JP2022077900A - Water dispersion composition and applications thereof - Google Patents

Abstract

To provide a water dispersion composition which achieves good film formation even in a cold and dry condition, and may exhibit excellent water resistance and excellent adhesion to a hardly adhesive substrate such as a polyolefin resin substrate.SOLUTION: The water dispersion composition at least comprises: a component (A), which is a modified polyolefin resin in which at least one selected from α,β-unsaturated carboxylic acids and anhydrides thereof is grafted to a polyolefin resin; and a component (B), which is a hydroxy compound having a boiling point of 180°C or more and a solubility in water of 1.0 or less. The water dispersion composition is useful in various applications such as a primer, an adhesive, a paint binder and an ink binder.SELECTED DRAWING: None

Description

The present invention relates to an aqueous dispersion composition and its use.

The water-based modified polyolefin resin modified with unsaturated carboxylic acid and / or its anhydride is used as a coating pretreatment agent or an adhesive for a polyolefin resin base material which is a poorly adherent base material (for example, patent). Document 1).

Japanese Unexamined Patent Publication No. 2017-160375

However, when a conventional water-based resin is applied as a primer to a base material, dried at low temperature (preheat), and a water-based topcoat is applied, lifting (lifting of the coating film) may occur, and improvement is required. rice field. An object of the present invention is to provide an aqueous dispersion composition which has good film-forming property even under low-temperature drying conditions and can exhibit excellent adhesion and water resistance to a poorly adherent substrate such as a polyolefin resin substrate. Is.

The present invention provides the following [1] to [10].
[1] Component (A): A modified polyolefin resin in which at least one selected from α, β-unsaturated carboxylic acid or an anhydride thereof is grafted to a polyolefin resin, and
Component (B): An aqueous dispersion composition containing at least a hydroxy compound having a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or lower.
[2] The aqueous dispersion composition according to [1], wherein the content of the component (B) is 0.01 to 10% by weight.
[3] The polyolefin resin is one or more polyolefin resins selected from the group consisting of polypropylene, a propylene-butene copolymer, an ethylene-propylene copolymer, and an ethylene-propylene-butene copolymer [1]. Or the aqueous dispersion composition according to [2].
[4] The aqueous dispersion composition according to any one of [1] to [3], wherein the modified polyolefin resin has a weight average molecular weight of 10,000 to 250,000.
[5] Component (C): The aqueous dispersion according to any one of [1] to [4], further containing a hydroxy compound having a boiling point of less than 180 ° C. and a solubility in water of more than 1.0. Composition.
[6] The aqueous dispersion composition according to any one of [1] to [5], wherein the content of the component (C) is 0.01 to 10% by weight.
[7] A primer containing the aqueous dispersion composition according to any one of [1] to [6].
[8] An adhesive containing the aqueous dispersion composition according to any one of [1] to [6].
[9] A binder for a paint containing the aqueous dispersion composition according to any one of [1] to [6].
[10] A binder for ink containing the aqueous dispersion composition according to any one of [1] to [6].

According to the present invention, there is provided an aqueous dispersion composition that has good film-forming properties even under low-temperature drying conditions and can exhibit excellent adhesion and water resistance to a poorly adherent substrate such as a polyolefin resin substrate. ..

[(A) Modified Polyolefin Resin]
The component (A) is a modified polyolefin resin. The modified polyolefin resin is a resin in which at least one selected from α, β-unsaturated carboxylic acid and its anhydride is grafted on the polyolefin resin.

(Polyolefin resin)
Polyolefin resins are usually polymers containing olefin (α-olefin) structural units. As used herein, the olefin structural unit means a structural unit derived from an olefin (α-olefin). Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene and norbornene.

The polyolefin resin may be a single type olefin polymer or a copolymer of two or more types of olefin polymers. When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

The polyolefin resin includes polypropylene (propylene homopolymer), ethylene-propylene copolymer, and propylene-1-butene from the viewpoint of being able to exhibit sufficient adhesion to a non-polar resin substrate such as a polypropylene substrate. Polymers and ethylene-propylene-1-butene copolymers are preferred.

Here, "polypropylene" represents a polymer whose basic unit is a constituent unit derived from propylene. The "ethylene-propylene copolymer" represents a copolymer whose basic unit is a constituent unit derived from ethylene and propylene. The "propylene-1-butene copolymer" represents a copolymer whose basic unit is a constituent unit derived from propylene and butene. The "ethylene-propylene-1-butene copolymer" represents a copolymer whose basic unit is a constituent unit derived from ethylene, propylene and butene. As long as the amount does not significantly impair the original performance of the resin, these (co) polymers may contain a small amount of structural units derived from olefins other than the basic unit.

The polyolefin resin preferably contains 50 mol% or more of the propylene-derived constituent unit in 100 mol% of the constituent unit. When the constituent unit derived from propylene is included in the above range, the adhesiveness to a non-polar resin base material such as propylene resin can be maintained.

When the ethylene-propylene copolymer or the propylene-1-butene copolymer is a random copolymer, preferably, 3 to 50 mol of the ethylene-derived constituent unit or the butene-derived constituent unit is contained in 100 mol% of the constituent unit. %, And the constituent unit derived from propylene is 50 to 97 mol%.

The lower limit of the melting point of the polyolefin resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. When the melting point of the polyolefin resin is 50 ° C. or higher, sufficient coating film strength can be exhibited when the modified polyolefin resin is used for inks, paints and the like. Therefore, the adhesiveness to the base material can be sufficiently exhibited. Further, when used as an ink, blocking during printing can be suppressed. The upper limit thereof is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower. When the melting point of the polyolefin resin is 120 ° C. or lower, it is possible to prevent the coating film from becoming too hard when the modified polyolefin resin is used for inks, paints and the like. Therefore, the coating film can exhibit appropriate flexibility.

As one embodiment of the melting point of the polyolefin resin, 50 to 120 ° C. is preferable, 60 to 110 ° C. is more preferable, and 60 to 100 ° C. is further preferable.

(Α, β-unsaturated carboxylic acid and its anhydride)
The α, β-unsaturated carboxylic acid and its anhydride are usually α, β-unsaturated carboxylic acid, its derivatives and their anhydrides, for example, maleic acid, maleic anhydride, fumaric acid, citraconic acid, anhydrous. Examples thereof include citraconic acid, mesaconic acid, itaconic acid, anhydrous itaconic acid, aconitic acid, anhydrous aconitic acid, anhydrous hymic acid, (meth) acrylic acid, and (meth) acrylic acid ester. The (meth) acrylic acid ester is preferably an ester of (meth) acrylic acid and a hydrocarbon group having 8 to 18 carbon atoms, and is, for example, lauryl (meth) acrylate, tridecyl (meth) acrylate, or octyl (meth) acrylate. , Isodecyl (meth) acrylate. Maleic anhydride is preferable as the α, β-unsaturated carboxylic acid and its anhydride in consideration of the graftability to the polyolefin resin.

The graft weight of α, β-unsaturated carboxylic acid and its anhydride is usually 0.1% by weight or more, preferably 0.2% by weight or more, and more preferably 0.3% by weight or more with respect to the polyolefin resin. be. The upper limit is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less. The graft weight can be determined by, for example, an alkaline titration method, and the graft weight of the (meth) acrylic acid ester can be determined by ¹ H-NMR.

The polyolefin resin may be modified with at least one selected from α, β-unsaturated carboxylic acid and its anhydride, and may be modified with a combination of two or more.

(Graft denaturation)
Examples of the method for modifying a polyolefin resin with α, β-unsaturated carboxylic acid or an anhydride thereof include graft modification (introduction by graft copolymerization). The conditions for graft copolymerization are not particularly limited, and may be carried out according to a known method such as a melting method or a solution method. In the case of the melting method, the operation is simple and the reaction can be performed in a short time. When the solution method is used, a uniform graft polymer with few side reactions can be obtained.

In the case of the melting method, for example, the polyolefin is heated and melted (heated and melted) in the presence of a radical reaction initiator to react. The temperature for heating and melting may be above the melting point and preferably above the melting point and below 300 ° C. Equipment such as a Banbury mixer, a kneader, and an extruder can be used for heating and melting. In the case of the solution method, for example, after dissolving the polyolefin in an organic solvent, the reaction is carried out by heating and stirring in the presence of a radical reaction initiator. As the organic solvent, aromatic solvents such as toluene and xylene are preferable. The temperature during the reaction is preferably 100 to 180 ° C. Examples of the radical reaction initiator used in the melting method and the solution method include organic peroxide compounds and azonitriles. Examples of the organic peroxide compound include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-. Di (tert-butylperoxy) hexane, cumenehydroperoxide, tert-butylhydroperoxide, 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (tert) -Butylperoxy) -Cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy -2-Ethylhexanoate, tert-butylperoxyisopropylcarbonate, cumylperoxyoctate and the like can be mentioned. Examples of azonitriles include 2,2-azobis (2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), and 2,2. -Azobis (4-methoxy-2,4-dimethylvaleronitrile) can be mentioned.

(Chlorination)
The modified polyolefin may be chlorinated.
Examples of the chlorination method include a method of injecting chlorine gas into the copolymer and introducing chlorine atoms. More specifically, the polyolefin, or a polyolefin that has been modified with another modifier, is dispersed or dissolved in a solvent, if necessary, and then in the presence of a catalyst or under irradiation with ultraviolet light, under pressure or normal pressure. This can be done by blowing chlorine gas in a temperature range of 50 to 140 ° C. Examples of the solvent include water and chlorine-based solvents (for example, chloroform, methylene chloride, carbon tetrachloride), and chlorine-based solvents are preferable. The chlorinated solvent may be distilled off by reducing the pressure at the end of chlorination, or may be replaced with another organic solvent. Examples of the catalyst include a radical polymerization initiator. Examples of the radical polymerization initiator include organic peroxide compounds and azonitriles (for example, 2,2-azobisisobutyronitrile). Examples of the organic peroxide compound include t-butyl peroxyoctate, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, and cumenhydro. Peroxide, t-butyl hydroperoxide, 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1 , 1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate , T-Butylperoxy-2-ethylhexanoate, t-butylperoxyisopropylcarbonate, cumylperoxyoctate, combinations of two or more of these, t-butylperoxyoctate, di-t- Butyl peroxide, dicumyl peroxide and dilauryl peroxide are preferred. The amount of the radical polymerization initiator added is preferably 1% by weight or more, more preferably 10% by weight or more, based on the total amount (weight) of the other modifiers added. This makes it possible to maintain a sufficient chlorine content. The upper limit may be 100% by weight or less, more preferably 50% by weight or less. This makes it possible to prevent a decrease in the weight average molecular weight of the modified polyolefin.

When the modified polyolefin is chlorinated, the order of chlorination and modification with α, β-unsaturated carboxylic acid or its anhydride is not particularly limited, but it is preferable to perform chlorination later.
The chlorine content of the chlorinated polyolefin is not particularly limited, but an example is as follows. It is usually 15% by weight or more, preferably 20% by weight or more. The upper limit is not particularly limited, but is usually 45% by weight or less, preferably 40% by weight or less. The chlorine content can be measured based on JIS-K7229. The chlorine content may be appropriately adjusted according to the conditions of, for example, the type of polyolefin resin, the scale of the chlorination reaction, the reaction apparatus used for chlorination, and the like, and can be adjusted by the amount or time of chlorine gas blown.

(Weight average molecular weight)
The weight average molecular weight of the modified polyolefin resin is preferably 200,000 or less, more preferably 180,000 or less, still more preferably 150,000 or less. The lower limit is usually 10,000 or more, preferably 20,000 or more, and more preferably 30,000 or more. The weight average molecular weight can be determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) method.

The component polyolefin resin (A) may be used alone or in combination of two or more.

[(B) High boiling point hydroxy compound]
The component (B) is a hydroxy compound having a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or lower. By adding the component (B), the water resistance of the composition during low temperature drying can be improved. It is presumed that the cause of the lifting of the coating film during low-temperature drying is probably that the primer layer absorbs water from the topcoat paint, and by adding the component (B), such water absorption can be suppressed. it is conceivable that.

As used herein, the hydroxy compound means a compound having at least one hydroxyl group. The hydroxy compound may further contain an ether bond. Examples of the hydroxy compound include alcohols and alkylene glycol monoalkyl ethers (preferably ethylene glycol monoalkyl ethers).

The hydroxy compound of the component (B) has a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or lower. The upper limit of the boiling point is usually 300 ° C. or lower, but is not particularly limited. As described above, the upper limit of the solubility in water is preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.3 or less. The lower limit of solubility in water is usually 0.05 or more, but is not particularly limited. As used herein, the solubility in water refers to the weight (g) of the component (B) that is completely dissolved when the component (B) is added to 100 g of water at 20 ° C.
Examples of hydroxy compounds having a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or lower include ethylene glycol 2-ethylhexyl ether, ethylene glycol monohexyl ether, 2-ethylhexanol, α-terpineol, 1-octanol, and lauryl alcohol. , Cetyl alcohol, stearyl alcohol, oleyl alcohol, diethylene glycol dibutyl ether, diethylene glycol mono2-ethylhexyl ether, preferably ethylene glycol 2-ethylhexyl ether, ethylene glycol monohexyl ether, 2-ethylhexanol.

[Hydroxy compounds other than (C) and (B)]
The component (C) is a hydroxy compound having a boiling point of less than 180 ° C. and a solubility in water of more than 1.0. By using the component (C), the effect of adding the component (B) can be efficiently exhibited.

The hydroxy compound of the component (C) has a boiling point of less than 180 ° C. and a solubility in water of more than 1.0. As a hydroxy compound having a boiling point of less than 180 ° C. and a solubility in water of more than 1.0, the lower limit of the boiling point and the upper limit of the solubility in water are not particularly limited, but the boiling points are usually 120 ° C. or higher and lower than 180 ° C. Solubility in water is 5.0 to easy solubility. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene. Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methyl-3-methoxybutanol can be mentioned, with preference given to ethylene glycol monobutyl ether.

〔composition〕
-Amount of component (B)-
The amount of the component (B) is usually 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more with respect to the aqueous dispersion composition. The upper limit is usually 10% by weight or less, preferably 5% by weight or less. Therefore, it is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, and more preferably 0.1 to 5% by weight.

-Amount of component (C)-
When the component (C) is contained, the amount thereof is usually 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 1% by weight or more with respect to the aqueous dispersion composition. The upper limit is usually 10% by weight or less, preferably 5% by weight or less, and more preferably 3% by weight or less. Therefore, it is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and more preferably 1 to 3% by weight.

-Amount of component (A) (solid content)-
The amount (solid content) of the component (A) is usually 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more with respect to the aqueous dispersion composition. The upper limit is usually 50% by weight or less, preferably 40% by weight or less, and more preferably 35% by weight or less. Therefore, it is usually 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.

-Component (B) + (C)-
When both the components (B) and (C) are contained, the total amount is usually 0.08 to 15% by weight, preferably 1 to 10% by weight.

-Component (B) / (C)-
When both the components (B) and (C) are contained, the ratio (B / C) of the amount of the component (B) to the amount of (C) is usually 0.05 to 3%, preferably 0.1 to 2 %.

[Arbitrary component]
Examples of the other component include an unreacted raw material of the component (A) (unmodified polyolefin resin, α, β-unsaturated carboxylic acid or an anhydride monomer thereof), a resin component other than the component (A), and (B). And solvents other than (C), emulsifiers, stabilizers, basic substances, cross-linking agents, additive components (eg, lower alcohols, lower ketones, lower esters, metal salts, acids, preservatives, leveling agents, etc. Antioxidants, light stabilizers, UV absorbers, dyes, pigments, diluents, inorganic fillers, etc.) can be selected according to the application.

-Other resin components-
Examples of other resin components include urethane resin, epoxy resin, acrylic resin, phenol resin, alkyd resin, polyamide resin, polyimide resin, silicone resin, resin such as vitrified cotton, and a combination of two or more thereof. These resins may be blended as an aqueous product (for example, an aqueous acrylic resin or an aqueous polyurethane resin). The ratio of the compounding amount of the component (A) to the other resin (the total amount when the other resin is 2 or more) is in terms of solid matter, and is usually modified polyolefin resin: other resin = 1 to 99: 99 to 1. It is preferably 10 to 90:90 to 10, more preferably 20 to 80:80 to 20, and even more preferably 30 to 70:70 to 30.

-solvent-
The solvent is usually an aqueous solvent. The aqueous solvent is usually water, and other than (B) and (C), an alcohol solvent, a glycol solvent, a ketone solvent, and an ester solvent may be used in combination. Further, a small amount of an organic solvent (for example, toluene or xylene) may be contained.

-Emulsifier (surfactant)-
As the emulsifier (surfactant), either a nonionic surfactant or an anionic surfactant can be used. Nonionic surfactants are preferably used because the resulting aqueous dispersion composition has better water resistance.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, and polyoxyethylene sorbitan. Examples thereof include fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkyl amines, alkyl alkanolamides, and polyalkylene glycol (meth) acrylates. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkyl amine are preferable.

Examples of the anionic surfactant include an alkyl sulfate ester salt, a polyoxyethylene alkyl ether sulfate salt, an alkylbenzene sulfonate, an α-olefin sulfonate, a methyl taurylate, a sulfosuccinate, an ether sulfonate, and an ether carboxylate. Examples thereof include fatty acid salts, naphthalenesulfonic acid formarin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines and alkylamine oxides. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

The content of the surfactant is preferably small or no additives. The reason for this is that the addition of a surfactant may reduce the film performance when forming a film, or may cause a plastic effect or bleeding phenomenon when a dry film is formed, and blocking may occur. Because.

-Neutralizer-
The aqueous dispersion composition may further contain a neutralizing agent. Thereby, the dispersibility in the composition of the resin such as the component (A) can be further enhanced. Examples of the neutralizing agent include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, isobutylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, and tri. Ethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2 -Methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 2-aminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, morpholin, N-methylmorpholin, N-ethylmorpholin, piperazins, pyrrol, pyridine, sodium hydroxide, water Examples thereof include metal hydroxides such as potassium oxide and magnesium hydroxide. Of these, morpholine, N, N-dimethylethanolamine, N, N-diethylethanolamine, and 2-amino-2-methyl-1-propanol are preferable from the viewpoint of ease of emulsification and dispersion.

The boiling point of the neutralizer at normal pressure is preferably 200 ° C. or lower. If the boiling point is more than 200 ° C., for example, when the aqueous dispersion composition is used as a coating film, it may be difficult to remove the neutralizing agent by the drying treatment in the water removing step. Therefore, the water resistance and moisture resistance of the coating film, especially during low-temperature drying, may deteriorate, or the adhesiveness to a substrate such as a non-polar resin molded product may deteriorate.

The neutralizing agent may be used alone or in combination of two or more. In the case of a combination of two or more kinds, the compounding ratio of each compound is not particularly limited.

In the aqueous dispersion composition, the content of the neutralizing agent is not particularly specified, but it is preferably 3.0 times or less the equivalent of the carboxyl group in the graft modified product. Thereby, an excessive increase in pH of the aqueous dispersion composition can be suppressed. The lower limit is preferably 0.5 times equivalent or more. Thereby, it is possible to suppress an excessive decrease in pH of the aqueous dispersion composition.

-Stabilizer-
Examples of the stabilizer include compounds containing an epoxy ring, such as an epoxy-based stabilizer. Examples of the epoxy-based stabilizer include epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, the following compounds may be mentioned: epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid; oleic acid, tall oil fatty acid, soybean oil. Epoxidized fatty acid esters made by epoxidizing unsaturated fatty acids such as fatty acids; epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; bisphenol A or polyhydric alcohol fused with epichlorohydrin, for example, bisphenol A glycidyl ether. , Ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl Monoepoxy compounds typified by phenylglycidyl ether, tert-butylphenylglycidyl ether, phenolpolyethylene oxide glycidyl ether and the like. The stabilizer may be a compound containing no epoxy ring, for example, metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resin; dibutyltin dilaurate, dibutylmalate and the like. Organic metal compounds; examples include hydrotalcite compounds.

Further, a stabilizer containing no epoxy ring may be used, and for example, metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resin; organic metals such as dibutyltin dilaurate and dibutylmalate. Compounds; Examples thereof include hydrotalcite compounds.

The content of the stabilizer is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, based on 100% by weight of the modified polyolefin resin. Thereby, the stabilizing effect can be satisfactorily exhibited. The upper limit is preferably 15% by weight or less, more preferably 12% by weight or less, still more preferably 10% by weight or less. This makes it possible to satisfactorily develop the adhesiveness to a substrate such as polyolefin.

[Physical characteristics]
-viscosity-
The viscosity of the aqueous dispersion composition is preferably 1 to 200 mPa · s, more preferably 1 to 100 mPa · s. In the present specification, the viscosity is a measured value at 25 ° C. by a B-type viscometer.

-Average particle size-
The average particle size of the resin dispersed in the aqueous dispersion composition is preferably 300 nm or less, more preferably 200 nm or less. If it exceeds 300 nm, the storage stability of the aqueous dispersion composition and the compatibility with other resins may deteriorate. In addition, the physical characteristics of the film such as adhesion to the substrate, solvent resistance, water resistance, and blocking resistance when the film is formed may be deteriorated. The average particle size can be adjusted by conditions such as the composition of the modified polyolefin resin, the amount of the dispersion medium, the amount of the emulsifier added, the type, and the stirring power at the time of dispersion. In the present specification, the average particle size is a value obtained by measuring the particle size distribution using the light diffusion method. By increasing the amount of the emulsifier added, the particle size can be reduced as much as possible. However, by increasing the amount of the emulsifier added, the physical characteristics of the film such as adhesion to the substrate, water resistance, and gas hole resistance tend to decrease.

-PH-
The pH of the aqueous dispersion composition is preferably 5 or more, more preferably pH 6 to 11. If the pH is less than 5, neutralization may be insufficient and the modified polyolefin resin may not be dispersed in water. Further, even when dispersed, precipitation and separation are likely to occur over time, and storage stability may be inferior. On the other hand, if the pH exceeds 11, problems may occur in compatibility with other components and work safety. The pH can be adjusted by the amount of neutralizing agent added when preparing the aqueous dispersion composition.

-Melting point (Tm)-
The Tm of the aqueous dispersion composition is preferably 50 ° C. or higher and lower than 120 ° C., more preferably 60 ° C. or higher and lower than 110 ° C., and more preferably 60 ° C. or higher and lower than 100 ° C. When Tm is 50 ° C. or higher, sufficient water resistance under high temperature conditions can be further improved. On the other hand, when the melting point is less than 120 ° C., good film forming property at the time of baking the coating film can be ensured. In the present specification, the Tm of the dispersion composition is a dried product obtained by drying the dispersion composition at 40 ° C. for 24 hours, and using DSC (manufactured by TA Instruments) as in the case of the above-mentioned modified polyolefin resin Tm. Can be measured using.

[Use]
The aqueous dispersion composition of the present invention can function as an intermediate medium for a base material having low adhesiveness and difficult to apply such as a paint, for example, a non-polar resin molded product. For example, it is also useful as an adhesive between polyolefin-based substrates such as polypropylene and polyethylene, which have poor adhesiveness, regardless of whether or not the surface of the substrate such as a non-polar resin molded product is subjected to surface treatment such as plasma treatment or corona treatment. Can be used without.

Further, by laminating the dispersion composition of the present invention on the surface of a non-polar resin molded product such as a polyolefin-based substrate by a hot melt method and further applying a paint or the like on the dispersion, the adhesion stability of the paint and the like can be obtained. Can be improved.

Further, it is also suitable for polar substrates such as polyester such as polyethylene terephthalate, polyurethane and polyamide.

That is, the aqueous dispersion composition of the present invention can be suitably used as a primer, a paint, an ink, an adhesive and the like.

[Method for producing aqueous dispersion composition]
The method for producing the aqueous dispersion composition is not particularly limited. For example, a method including at least emulsification by blending the components (A) to (B), preferably the components (A) to (C) can be mentioned. By adding the component (B) at the time of emulsification, a high boiling point solvent can be encapsulated in the particles, whereby the component (B) can be uniformly distributed on the coating film at the time of film formation, and the obtained aqueous dispersion composition can be obtained. It is presumed that the water resistance effect of After emulsification, if necessary, the components (B) and (C) are distilled off leaving a part thereof, and then an aqueous solvent is usually added and dispersed in the system to obtain an aqueous dispersion composition. be able to. When a neutralizing agent is used, it is preferable to add the neutralizing agent when blending the components (A) to (C). When the dispersion composition contains other resin components, it is preferable to add the resin components after the above dispersion step. For example, after the dispersion step, a resin component blending step may be performed in which the resin component is blended and the solid content is adjusted as necessary (for example, a dispersion medium is added and diluted).

Hereinafter, the present invention will be described in detail with reference to Examples. The following examples are for the purpose of suitably explaining the present invention, and do not limit the present invention. Unless otherwise specified, the method for measuring the physical characteristic value is the measurement method described below.

[Example 1]
In a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, the component (A): propylene-butene random copolymer [P-B] (propylene component 70 mol%, butene component 30 mol%). ), Maleic anhydride [MAH] modified polyolefin resin (weight average molecular weight [Mw] 150,000, Tm = 75 ° C.) 100 g, surfactant Emulgen 420 (polyoxyethylene oleyl ether, manufactured by Kao Co., Ltd.) 10 g, toluene 45 g , 5 g of ethylene glycol 2-ethylhexyl ether and 45 g of component (C): ethylene glycol monobutyl ether were added and kneaded at an internal temperature of 95 ° C. for 60 minutes. Then, 4 g of a 90% aqueous solution of 2-amino-2-methyl-1-propanol [AMP-90] was added and kneaded for 30 minutes, and then 341 g of deionized water at 90 ° C. was added over 90 minutes. Subsequently, after removing a part of toluene and component (B): ethylene glycol 2-ethylhexyl ether and component (C): ethylene glycol monobutyl ether under reduced pressure, the mixture is cooled to room temperature with stirring, and solidified with deionized water. A modified polyolefin resin aqueous dispersion composition was obtained in which the amount was adjusted to 30% by weight. The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 139 nm and a viscosity of 14 mPa · s. Further, as a result of confirming the content of the component (B): ethylene glycol 2-ethylhexyl ether and the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin water dispersion composition by gas chromatography, the modified polyolefin resin water dispersion was performed. It was 0.9% by weight and 2.07% by weight, respectively, with respect to the body composition.

[Example 2]
A modified polyolefin resin aqueous dispersion composition was obtained by the same operation as in Example 1 except that the component (B) was changed to ethylene glycol monohexyl ether. The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 136 nm and a viscosity of 16 mPa · s. Further, as a result of confirming the content of the component (B): ethylene glycol monohexyl ether and the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition by gas chromatography, the modified polyolefin resin aqueous dispersion was obtained. It was 1.09% by weight and 2.14% by weight, respectively, based on the composition.

[Example 3]
The operation was the same as in Example 1 except that the component (B) was changed to 2-ethylhexanol, the amount of the component (C): ethylene glycol monobutyl ether was changed to 40 g, and 5 g of isopropyl alcohol was added. A modified polyolefin resin aqueous dispersion composition was obtained. The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 159 nm and a viscosity of 13 mPa · s. Further, as a result of confirming the content of the component (B): 2-ethylhexanol and the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition by gas chromatography, the modified polyolefin resin aqueous dispersion composition was obtained. It was 0.12% by weight and 1.26% by weight, respectively, with respect to the product.

[Example 4]
Component (B): The amount of ethylene glycol 2-ethylhexyl ether added was changed to 10 g, component (C): the amount of ethylene glycol monobutyl ether added was changed to 40 g, and 5 g of isopropyl alcohol was added. A modified polyolefin resin aqueous dispersion composition was obtained by the same operation. The average particle size of the obtained modified polyolefin resin aqueous dispersion composition was 170 nm and 56 mPa · s. Further, as a result of confirming the content of the component (B): ethylene glycol 2-ethylhexyl ether and the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin water dispersion composition by gas chromatography, the modified polyolefin resin water dispersion was performed. It was 1.77% by weight and 0.98% by weight, respectively, based on the body composition.

[Example 5]
Component (B): A modified polyolefin resin aqueous dispersion composition was obtained by the same operation as in Example 4 except that the amount of ethylene glycol 2-ethylhexyl ether added was changed to 15 g. The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 190 nm and a viscosity of 85 mPa · s. Further, as a result of confirming the content of the component (B): ethylene glycol 2-ethylhexyl ether and the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin water dispersion composition by gas chromatography, the modified polyolefin resin water dispersion was performed. It was 2.8% by weight and 2.2% by weight, respectively, based on the body composition.

[Comparative Example 1]
A modified polyolefin resin aqueous dispersion composition was obtained by the same operation as in Example 1 except that the component (B) was not used. The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 143 nm and a viscosity of 9 mPa · s. Further, as a result of confirming the content of the component (C): ethylene glycol monobutyl ether in the modified polyolefin resin aqueous dispersion composition by gas chromatography, 0.89% by weight with respect to the modified polyolefin resin aqueous dispersion composition. Met.

[Comparative Example 2]
A modified polyolefin resin aqueous dispersion composition was obtained by the same operation as in Example 1 except that diethylene glycol monoethyl ether was used as a high boiling point solvent instead of the component (B). The obtained modified polyolefin resin aqueous dispersion composition had an average particle size of 166 nm and a viscosity of 18 mPa · s. Further, as a result of confirming the content of the component (C): ethylene glycol monobutyl ether and the other component: diethylene glycol monoethyl ether in the modified polyolefin resin aqueous dispersion composition by gas chromatography, the modified polyolefin resin aqueous dispersion composition was obtained. On the other hand, it was 0.9% by weight and 0.9% by weight, respectively.

[Average particle size (nm)]
The average particle size was measured using a Zetasizer Nano ZS (manufactured by Malvern), which is a measuring device using a dynamic light scattering method. The emulsifying property was evaluated according to the following evaluation criteria.
(Evaluation criteria: emulsifying property)
〇: Average particle diameter less than 180 nm Δ: Average particle diameter 180 or more and less than 250 nm nm ×: Average particle diameter more than 250 μm or poor emulsification

[Viscosity measurement (mPa · s)]
The measurement was performed using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of a measurement temperature of 25 ° C. and a rotor rotation speed of 60 rpm.

[Adhesive force measurement]
<Preparation of test piece>
The surface of the ultra-high rigidity polypropylene plate is degreased with isopropyl alcohol, and a modified polyolefin resin aqueous dispersion composition (adding 1.5% of a wetting agent to the appearance) is spray-painted so that the dry film thickness is 15 or more and 20 μm or less. , 80 ° C. for 5 minutes. After allowing to stand at room temperature for 10 minutes, the topcoat paint was mixed with a predetermined curing agent, the viscosity was adjusted with a special thinner, and then spray coating was performed so that the dry film thickness was 100 μm. Next, a baking treatment was performed at 80 ° C. for 30 minutes to prepare a test piece. The following tests were performed using this test piece.

<Adhesive force measurement>
Tensilon (manufactured by Orientec Co., Ltd./RTG-1210) was used for the adhesion measurement. The coating film obtained by the spray coating was cut into a width of 10 mm, and the adhesive strength to the substrate was measured. The peeling conditions were a peeling angle of 180 ° and a peeling speed of 50 mm / min, and evaluation was performed according to the following evaluation criteria.
(Evaluation criteria)
〇: 900 gf / cm or more ×: less than 900 gf / cm

[Water resistance test]
<Preparation of test piece>
The surface of the ultra-high rigidity polypropylene plate is degreased with isopropyl alcohol, and a modified polyolefin resin aqueous dispersion composition (adding 1.5% of wettable agent to the appearance) is spray-coated so that the dry coating film is 15 or more and 20 μm or less. , 60 ° C. for 5 minutes. After allowing to stand at room temperature for 10 minutes, it was baked at 60 ° C. or 70 ° C. for 30 minutes to prepare a test piece. The following tests were performed using this test piece.

<Water resistance test>
Approximately 0.1 ml of deionized water was dropped onto the test piece obtained by the spray coating, covered with a petri dish and held for 3 minutes, then the ion-exchanged water was removed, and the appearance of the coating film (presence or absence of blister generation, etc.) was determined according to the following criteria. Evaluated according to. The test was conducted twice.
(Evaluation criteria: Appearance of coating film)
〇: No abnormality at baking temperatures of 60 ° C and 70 ° C Δ: Blister generated only at baking temperature of 60 ° C ×: Blister generated at baking temperatures of 60 ° C and 70 ° C

From Tables 1 and 2, Comparative Example 1 in which component (B) was not used, and comparative examples in which other components having a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or higher were used instead of component (B). In the example using the component (B), the appearance of the coating film after the water resistance test was better than that in 2. These results show that the modified polyolefin resin aqueous dispersion composition of the present invention exhibits good adhesion to a substrate such as a polyolefin resin substrate even at a low baking temperature, and exhibits excellent water resistance. , Shows that it can have good film-forming properties.

Claims (10)

Component (A): A modified polyolefin resin in which at least one selected from α, β-unsaturated carboxylic acid or an anhydride thereof is grafted to a polyolefin resin, and
Component (B): An aqueous dispersion composition containing at least a hydroxy compound having a boiling point of 180 ° C. or higher and a solubility in water of 1.0 or lower. The aqueous dispersion composition according to claim 1, wherein the content of the component (B) is 0.01 to 10% by weight. The polyolefin resin is one or more selected from the group consisting of polypropylene, a propylene-butene copolymer, an ethylene-propylene copolymer, and an ethylene-propylene-butene copolymer, according to claim 1 or 2. The aqueous dispersion composition according to the above. The aqueous dispersion composition according to any one of claims 1 to 3, wherein the modified polyolefin resin has a weight average molecular weight of 10,000 to 250,000. Component (C): The aqueous dispersion composition according to any one of claims 1 to 4, further comprising a hydroxy compound having a boiling point of less than 180 ° C. and a solubility in water of more than 1.0. The aqueous dispersion composition according to any one of claims 1 to 5, wherein the content of the component (C) is 0.01 to 10% by weight. A primer containing the aqueous dispersion composition according to any one of claims 1 to 6. An adhesive containing the aqueous dispersion composition according to any one of claims 1 to 6. A binder for a paint containing the aqueous dispersion composition according to any one of claims 1 to 6. A binder for ink containing the aqueous dispersion composition according to any one of claims 1 to 6.