. Therefore, in order to ensure sufficient adhesion and water resistance, the types of plastic substrates are limited for each water-based coating, and it is very difficult to respond to polyolefin substrates and other plastic substrates with the same water-based coating.

In view of the above-mentioned problems, the present inventors have made intensive studies and found that by using an aqueous resin dispersion containing a plurality of specific resins, it is not only for polyolefin substrates, but also for ABS, polycarbonate, polyamide, and FRP. After the plastic substrate also exhibits good adhesion, the present invention is completed.
[Solution to the problem]

In order to achieve the above-mentioned problems, the inventors of the present invention have made intensive studies and have proposed the following inventions.

An aqueous dispersion composition containing a modified polyolefin (A), a polyolefin (B) different from the modified polyolefin (A), an adhesion-imparting agent (C), and an epoxy resin (D).

The acid-modified polyolefin (A) is preferably an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).

The aforementioned polyolefin (B) is preferably an ethylene- (meth) acrylate-maleic anhydride copolymer.

The adhesion-imparting agent (C) is preferably at least one selected from a rosin-based resin, a terpene-based resin, a coumarone-indene resin, and a petroleum resin.

The epoxy resin (D) is preferably a bisphenol epoxy resin (D1) and / or a novolac epoxy resin (D2).

Any of the foregoing aqueous dispersion compositions can be used as a coating.

Any of the foregoing aqueous dispersion compositions can be used as an adhesive.
[Effect of the invention]

The aqueous dispersion composition of the present invention not only exhibits good adhesion to polyolefin substrates, but also any plastic substrate such as ABS, polycarbonate, polyamide, FRP, and has excellent water resistance.

Hereinafter, embodiments of the present invention will be described in detail.

<Modified Polyolefin (A)>
The modified polyolefin (A) used in the present invention is preferably an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).

In the aqueous dispersion composition of the present invention, modified polyolefin (A), polyolefin (B) different from modified polyolefin (A), adhesion-imparting agent (C), and epoxy resin (D) are provided. When the total is 100% by mass, the content of the modified polyolefin (A) is preferably 10% by mass or more and 60% by mass or less. When the content of the modified polyolefin (A) is less than 10% by mass, the adhesion to the polyolefin substrate may be deteriorated. When the content of the modified polyolefin (A) is more than 60% by mass, it is suitable for plastics other than polyolefins. The adhesiveness of the base material may be deteriorated.

<Acid-modified polyolefin (A1)>
The acid-modified polyolefin (A1) used in the present invention is not limited, and is preferably obtained by grafting at least one of α, β-unsaturated carboxylic acid and its anhydride with respect to the constituent unit of the polyolefin copolymer. Those are better.

At least one of α, β-unsaturated carboxylic acid and its anhydride, for example, maleic acid, itaconic acid, citraconic acid, and the like. Among these, acid anhydride is preferable, and maleic anhydride is more preferable. More preferable examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene. Copolymers and the like can be used alone or in combination of two or more of these acid-modified polyolefins.

The acid-modified polyolefin (A1) is not limited, but is preferably polyethylene, polypropylene, and a propylene-α-olefin copolymer. A propylene-α-olefin copolymer is a copolymer of α-olefins mainly composed of propylene. As the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate can be used. Among these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited. The propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.

<Acid-modified chlorinated polyolefin (A2)>
The acid-modified chlorinated polyolefin (A2) used in the present invention is not limited, and for example, it is preferably obtained by chlorinating the acid-modified polyolefin (A1).

The method for producing the acid-modified chlorinated polyolefin (A2) is not particularly limited. For example, the acid-modified polyolefin (A1) can be obtained by dissolving a halogenated hydrocarbon such as chloroform and introducing chlorine.

The lower limit of the chlorine content of the acid-modified chlorinated polyolefin (A2) is 5% by mass or more in consideration of the stability of the solution and the adhesion to the polyolefin substrate, the resin substrate, or the metal substrate. , More preferably 8 mass% or more, still more preferably 10 mass% or more, particularly preferably 12 mass% or more, and most preferably 14 mass% or more. Especially in the case of an acid-modified chlorinated homopolypropylene, if it is in the said range, it will show favorable adhesive strength with respect to a polyolefin base material. The upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, still more preferably 35% by mass or less, even more preferably 32% by mass or less, and most preferably 30% by mass or less. When it exceeds the said value, the crystallinity of an acid-modified chlorinated polyolefin may fall and adhesive strength may fall.

The chlorine content of the acid-modified chlorinated polyolefin (A2) can be measured by titration in accordance with JIS K-7229-1995.

The manufacturing method of the modified polyolefin (A) is not particularly limited, such as a radical graft reaction (that is, to generate a radical species for a polymer that becomes a main chain, and use the radical species as a polymerization starting point to make unsaturated carboxylic acid And acid anhydride graft polymerization).

The radical generator is not particularly limited, and an organic peroxide is preferably used. The organic peroxide is not particularly limited, and examples include di-tert-butyl peroxyphthalate, tertiary-butyl hydrogen peroxide, dicumyl peroxide, benzoylperoxide, tert-butyl peroxybenzoate, Peroxy-2-ethylhexanoic acid third butyl ester, trimethyl peroxy tributyl acetate, methyl ethyl ketone peroxide, second third butyl peroxide, lauryl peroxide and other peroxides; azobis Azonitrile such as isobutyronitrile and azobisisopropionitrile.

The amount of acid modification of the modified polyolefin (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.8% by mass or more, and most preferably 1% by mass or more. Moreover, 10 mass% or less is preferable, 8 mass% or less is more preferable, 7 mass% or less is more preferable, 6 mass% or less is more preferable, and 5 mass% or less is most preferable. If it is too small, it may be difficult to sufficiently disperse it in water, and if it is too large, it may adversely affect the water resistance of the coating film.

The amount of acid modification when performing acid modification with maleic anhydride can be determined by FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC). First, maleic anhydride is dissolved at an arbitrary concentration to prepare a calibration curve solution. The FT-IR measurement of the calibration curve solution was performed, and the calibration curve was prepared by using the absorbance of the stretching peak portion (1780 cm ^-1 ) of the carbonyl (C = O) bond of maleic anhydride. The acid-modified polyolefin (A) was dissolved in chloroform, and FT-IR measurement was performed. According to the aforementioned calibration curve, the absorbance of the stretching peak portion (1780 cm ^-1 ) of the carbonyl bond of maleic anhydride was used to determine the acid of maleic anhydride. Modification amount.

The weight average molecular weight (Mw) of the modified polyolefin (A) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, even more preferably in the range of 70,000 to 140,000, and most preferably in the range of 80,000 to 130,000. If it is too small, the cohesive force is weakened and the adhesiveness is sometimes poor. On the other hand, if it is too large, the solubility is lowered, which may cause problems in the production of the aqueous dispersion composition.

In the present invention, the weight average molecular weight is a value measured by a gel permeation chromatography (hereinafter also referred to as GPC. Reference material: polystyrene resin, mobile phase: tetrahydrofuran) in a gas environment at 40 ° C.

The modified polyolefin (A) is preferably one having better crystallinity. Since it is crystalline, it is more cohesive than amorphous, and it is useful because it has excellent adhesion, water resistance, heat resistance, and chemical resistance.

The crystallinity in the present invention refers to a differential scanning calorimeter (hereinafter also referred to as DSC. TA Instrument Japan, Q-2000), and when the temperature is raised from -100 ° C to 250 ° C at 10 ° C / min, This heating process shows a clear meaning of melting peaks. The measurement of the melting point is a value measured using DSC at a rate of 10 ° C./min. To increase the temperature of the melt, cool the resin, and measure the temperature from the peak top temperature of the melting peak at the time of increasing the temperature again.

The melting point (Tm) of the modified polyolefin (A) is preferably in a range of 50 ° C to 120 ° C. The temperature is more preferably in a range of 60 ° C to 100 ° C, and most preferably in a range of 70 ° C to 90 ° C. If it does not reach the said value, the cohesive force from a crystal | crystallization will fall, and adhesiveness, water resistance, heat resistance, and chemical-resistance may be inferior in some cases. On the other hand, when it exceeds the said value, solubility may fall and a problem may arise in the manufacture of an aqueous dispersion composition.

The manufacturing method of the aqueous dispersion of a modified polyolefin (A) is not specifically limited, For example, the following manufacturing methods are mentioned. That is, the modified polyolefin (A) is dissolved in one or more solvents selected from the group consisting of an ether solvent, an alcohol solvent, and an aromatic solvent, and water, and an alkaline substance is added and cooled. Then, these solvents are removed to obtain.

The ether-based solvent is not particularly limited, and examples thereof include tetrahydrofuran (hereinafter also referred to as THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. One of them may be used alone or two or more thereof may be used in combination. Among them, tetrahydrofuran is preferred.

The alcohol-based solvent is not particularly limited, and examples thereof include aliphatic alcohols, aromatic alcohols, and alicyclic alcohols having 1 to 7 carbon atoms. One of them may be used alone or two or more of them may be used in combination. Among them, an aliphatic alcohol having 3 to 5 carbon atoms is preferable, and isopropyl alcohol (hereinafter also referred to as IPA) is more preferable.

Examples of the aromatic solvent include benzene, toluene, xylene, ethylbenzene, cumene, solvent naphtha, and the like. One of them may be used alone or two or more thereof may be used in combination. Among them, toluene is preferred.

The amount of solvent and water can be arbitrarily selected, preferably modified polyolefin: water: solvent = 100: 50 ~ 800: 11 ~ 900 (mass ratio) is ideal, 100: 200 ~ 400: 43 ~ 233 (mass ratio) More ideal. When there is a large amount of water or a solvent, dispersion of the modified polyolefin with water is easy to proceed, but it takes time to concentrate or the volumetric efficiency decreases, so it is economically disadvantageous and impractical. When water is low, it is obviously impossible to disperse. When there are few solvents, the viscosity will increase remarkably during heating and dissolving, and finally, it may not be uniformly dispersed.

The alkaline substance is not particularly limited, and a volatile alkaline substance is preferred, among which ammonia and amines are preferred. The amines are not particularly limited, monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-amine group Ethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, and N, N-dimethylpropanolamine, etc. Particularly preferred are triethylamine and N, N-dimethylethanolamine. These volatile amines can be used alone or in combination of two or more.

The basic substance is preferably 0.5 part by mass or more with respect to 100 parts by mass of the modified polyolefin (A), more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. Moreover, 10 mass parts or less is preferable, 9 mass parts or less is more preferable, 8 mass parts or less is more preferable, and 7 mass parts or less is more preferable. If it is too small, the particle diameter of the dispersed particles of the obtained aqueous dispersion composition is large, and storage stability may be reduced, and if it is too large, the water resistance of the coating film may be reduced.

The temperature at the time of heating and dissolving is not particularly limited, and 50 ° C or higher is preferable. When the temperature is 75 ° C or lower, the boiling point of an organic solvent or lower is used, and it is not necessary to use a pressure vessel for heating and dissolving. There is no special limitation on the dissolution time, usually it can be completely dissolved in 1 to 2 hours.

The aqueous dispersion of the modified polyolefin (A) is not necessary, and an emulsifier may be blended and used within the range not impairing the performance of the present invention, if necessary.

The emulsifier blended in the aqueous dispersion of the modified polyolefin (A) is not particularly limited, and examples thereof include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, or amphoteric emulsifiers, except for emulsification in general. In addition to users during polymerization, surfactants are also included. For example, the anionic emulsifier may include a sulfate ester salt of a higher alcohol, a higher alkyl sulfonate, a higher carboxylic acid salt, an alkyl benzene sulfonate, a polyoxyethylene alkyl sulfate, a polyoxyethylene alkyl phenyl ether sulfate Salt, vinyl sulfosuccinate, etc. Examples of nonionic emulsifiers include polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyalkylene styrenated phenyl ethers such as polyoxyethylene styrenated phenyl ether, and polyoxyethylene nonylphenyl ethers. Polyoxy alkenyl alkyl phenyl ether type, polyoxy alkenyl amine type such as polyoxyethylene stearylamine, polyoxy alkenyl amine type such as polyoxyethylene polyoxypropylene monoamine, polyoxyethylene oleylamine, etc. Polyoxyalkylene fatty acid esters such as oxyalkenyl alkylammonium type, polyoxyethylene monolaurate, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene tridecyl ether, and other ethylene oxide propylene block polymerization Type, ethylene oxide propylene oxide random polymerization type, polyoxyethylene sorbitan monostearate, and other polyoxyethylene sorbitan fatty acid esters. Examples of the amphoteric emulsifier include lauryl betaine, lauryl dimethylamine oxide, and the like. They can be used alone or in combination of two or more.

When the emulsifier is blended, it is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, 4 parts by mass or more, and 5 parts by mass relative to 100 parts by mass of the modified polyolefin (A). More than ideal. In addition, 30 parts by mass or less is preferable, 28 parts by mass or less is more preferable, 25 parts by mass or less is more preferable, 22 parts by mass or less is more preferable, and 20 parts by mass or less is most preferable. If it is too small, emulsification may be difficult, and if it is too large, the water resistance of the coating film may decrease.

The blending method of the emulsifier is not particularly limited. For example, the emulsifier may be blended without dilution with water or the like, and may be blended in the form of a 1-50% by mass aqueous solution. In order to quickly disperse in the aqueous dispersion composition, it is preferable to blend in a form diluted to an aqueous solution of 1 to 50% by mass. Since the emulsifier in the state of an aqueous solution is incorporated in the aqueous dispersion composition, the emulsifier is quickly adsorbed to the particles.

<Polyolefin (B)>
The polyolefin (B) and the modified polyolefin (A) used in the present invention have different compositions. The polyolefin (B) preferably contains ethylene as a constituent unit, more preferably an ethylene-based copolymer containing ethylene as a main component, and most preferably contains ethylene, (meth) acrylate, and maleic anhydride as constituent units. Metacopolymer. The content of the ethylene component in the ethylene-based copolymer containing ethylene as the main component is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more of the ethylene copolymer. Thing. The terpolymer copolymerized polyolefin may be any of a random copolymer, a block copolymer, and a graft copolymer of ethylene, (meth) acrylate, and maleic anhydride, but is preferably a random copolymer.

When the polyolefin (B) used in the present invention is a terpolymer containing ethylene, (meth) acrylate, and maleic anhydride as constituent units, if the ethylene component, (meth) acrylate component, and horse The total content of the anhydride component is 100% by mass. The content of the ethylene component is preferably 50% by mass or more and 95% by mass, more preferably 50% by mass or more and less than 95% by mass, and more preferably 60% by mass or more and 90% by mass or less. It is particularly preferably 70% by mass or more and 85% by mass or less. When the content of the ethylene component is less than 50% by mass, the hydrophobicity of the polyolefin may decrease too much, and the adhesion to the olefin substrate may be reduced. When the content of the ethylene component is more than 95% by mass, the crystallinity of the polyolefin is increased, so that water dispersion may become difficult.

(Meth) acrylates, for example: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Esters, etc. The "(meth) acrylic acid" means "acrylic or methacrylic acid". When the total of the ethylene component, the (meth) acrylate component, and the maleic anhydride component is 100% by mass, the content of the (meth) acrylate component is preferably 5% to 49% by mass, and more preferably 10% by mass. % To 40% by mass, and more preferably 15 to 30% by mass. When the content of the (meth) acrylate component is less than 5% by mass, the copolymerized polyolefin has a high melting point, and it may not be suitable for use in an olefin substrate. When the content of the (meth) acrylic acid ester component is more than 49% by mass, the crystallinity of the polyolefin is significantly reduced, and there is a possibility that the adhesiveness is reduced.

When the total of the ethylene component, the (meth) acrylate component, and the maleic anhydride component is 100% by mass, the content of the maleic anhydride component is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more. 4 Mass% or less, more preferably 1 mass% or more and 3 mass% or less. When the content of the maleic anhydride component is less than 0.01% by mass, the copolymerized polyolefin may become difficult to disperse in water. When the content of the maleic anhydride component is more than 5% by mass, the polarity of the polyolefin increases, and the adhesion to low-polarity substrates such as polyolefins may decrease.

The melting point of the polyolefin (B) is preferably from 50 ° C to 150 ° C, more preferably from 55 ° C to 100 ° C, and even more preferably from 60 ° C to 90 ° C. When the melting point of the copolymerized polyolefin is lower than 50 ° C, the heat resistance when used as an adhesive may be inferior. When the melting point of the polyolefin (B) is higher than 150 ° C, the film-forming property of the coating film is deteriorated, and it may not be suitable for use in a polyolefin substrate.

The MFR (melt flow rate) of polyolefin (B) at 190 ° C and a load of 2160g is preferably 0.1 g to 300 g / 10 minutes, more preferably 1 g to 100 g / 10 minutes, and even more preferably 3 g to 30 g / 10 points. When the MFR is less than 0.1 g / 10 minutes, resin sag may occur when used as an adhesive. When the MFR is more than 300 g / 10 minutes, the moisture permeability to the base material is poor, and the adhesion may be reduced.

The content of the polyolefin (B) in the aqueous dispersion composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and most preferably 18 parts by mass or more based on 100 parts by mass of the modified polyolefin (A). . In addition, it is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, and most preferably 600 parts by mass or less. When it is less than 5 parts by mass, the adhesion to plastic substrates other than polyolefin may be deteriorated. When it exceeds 1,000 parts by mass, the adhesion to polyolefin substrates may be deteriorated.

The polyolefin (B) is preferably used in the form of an aqueous dispersion. Although not necessary, an emulsifier may be blended if necessary. The manufacturing method of the aqueous dispersion of polyolefin (B) is not specifically limited, For example, the method similar to the case of the said modified polyolefin (A) can be used.

<Adhesion imparting agent (C)>
The adhesion-imparting agent used in the present invention is not particularly limited, and a rosin-based resin, a terpene-based resin, a coumarone-indene resin, a petroleum resin, and the like can also be used.

The softening point of the adhesion-imparting agent is not particularly limited. From the viewpoint of adhesion and heat resistance, 60 ° C to 160 ° C is preferable, 70 ° C to 150 ° C is more preferable, and 80 ° C to 140 ° C is more preferable. When the softening point of the adhesion-imparting agent is less than 60 ° C, there is a concern that the heat resistance when used as an adhesive is insufficient. When the softening point of the adhesion-imparting agent exceeds 160 ° C, the moisture permeability to the substrate is poor, and the adhesion may be reduced.
The softening point of the adhesion-imparting agent (C) can be measured by the ring and ball method in accordance with JIS K-5902-1969.

The SP value of the adhesion-imparting agent is also not particularly limited, and an appropriate adhesion-imparting agent may be selected according to the substrate. For example, for polyolefins such as polyethylene and polypropylene, the SP value of the adhesion-imparting agent is preferably 8.4 to 8.9 (J / cm ³ ) ^1/2 based on the value obtained by the calculation formula of Hoy. It is known that the SP value (δ) of a polymer compound such as an adhesion-imparting agent, which is obtained by using the calculation formula of Hoy, can be calculated as follows.
δ (polymer compound) = ρΣE / M
Here, ρ: the density of the polymer compound, M: the molecular weight of the repeating structural unit of the polymer compound, and E: the Mohr condensation energy constant of each of the structural units constituting the polymer compound. The value of E can be the value disclosed in various documents. Examples of the literature describing numerical values include J. Paint Technology vol. 42 76-118 (1970).

The content of the adhesion-imparting agent (C) in the aqueous dispersion composition of the present invention is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more when the modified polyolefin (A) is 100 parts by mass. More than mass parts is more desirable, more than 40 mass parts is more desirable, and more than 90 mass parts is even better. The upper limit is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and even more preferably 500 parts by mass or less. If it is less than 0.5 parts by mass, the adhesiveness is insufficient, and in particular, the adhesiveness with the polyolefin substrate may be deteriorated. Moreover, when it exceeds 1000 mass parts, the film strength of a resin composition will become weak, and there exists a possibility that the adhesiveness with respect to the plastic base material including a polyolefin base material may worsen.

The addition form of the adhesion-imparting agent (C) is not particularly limited, and it is generally preferable to add it in the form of an aqueous dispersion in which the adhesion-imparting agent is dispersed in water in advance. Such an aqueous dispersion of the adhesion-imparting agent may be a commercially available product, or the desired adhesion-imparting agent may be dispersed in water using a disperser or the like and used.

The emulsification method is not particularly limited, and a known emulsification method such as a high-pressure emulsification method and a phase inversion emulsification method can be used.

The above-mentioned high-pressure emulsification method is a method in which the adhesion-imparting agent is first brought into a liquid state, the emulsifier and water are pre-mixed, and the emulsifier is finely emulsified using a high-pressure emulsifier, and then the solvent is removed if necessary. The method for making the adhesion-imparting agent into a liquid state may be heating only, or heating after dissolving in a solvent, or heating after mixing with a non-volatile substance such as a plasticizer, but it is preferable to heat only without using a solvent. . Examples of the solvent include organic solvents capable of dissolving the adhesion-imparting agent such as toluene, xylene, methylcyclohexane, and ethyl acetate.

The above-mentioned phase inversion emulsification method is to heat and melt the adhesion imparting agent, and then add emulsifier and water while stirring to form a W / O emulsion, and then use water addition, temperature change, etc. to make it phase invert to O / W. Emulsion method.

The aqueous dispersion of the adhesion-imparting agent (C) may be used after being blended with an emulsifier within a range that does not impair the performance of the present invention, if necessary, but it is not necessary.

The emulsifier incorporated in the aqueous dispersion of the adhesion-imparting agent (C) is not particularly limited, and examples thereof include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers, except that they are generally used in emulsion polymerization. Others include surfactants. For example, the anionic emulsifiers include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylic acid salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkyl phenyl ether sulfates. Salt, vinyl sulfosuccinate, etc. Examples of nonionic emulsifiers include polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyalkylene styrenated phenyl ethers such as polyoxyethylene styrenated phenyl ether, and polyoxyethylene nonylphenyl ethers. Polyoxy alkenyl alkyl phenyl ether type, polyoxy alkenyl amine type such as polyoxyethylene stearylamine, polyoxy alkenyl amine type such as polyoxyethylene polyoxypropylene monoamine, polyoxyethylene oleylamine, etc. Polyoxyalkylene fatty acid esters such as oxyalkenyl alkylammonium type, polyoxyethylene monolaurate, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene tridecyl ether, and other ethylene oxide propylene block polymerization Type, ethylene oxide propylene oxide random polymerization type, polyoxyethylene sorbitan monostearate, and other polyoxyethylene sorbitan fatty acid esters. Examples of the amphoteric emulsifier include lauryl betaine, lauryl dimethylamine oxide, and the like. These can be used individually or in combination of 2 or more types.

When an emulsifier is blended in the water dispersion of the adhesion-imparting agent (C), the emulsifier is more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more with respect to 100 parts by mass of the adhesion-imparting agent (C). Ideal, 4 mass parts or more is more desirable, and 5 mass parts or more is most desirable. In addition, 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is most preferable. If it is too small, emulsification may become difficult, and if it is too large, the water resistance of the coating film may decrease.

The blending method of the emulsifier is not particularly limited. For example, the emulsifier may be blended without dilution with water or the like, and may be blended in the form of a 1-50% by mass aqueous solution. In order to quickly disperse in the aqueous dispersion composition, it is preferable to blend in a form diluted to an aqueous solution of 1 to 50% by mass. Since the emulsifier in the state of an aqueous solution is incorporated in the aqueous dispersion composition, the emulsifier is quickly adsorbed to the particles.

Commercially available aqueous dispersions of adhesion-imparting agents such as SUPER ESTER E-720, SUPER ESTER E-730-55, SUPER ESTER E-625, SUPER ESTER E-650, SUPER ESTER E-865, SUPER ESTER E- 865NT, SUPER ESTER NS-100H, SUPER ESTER NS-120A, SUPER ESTER NS-125A, TAMANOL E-100, TAMANOL E-200NT, Emulsion AM-1002, Emulsion SE-50 (The above are manufactured by Arakawa Chemical Industries, Ltd.) , HARIESTER SK-508H, HARIESTER SK-816E, HARIESTER SK-822E, HARIESTER SK-501NS, HARIESTER SK-385NS, HARIESTER SK-218NS, HARIESTER SK-370N, HARIESTER SK-323NS (the above are manufactured by HARIA CHEMICALS) , Nanoretto N-1250, Nanoretto N-1050 (the above is made by YASUHARA CHEMICAL (stock)), etc.

＜ Epoxy resin (D) ＞
The epoxy resin (D) used in the present invention is preferably a bisphenol epoxy resin (D1) and / or a novolac epoxy resin (D2).

＜ Bisphenol epoxy resin (D1) ＞
The bisphenol type epoxy resin (D1) used in the present invention is not limited, and there are manufacturers using a condensation reaction between bisphenol and epichlorohydrin, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol Phenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin and the like. These epoxy resins may be used alone or in combination of two or more.

＜ Novolac epoxy resin (D2) ＞
The novolac-type epoxy resin (D2) used in the present invention is not limited. For example, the manufacturer uses a condensation reaction of a phenol novolac resin and epichlorohydrin, such as a phenol novolac-type epoxy resin, a cresol novolac-type epoxy resin Wait. These epoxy resins may be used alone or in combination of two or more.

In the aqueous dispersion composition of the present invention, when the content of the epoxy resin (D) is 100 parts by mass of the modified polyolefin (A), it is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more. 8 parts by mass or more is more preferable. The upper limit is preferably 600 parts by mass or less, more preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and 300 parts by mass or less. If it is less than 2 parts by mass, water resistance may be deteriorated. If it exceeds 600 parts by mass, the composition may gel due to a reaction between the epoxy resin and another resin.

The addition form of the epoxy resin (D) is not particularly limited, and it is usually preferable to add it in the form of an aqueous dispersion in which the epoxy resin is dispersed in water in advance. Such an aqueous epoxy resin dispersion may be a commercially available product, or one obtained by dispersing the desired epoxy resin in water using a disperser or the like may be used.

The emulsification method is not particularly limited, and a known emulsification method such as a high-pressure emulsification method and a phase inversion emulsification method can be used.

The above-mentioned high-pressure emulsification method is a method in which an epoxy resin is first made into a liquid state, an emulsifier is pre-mixed with water, and the emulsifier is finely emulsified using a high-pressure emulsifier, and then the solvent is removed as necessary. The method for making the epoxy resin into a liquid state may be heating only, or heating after dissolving in a solvent, or mixing with a non-volatile substance such as a plasticizer and heating, but it is preferable to heat without using a solvent. . Examples of the solvent include organic solvents capable of dissolving epoxy resins, such as toluene, xylene, methylcyclohexane, and ethyl acetate.

The above-mentioned phase inversion emulsification method is to heat and melt the epoxy resin, and then add emulsifier and water while stirring to form a W / O emulsion, and then use water addition, temperature change, etc. to invert it to O / W. Emulsion method.

The aqueous dispersion of the epoxy resin (D) may be used after being blended with an emulsifier within a range that does not impair the performance of the present invention, but it is not necessary.

The emulsifier incorporated in the aqueous dispersion of the epoxy resin (D) is not particularly limited, and examples thereof include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers, except that they are generally used in emulsion polymerization. Others include surfactants. For example, the anionic emulsifier may include a sulfate ester salt of a higher alcohol, a higher alkyl sulfonate, a higher carboxylic acid salt, an alkyl benzene sulfonate, a polyoxyethylene alkyl sulfate, a polyoxyethylene alkyl phenyl ether sulfate Salt, vinyl sulfosuccinate, etc. Examples of nonionic emulsifiers include polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyalkylene styrenated phenyl ethers such as polyoxyethylene styrenated phenyl ether, and polyoxyethylene nonylphenyl ethers. Polyoxy alkenyl alkyl phenyl ether type, polyoxy alkenyl amine type such as polyoxyethylene stearylamine, polyoxy alkenyl amine type such as polyoxyethylene polyoxypropylene monoamine, polyoxyethylene oleylamine, etc. Polyoxyalkylene fatty acid esters such as oxyalkenyl alkylammonium type, polyoxyethylene monolaurate, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene tridecyl ether, and other ethylene oxide propylene block polymerization Type, ethylene oxide propylene oxide random polymerization type, polyoxyethylene sorbitan monostearate, and other polyoxyethylene sorbitan fatty acid esters. Examples of the amphoteric emulsifier include lauryl betaine, lauryl dimethylamine oxide, and the like. These can be used individually or in combination of 2 or more types.

When the emulsifier is blended in the aqueous dispersion of the epoxy resin (D), the emulsifier is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the epoxy resin (D). The above is more desirable, more than 4 parts by mass is more desirable, and more than 5 parts by mass is most desirable. In addition, 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is most preferable. If it is too small, emulsification may become difficult, and if it is too large, the water resistance of the coating film may decrease.

The blending method of the emulsifier is not particularly limited. For example, the emulsifier may be blended without dilution with water or the like, and may be blended in the form of a 1-50% by mass aqueous solution. In order to quickly disperse in the aqueous dispersion composition, it is preferable to blend in a form diluted to an aqueous solution of 1 to 50% by mass. Since the emulsifier in the state of an aqueous solution is incorporated in the aqueous dispersion composition, the emulsifier is quickly adsorbed to the particles.

Commercially available aqueous dispersions of epoxy resins, such as: JER W2801R70, JER W3435R67, JER W8735R70, JER W1155R55 (the above are manufactured by Mitsubishi Chemical Corporation), EPIKOTE 3520-WY55, EPIKOTE 3540-WY55, EPIKOTE 5003-W55, EPIKOTE 5522-WY55, EPIKOTE 6006-W68 (above manufactured by Hexion Inc), WEX-5002, WEX-5030 (above manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) DENACOL EM-160 (made by NAGASE CHEMTEX) .

<Aqueous dispersion composition>
The aqueous dispersion composition of the present invention is an aqueous dispersion composition containing a modified polyolefin (A), a polyolefin (B), an adhesion-imparting agent (C), and an epoxy resin (D). The modified polyolefin (A), polyolefin (B), adhesion-imparting agent (C), and epoxy resin (D) can be mixed in advance to prepare an aqueous dispersion, or (A), (B), and The respective aqueous dispersions of (C) and (D) are mixed to form an aqueous dispersion composition. Any of (A), (B), (C), and (D) may be water-soluble, or, for example, (A) an aqueous dispersion in which (C) is encapsulated may be used. An aqueous dispersion composition obtained by mixing the respective aqueous dispersions is preferable because the dispersion has good stability. The total content of solid components (A), (B), (C), and (D) is preferably 12 parts by mass or more and more preferably 15 parts by mass or more in 100 parts by mass of the aqueous dispersion composition, 20 mass parts or more is more desirable, 22 mass parts is particularly good, and 25 mass parts or more is most desirable. 60 mass parts or less is preferable, 55 mass parts or less is more preferable, 50 mass parts or less is more preferable, 45 mass parts or less is particularly preferable, and 40 mass parts or less is most preferable. If it is less than 12 parts by mass, the drying of water may be insufficient during coating, and if it exceeds 60 parts by mass, the stability of the aqueous dispersion composition may be insufficient.

In addition, in order to make properties such as water resistance and solvent resistance better, a hardener may be optionally added to the aqueous dispersion composition of the present invention. The hardener is not particularly limited, such as an aqueous polyfunctional carbodiimide resin, an aqueous dispersion of a polyfunctional isocyanate compound, an aqueous polyfunctional oxazoline resin, a water-soluble silane coupling agent containing a polyfunctional silicon group, and an aqueous melamine compound Wait. These hardeners are preferably blended at 2 to 30% by mass based on 100% by mass of the resin in the aqueous dispersion composition of the present invention.

Moreover, various additives, such as a filler, a pigment, a coloring agent, an antioxidant, etc. can be mix | blended with the aqueous dispersion composition of this invention in the range which does not reduce the effect of this invention. The blending amount of these additives is preferably 100% by mass or less with respect to 100% by mass of the resin in the aqueous dispersion composition, more preferably 50% by mass or less, and still more preferably 30% by mass or less. 5 mass% or more is preferable, and 2 mass% or more is more preferable. By being in the said range, the excellent effect of this invention can be exhibited.

The aqueous dispersion composition of the present invention has excellent adhesion to various plastic substrates, so it is used as a primer, coating, printing ink, coating agent, and adhesive when coating, printing, bonding, and coating. it works.
[Example]

The following specifically describes the present invention according to examples, but the present invention is not limited by these examples. In the examples and comparative examples, "parts" are simply expressed as parts by mass. The measurement and evaluation methods used in the present invention are as follows.

1) Determination of the solid content of the emulsion Approximately 1 g of the emulsion of the sample was put in a 50 ml glass weighing bottle and the scale was finely weighed. Next, the weighing bottle filled with the sample was dried in a hot air dryer at 120 ° C for 2 hours, and the taken weighing bottle was placed in a drier and left to cool at room temperature for 30 minutes. Take out the weighing bottle from the drier, finely weigh the mass, and calculate the mass% of the solid content concentration of the emulsion from the weight change (the following formula) before and after the hot air drying.
Emulsion solid content concentration (% by mass) = [(sample mass before hot air drying)-(sample mass after hot air drying)] / (sample mass before hot air drying) x 100

2) The emulsion viscosity was measured using a "Viscometer TV-22" (E-type viscosity meter) manufactured by Toki Sangyo Co., Ltd., and a 0.6g sample was rotor No. 0.8˚ (= 48 ') × R24, amplitude H, speed Measured at 5 rpm and 25 ° C.

3) Emulsion pH was measured using a "pH meter F-52" manufactured by Horiba, Ltd. and measured at 25 ° C. The calibration of the measuring device was performed by Wako Pure Chemical Industries, Ltd., a phthalate pH standard solution (pH: 4.01), a neutral phosphate pH standard solution (pH: 6.86), and a borate pH standard solution ( pH 9.18), and measured at three points.

4) Measurement of the average particle diameter of the emulsion Z Using "ZETA SIZER NANO Nano-ZS Model ZEN3600" manufactured by Malvern, a sample prepared at a concentration of 0.05 g / L was measured 3 times at 25 ° C, and the average value was determined.

Water dispersion of modified polyolefin (A), water dispersion of polyolefin (B), water dispersion of adhesion imparting agent (C), water of epoxy resin (D) used in the following examples and comparative examples The composition of the dispersion is shown in Table 1.

(Manufacturing example 1)
A 1-liter autoclave was charged with 100 parts by mass of a propylene-butene copolymer ("TAFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals Co., Ltd.), 300 parts by mass of toluene, and 15 parts by mass of maleic anhydride, and the temperature was raised to 130 ° C. 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. After the obtained reaction solution was cooled, it was poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Then, the liquid containing the resin is centrifuged to separate and purify the acid-modified propylene-butene copolymer having maleic anhydride graft polymerization from the ungrafted maleic anhydride and low molecular weight substances. Thereafter, it was dried at 70 ° C. for 5 hours under reduced pressure to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, a modified amount of maleic anhydride of 1.0% by mass, a weight average molecular weight of 80,000, and a melting point of 83 ° C). 210 parts by mass of deionized water, 100 parts by mass of PO-1, 110 parts by mass of tetrahydrofuran, 45 parts by mass of isopropanol, and 55 parts by mass of toluene were charged into a flask equipped with a stirrer, and the temperature was raised to 70 ° C. Then, it melt | dissolved by heating at the same temperature for 1 hour. Then, 3.6 parts by mass of N, N-dimethylethanolamine was added, and after slowly cooling to 40 ° C for 1 hour, the organic solvent was distilled off at a reduced pressure of 91 kPa. An opaque maleic anhydride-modified polyolefin aqueous dispersion (a1-1) (aqueous dispersion is also referred to as an emulsion) was obtained. The solid content concentration of the aqueous dispersion (a1-1) was 30% by mass, the viscosity at 25 ° C. was 48 mPa · s, the pH was 8.1, and the average Z particle diameter was 128 nm.

(Manufacturing example 2)
A 1-liter autoclave was charged with 100 parts by mass of polypropylene (homopolypropylene, "PRIMEPOL YPRO (registered trademark) J105G" manufactured by PRIMEPOLYMER (stock)), 300 parts by mass of toluene, and 10 parts by mass of maleic anhydride, and the temperature was raised to 130 ° C. 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. Thereafter, the obtained reaction solution was cooled and then poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. The resin-containing liquid is then centrifuged to separate and purify the acid-modified polypropylene having maleic anhydride graft polymerization and the ungrafted maleic anhydride and low molecular weight substances. Thereafter, it was dried at 70 ° C. for 5 hours under reduced pressure to obtain maleic anhydride-modified polypropylene. Next, a 2L glass-lined reaction tank was charged with 100 parts by mass of maleic anhydride-modified polypropylene and 1700 parts by mass with chloroform, and then sealed. The liquid in the reaction tank was stirred and heated while being dispersed, and dissolved in the tank at a temperature of 120 ° C for 1 hour. After the temperature in the tank was cooled to 110 ° C, 0.5 part by mass of tert-butylperoxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. The temperature in the tank was cooled to 60 ° C., and 1400 parts by mass of chloroform was distilled off, and then 4 parts by mass of p-third butylphenyl glycidyl ether was added as a stabilizer. Thereafter, it was dried to obtain maleic anhydride-modified chlorinated polypropylene (CPO-1, a chlorine content of 24% by mass, a modified amount of maleic anhydride of 1.0% by mass, a weight average molecular weight of 110,000, and a melting point of 78 ° C). 210 parts by mass of deionized water, 100 parts by mass of CPO-1, 110 parts by mass of tetrahydrofuran, 45 parts by mass of isopropanol, 55 parts by mass of toluene, and 10 parts by mass of polyoxyethylene lauryl ether were charged The temperature in the flask with a stirrer was raised to 70 ° C, and the mixture was heated and dissolved at the same temperature for 1 hour. Then, 3.6 parts by mass (2 chemical equivalents) of N, N-dimethylethanolamine was added, and it took 1 hour to slowly cool to 40 ° C, and then the organic solvent was distilled off at a reduced pressure of 91 kPa. An opaque maleic anhydride-modified chlorinated polyolefin aqueous dispersion (a2-1) was obtained. The solid content concentration of the aqueous dispersion (a2-1) was 30% by mass, the viscosity at 25 ° C was 13 mPa ･ s, the pH was 7.8, and the average Z particle diameter was 106 nm.

(Manufacture example 3)
188 parts by mass of deionized water, a copolymerized polyolefin ("REXPEARL (registered trademark) ET330H") made by Japan Polyethylene Corporation, and an ethylene- (meth) acrylate-maleic anhydride terpolymer (mass ratio: 81.5-16.0-2.5), MFR: 10g / 10 minutes, melting point: 86 ° C, 50 parts by mass, 70 parts by mass of tetrahydrofuran, 5 parts by mass of isopropanol, and 5 parts by mass of toluene were charged into an autoclave, and the temperature was raised to 120 ° C Then, it melt | dissolved by heating at the same temperature for 2 hours. Then, 5.0 parts by mass of an emulsifier ("DKS (registered trademark) NL-180"; polyoxyethylene lauryl ether, HLB: 16.1) made by Daiichi Kogyo Pharmaceutical Co., Ltd. was added, and it was dissolved by heating for 1 hour. Thereafter, 2.5 parts by mass of dimethylethanolamine was added, and after dispersing for 1 hour, it was cooled to 40 ° C. Thereafter, the organic solvent / water was distilled off at a reduced pressure of 91 kPa to obtain a cloudy copolymer aqueous polyolefin dispersion (b-1). The solid content concentration of the aqueous dispersion (b-1) was 30.2% by mass, the viscosity at 25 ° C was 17 mPa ･ s, the pH was 8.7, and the average Z particle diameter was 121 nm.

(Manufacturing example 4)
The copolymerized polyolefin was changed to a copolymerized polyolefin made by Japan Polyethylene Corporation ("REXPEARL (registered trademark) ET350X"); an ethylene- (meth) acrylate-maleic anhydride terpolymer (mass ratio: 75.0 -23.0-2.0), MFR: 12 g / 10 minutes, melting point: 73 ° C), and the same procedure as in Production Example 3 was performed to obtain a copolymerized polyolefin aqueous dispersion (b-2). The solid content concentration of the aqueous dispersion (b-2) was 30.3% by mass, the viscosity at 25 ° C was 11 mPa ･ s, the pH was 8.2, and the average Z particle diameter was 97 nm.

As the adhesion-imparting agent (C), SUPER ESTER E-720 (c-1, manufactured by Arakawa Chemical Industries, Ltd., rosin-based resin, solid content concentration: 50% by mass, softening point: 100 ° C), HARIESTER SK-385NS (c- 2. Made by HARIMA CHEMICAL (stock), rosin-based resin, solid content concentration: 50% by mass, softening point: 85 ° C).

As the epoxy resin (D), JER W2821R70 (d-1, manufactured by Mitsubishi Chemical Corporation, bisphenol epoxy resin, solid content concentration of 70% by mass), DENACOL EM-160 (d-2, NAGASE CHEMTEX ( ), Novolac epoxy resin, solid content concentration 50% by mass).

(Adhesiveness of coating film)
After the coating substrate described below was left to stand in a gas environment at 25 ° C for 36 hours, 100 checkerboards were formed on the coating surface with a cutter at 2 mm intervals, and cellophane tape was closely adhered thereto at 60 °. The angle peels off. Use new Saifan tape and peel off, repeat 10 times. After 10 repetitions, the coating surface was rated as 10 points when there was no change, 9 points when peeling occurred for the 10th time, and the following were rated as 8, 7, and 6 points in sequence, and 0 points when peeling for the first time. The results are shown in Table 1.

(Water resistance of coating film)
The coating substrate described later was left to stand in a gas environment at 25 ° C for 36 hours, and then immersed in warm water at 40 ° C for 10 days. After confirming the change of the coating film, evaluation of adhesion was performed. There was no change in the coating film, and when the evaluation of the adhesion was 10 points, it was good, and was rated ○. There was no change in the coating film, and when the adhesion evaluation was 9 points, it was rated as △. When bubbles of the coating film appeared or the evaluation of the adhesion was 8 points or less, it was regarded as bad, and was evaluated as ×. The results are shown in Table 1.

(Example 1)
In a container with a mixer, add (a1-1) 100 parts by mass, (b-1) 100 parts by mass, (c-1) 60 parts by mass, (d-1) 14.3 parts by mass, and 59 parts by mass of deionized water, Stir well. To 100 parts by mass of the total solid content of (A), (B), (C), and (D) of this aqueous dispersion composition, a moisture-permeable agent (OLFINE (registered trademark) E1004, Nissin Chemical Industry (stock) Manufacture) 10 parts by mass as samples for evaluation. The sample for evaluation was applied to a polypropylene substrate (model: TYC1175P G01 Blk, manufactured by Standard Plaque Inc), an ABS substrate (manufactured by NIPPON TESTPANEL), and a polycarbonate substrate (NIPPON TESTPAN EL) using a coating bar. (Product), 6,6-nylon substrate (manufactured by NIPPON TESTPANEL), and FRP substrate (manufactured by NIPPON TESTPANEL), so that the dry film thickness is 5 μm. The coated surface was preliminarily dried in a warm air dryer under a gas environment of 80 ° C for 10 minutes, and then a two-liquid urethane coating was applied by a spray gun, and dried in a warm air dryer under a gas environment of 80 ° C for 35 minutes. A coated substrate was obtained. Each test was performed using this coating base material.

(Examples 2 to 8, Comparative Examples 1 to 4)
The water dispersion composition having the composition shown in Table 1 was subjected to each test in the same manner as in Example 1.

(Comparative example 5)
The maleic anhydride-modified propylene-butene copolymer (PO-1) in Production Example 1 was replaced with an unmodified propylene-butene copolymer (weight average molecular weight 100,000, melting point 80 ° C). As a result, the dispersion was poor. An aqueous dispersion (a3-1) was obtained.

【Table 1】 [Industrial availability]

The aqueous dispersion composition of the present invention exhibits excellent adhesion not only to polyolefin substrates but also to other plastic substrates. Therefore, it is suitable for primers, coatings, inks, etc. during coating, printing, bonding, and coating. Useful as a coating agent and an adhesive.

Claims (7)

An aqueous dispersion composition containing a modified polyolefin (A), a polyolefin (B) different from the modified polyolefin (A), an adhesion-imparting agent (C), and an epoxy resin (D). For example, the aqueous dispersion composition according to the first patent application range, wherein the modified polyolefin (A) is an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2). For example, the aqueous dispersion composition according to item 1 or 2 of the patent application scope, wherein the polyolefin (B) is an ethylene- (meth) acrylate-maleic anhydride copolymer. For example, the aqueous dispersion composition according to item 1 or 2 of the patent application scope, wherein the adhesion-imparting agent (C) is selected from the group consisting of rosin-based resin, terpene-based resin, coumarone-indene resin, and petroleum resin. At least one of them. For example, the aqueous dispersion composition according to item 1 or 2 of the application scope, wherein the epoxy resin (D) is a bisphenol epoxy resin (D1) and / or a novolac epoxy resin (D2). A coating material comprising the aqueous dispersion composition according to any one of claims 1 to 5 of the patent application scope. An adhesive contains an aqueous dispersion composition as set forth in any one of claims 1 to 5 of the scope of patent application.