TW202104414A - Aqueous dispersion composition - Google Patents

Abstract

To provide an aqueous dispersion composition which, even with respect to a plastic base material, such as a polyolefin base material, ABS, FRP or the like, not only exhibits excellent adhesion and water resistance, but also satisfies an adhesive strength requirement. An aqueous dispersion composition containing a modified polyolefin (A) and a conjugated diene copolymer (B), wherein the conjugated diene copolymer (B) includes a cyano group, and the mass ratio (A)/(B) is 70/30 to 30/70.

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, and FRP.

Plastic substrates represented by polyolefin and ABS are often used in various molded products such as automobile parts because of their excellent performance and lightweight materials, and they are used for the purpose of surface protection, decoration, and tactile improvement. Coating plastic paint. In the past, the plastic coatings were generally organic solvent-based coatings obtained by dissolving resin in organic solvents. However, because of the toxicity and flammability derived from organic solvents, and the doubts about air pollution, they have gradually Replace it with water-based paint.

However, in general, compared with organic solvent-based coatings, water-based coatings have poorer adhesion to plastic substrates, and especially have the problem of poor water resistance. Therefore, in order to ensure sufficient adhesion and water resistance, the type of plastic substrate is limited when facing various water-based coatings. Especially, the same water-based coating must be used to cope with polyolefin substrates and other plastic substrates. difficult.

With regard to water-based coating materials that have improved adhesion to both polyolefin substrates and ABS substrates, for example, Patent Document 1 discloses a resin composition for water-based coatings, which contains a vinyl group-containing cyano group. Aqueous dispersions of monomers and hydroxyl-containing vinyl monomers with a carbon number of 4 or more, and chlorinated polyolefin aqueous dispersions; and the mass ratio of the copolymer/chlorinated polyolefin is 50~95/50~5.

In addition, with regard to water-based coating materials with improved adhesion to polyolefin substrates, ABS substrates, and polycarbonate substrates, Patent Document 2 discloses a resin composition for water-based coatings, which contains a resin composition having a specific melting point. 2 types of non-chlorinated polyolefin (A) and acrylic-styrene copolymer (B) with specific glass transition temperature; and the mass ratio of (A)/(B) is 30-50/70-50. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent 5741838 [Patent Document 2] Japanese Patent 5499809

[The problem to be solved by the invention]

In recent years, polyolefin substrates, ABS substrates, and FRP substrates are equivalent to coatings for automotive substrates. Considering the scratch resistance of the coating film, it is not only necessary to adhere to the substrate, but also for the adhesion strength. The requirements have also increased. However, although the resin compositions for water-based coatings described in Patent Documents 1 and 2 have improved adhesion to ABS substrates or polycarbonate substrates, there is still room for improvement in adhesion strength. In particular, in Patent Documents 1 and 2, the blending ratio of the modified polyolefin must be set to be low. Therefore, there is a problem that the adhesion strength with the polyolefin base material is insufficient.

The present invention is made in view of the above problems and aims to provide an aqueous dispersion that not only exhibits good adhesion and water resistance to any plastic substrate such as polyolefin substrates, ABS, FRP, etc., but also meets the requirements of adhesion strength. Body composition. [Means to solve the problem]

The inventors of the present case studied hard and found that the use of a conjugated diene-based copolymer containing a specific amount of cyano groups and a specific modified polyolefin, and an aqueous dispersion in which they are blended in a specific ratio can solve the above-mentioned problems. this invention. The proposed invention is as follows.

An aqueous dispersion composition containing modified polyolefin (A) and conjugated diene copolymer (B), the conjugated diene copolymer (B) has a cyano group, and (A)/(B) The mass ratio is 70/30~30/70.

The modified polyolefin (A) is preferably an acid-modified or chlorinated acid-modified polyolefin with a melting point above 50°C and below 120°C, and the weight average molecular weight of the modified polyolefin (A) is preferably 40,000 to 120,000.

The cyano group of the conjugated diene copolymer (B) is preferably derived from an acrylonitrile component, and it is more preferable that the cyano group-containing monomer contains 10% by mass or more and 60% by mass or less.

The aqueous dispersion composition described in any of the above can be used in paints, automotive paints, primers, or adhesives. [Effects of Invention]

The aqueous dispersion composition of the present invention has excellent adhesion and water resistance to any plastic substrates such as polyolefin substrates, ABS substrates, and FRP substrates, and also has excellent adhesion strength.

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

＜Modified polyolefin (A)＞ The modified polyolefin (A) used in the present invention is a modified polyolefin, preferably acid-modified polyolefin or acid-modified chlorinated polyolefin.

＜Acid modified polyolefin＞ The acid-modified polyolefin used in the present invention is not limited. By grafting at least one of α, β-unsaturated carboxylic acid and its anhydride to polyethylene, polypropylene and propylene-α-olefin copolymer At least one of the obtained products is preferable.

Propylene-α-olefin copolymers are made of propylene as the main component and copolymerized with α-olefins. Regarding the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, and the like can be used. Among these α-olefins, ethylene and 1-butene are preferable. The ratio between the propylene component and the α-olefin component of the propylene-α-olefin copolymer is not limited. The propylene component is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more, 65 mass% Above% is particularly ideal. If it falls within the above range, the adhesion and adhesion to polyolefin substrates including acrylic substrates are good.

The acid-modified polyolefin preferably contains a propylene component in terms of the olefin component. The propylene content is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more. If the propylene content is 30% by mass or more, the adhesion and adhesion to the polyolefin substrate including the propylene substrate are good.

As for at least one of α,β-unsaturated carboxylic acids and anhydrides thereof, for example, maleic acid, itaconic acid, citraconic acid, and their anhydrides can be mentioned. Among them, acid anhydride is particularly desirable, and maleic anhydride is more desirable. Specifically, for example, maleic anhydride modified polypropylene, maleic anhydride modified propylene-ethylene copolymer, maleic anhydride modified propylene-butene copolymer, maleic anhydride modified propylene-ethylene-butene copolymer For materials and the like, one kind of these acid-modified polyolefins can be used, or two or more kinds can be used in combination.

There are no particular limitations on the production method of acid-modified polyolefins, such as free radical grafting reaction (that is, the generation of radical species to the polymer that becomes the main chain, and the radical species as the starting point for polymerization). The reaction of graft polymerization of unsaturated carboxylic acid and acid anhydride) and so on.

The radical initiator is not particularly limited, and examples thereof include organic peroxides and azo nitriles, and organic peroxides are preferably used. Organic peroxides are not particularly limited, and examples include di-tert-butylperoxy phthalate, tert-butanol peroxide, diisopropyl benzene peroxide, benzyl peroxide, peroxy Tert-butyl benzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy tert-amyl ester, methyl ethyl ketone peroxide, di-tert-butyl peroxide, laurel peroxide, etc.; As for azo nitriles, for example, azobisisobutyronitrile, azobisisopropionitrile and the like can be mentioned.

The acid modification amount of the acid-modified polyolefin 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 particularly preferable, and 5 mass% or less is most preferable. If it is 0.1% by mass or more, the dispersibility in water is likely to be improved, and if it is 10% by mass or less, the water resistance of the coating film is likely to be improved.

The weight average molecular weight (Mw) of the modified polyolefin (A) is preferably within the range of 40,000 to 120,000. The range of 50,000~115,000 is more ideal, the range of 60,000~110,000 is more ideal, the range of 70,000~105,000 is particularly ideal, and the range of 80,000~100,000 is the most ideal. If it is 40,000 or more, the cohesive force becomes stronger and the adhesiveness tends to become better. On the other hand, if it is 120,000 or less, the solubility becomes better and the production of the aqueous dispersion composition tends to be easier.

The weight average molecular weight of the present invention is a value measured by a gel permeation chromatograph (hereinafter referred to as GPC. Standard material: polystyrene resin, mobile phase: tetrahydrofuran) under an environment of 40°C.

The modified polyolefin (A) is more crystalline. If it is crystalline, it is advantageous because it has stronger cohesive force than amorphous, and is superior in adhesiveness, water resistance, heat resistance, and chemical resistance.

The term “crystallinity” in the present invention refers to the use of a differential scanning calorimeter (hereinafter referred to as DSC. Q-2000 manufactured by TA Instruments Japan) at a temperature of 10°C/min from -100°C to 250°C. Those who show a clear melting peak during the heating process. The melting point and heat of fusion are measured by using DSC at a rate of 10°C/min. The highest temperature and area of the melting peak after heating and melting, cooling the resin, and then heating and melting.

The melting point (Tm) of the modified polyolefin (A) is preferably 50°C or higher. Above 60°C is more desirable, above 70°C is even more desirable, and above 75°C is particularly desirable. Also, it is preferably 120°C or less, more preferably 100°C or less, and even more preferably 90°C or less. If it is 50°C or higher, the cohesive force derived from crystals becomes stronger, and the adhesiveness, water resistance, heat resistance, and chemical resistance become better. On the other hand, if the temperature is below 120°C, it will be easy to obtain an aqueous dispersion composition with good solubility.

＜Acid modified chlorinated polyolefin＞ The modified polyolefin (A) used in the present invention is not limited, and a chlorinated product can also be used. As for the chlorinated polyolefin, an acid-modified chlorinated polyolefin obtained by chlorinating the above-mentioned acid-modified polyolefin is preferable.

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

When the modified polyolefin (A) is an acid-modified chlorinated polyolefin, the chlorine content of the acid-modified chlorinated polyolefin takes into account the stability of the solution and the adhesion between the polyolefin substrate and the resin substrate or the metal substrate From the viewpoint of sex, the lower limit is preferably 5% by mass or more, more preferably 8% by mass or more, more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably 14% by mass or more. If it is 5% by mass or more, the stability of the solution becomes better and it becomes easy to emulsify. The upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. If it is 40% by mass or less, the crystallinity of the acid-modified chlorinated polyolefin will increase, and the adhesive strength will tend to increase.

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

＜Conjugated diene copolymer (B)＞ The invention of this application, by containing modified polyolefin (A) and conjugated diene copolymer (B), in addition to low-polarity substrate polyolefin substrate, and high-polarity substrate FRP, The adhesion, water resistance, and adhesion strength of the ABS substrate are also excellent. The conjugated diene-based copolymer (B) is a copolymer of one or more types of conjugated diene-based monomers and one or more types of monomers copolymerizable with the conjugated diene-based monomers. By combining the above-mentioned monomers, an emulsion polymerization method or a solution polymerization method can be used, and it is preferably produced by an emulsion polymerization method.

At least one of the conjugated diene-based monomers or monomers copolymerizable with the conjugated diene-based monomer has a cyano group, especially the monomers copolymerizable with the conjugated diene-based monomer has a cyano group The base is more ideal. The conjugated diene monomer of the conjugated diene copolymer (B) is not particularly limited, and examples thereof include 1,3-butadiene, 2-methyl 1,3-butadiene, and 2-cyano -1,3-butadiene, 2,3-dimethyl-1,3-butadiene and other conjugated butadienes; 1,3-pentadiene and other conjugated pentadienes; 1,3 -Conjugated hexadienes such as hexadiene and 5-methyl-1,3-hexadiene. These may be used individually by 1 type, and may use 2 or more types together. Among them, conjugated butadienes are particularly ideal. The monomer copolymerizable with the conjugated diene monomer is not particularly limited, and examples include α, β-ethylenically unsaturated nitrile monomers such as acrylonitrile, methacrylonitrile, crotononitrile, and vinylene cyanide. Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; styrene, Vinyl aromatic monomers such as α-methylstyrene and divinylbenzene, etc., cyano group-containing monomers (cyano group-containing monomers) are preferable. The cyano group-containing monomers can be α,β-ethylenically unsaturated nitrile monomers, or copolymerizable monomers such as saturated carboxylic acids, unsaturated carboxylic acid esters, and vinyl aromatic monomers modified by cyanide. body. Furthermore, it is more preferable to be an α,β-ethylenically unsaturated nitrile monomer, and it is more preferable to be acrylonitrile.

The conjugated diene copolymer (B) used in the present invention contains a cyano group. The cyano group is preferably derived from an α,β-ethylenically unsaturated nitrile monomer component. The cyano group-containing conjugated diene copolymer (B) is not particularly limited, and examples include acrylonitrile-butadiene copolymers, methacrylonitrile-butadiene copolymers, and acrylonitrile-isoprene copolymers. Diene copolymer, methacrylonitrile-isoprene copolymer, acrylonitrile-butadiene-isoprene copolymer, methacrylonitrile-butadiene-isoprene copolymer, acrylonitrile- Butadiene-methyl acrylate copolymers, acrylonitrile-butadiene-acrylic acid copolymers, etc., among which acrylonitrile-butadiene copolymers are particularly preferred.

The cyano group in the conjugated diene copolymer (B) is preferably 1,880 meq/kg or more. More than 3,760 milliequivalents/kg is more desirable, and more than 5,640 milliequivalents/kg is more desirable. Furthermore, it is preferably 9,400 milliequivalents/kg or less, more preferably 8,460 milliequivalents/kg or less, and even more preferably 7,520 milliequivalents/kg or less.

The content of the cyano group-containing monomer component in the conjugated diene copolymer (B) is preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more . Also, it is preferably 60% by mass or less, more preferably 55% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less. When the cyano group-containing monomer component is 10% by mass or more, the adhesion to the ABS material is likely to be improved. If the cyano group-containing monomer component is 60% by mass or less, since the flexibility of the conjugated diene copolymer (B) becomes better, the adhesion to the olefin substrate tends to become particularly better. The content of the cyano group-containing monomer can be determined by measuring the conjugated diene copolymer (B) by 1H-NMR and 13C-NMR. Specifically, it can be calculated by using a nuclear magnetic resonance device to dissolve the conjugated diene copolymer (B) in a heavy solvent such as deuterated chloroform and heavy DMSO, and then measuring by 1H-NMR and 13C-NMR. When the conjugated diene copolymer (B) is an aqueous dispersion, dry the sample before use.

The conjugated diene-based monomer in the conjugated diene-based copolymer (B) is preferably 40% by mass or more. More preferably, it is 45% by mass or more, and even more preferably 50% by mass or more. In addition, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. If it is 40% by mass or more, since the flexibility of the conjugated diene copolymer (B) becomes better, the adhesiveness to the olefin substrate tends to be particularly good. If it is 90% by mass or less, the adhesion to a substrate of higher polarity than the polyolefin substrate tends to become better.

The glass transition temperature of the conjugated diene copolymer (B) is preferably -30°C or higher. It is more desirable to be above -20°C, and it is more desirable to be above -15°C. In addition, it is preferably 30°C or less, more preferably 20°C or less, and particularly preferably 5°C or less.

Regarding the cyano group-containing conjugated diene copolymer (B), there is a very high nitrile with a content of bonded acrylonitrile (hereinafter referred to as "AN content") of 43% or more such as NBR on the market. NBR, high nitrile NBR with an AN content of 36% or more and less than 43%, medium-high nitrile NBR with an AN content of 31% or more and less than 36%, medium nitrile NBR with an AN content of 25% or more and less than 31%, Products with a wide range of grades such as low nitrile NBR with an AN content of less than 25% can be used. As for the commercially available NBR, Nipol (registered trademark) series manufactured by ZEON Corporation of Japan, etc. can be cited.

In the aqueous dispersion composition of the present invention, when the total of the modified polyolefin (A) and the conjugated diene copolymer (B) is 100 parts by mass, the ratio of the modified polyolefin (A) is 30 parts by mass 70 parts by mass or more. It is more preferably 40 parts by mass or more, more preferably 45 parts by mass or more, more preferably 48 parts by mass or more, particularly preferably 50 parts by mass or more, and more preferably 53 parts by mass or more. In addition, it is preferably 68 parts by mass or less, more preferably 65 parts by mass or less, more preferably 63 parts by mass or less, and particularly preferably 60 parts by mass or less. When the ratio of the modified polyolefin (A) is 30 parts by mass or more, the adhesion to the polyolefin substrate, water resistance, and adhesion strength tend to improve. In addition, when the ratio of the modified polyolefin (A) is 70 parts by mass or less, the adhesion and water resistance to the ABS substrate or the FRP substrate become particularly good.

The total content of the modified polyolefin (A) and the conjugated diene copolymer (B) in the aqueous dispersion is preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass or more . In addition, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. If it is 20% by mass or more, the coating efficiency becomes better, and if it is 50% by mass or less, the coating workability at the time of coating becomes better.

The Z average particle diameter in the aqueous dispersion containing the modified polyolefin (A) is preferably 50 nm or more. It is more preferably 70 nm or more, and more preferably 90 nm or more. In addition, it is preferably 250 nm or less, more preferably 230 nm or less, and even more preferably 200 nm or less. If it is 50 nm or more, the storage stability of the water dispersion becomes better, and if it is 250 nm or less, it tends to have better moisture permeability to the substrate and good adhesion to the substrate.

The viscosity of the water dispersion containing the modified polyolefin (A) is preferably 5mPa･s or more, and more preferably 10mPa･s or more. In addition, 300mPa･s or less is preferable, and 250mPa･s or less is more preferable.

The average Z particle diameter in the aqueous dispersion composition of the present invention is preferably 50 nm or more. It is more desirable that it is 70 nm or more, and it is more desirable that it is 90 nm or more. In addition, it is preferably 250 nm or less, more preferably 230 nm or less, and even more preferably 250 nm or less. If it is 50 nm or more, the storage stability of the water dispersion becomes better, and if it is 250 nm or less, it tends to have better moisture permeability to the substrate and good adhesion to the substrate.

The aqueous dispersion composition of the present invention is not limited. For example, it can be obtained by uniformly mixing an aqueous dispersion containing a modified polyolefin (A) and an aqueous dispersion containing a conjugated diene copolymer (B). The aqueous dispersion composition can be used as a binder. In addition, a paint can be obtained by mixing the aqueous dispersion composition of the present invention and a pigment dispersion liquid, and it can also be used as a paint for automobiles. The manufacturing method of the aqueous dispersion of the said modified polyolefin (A) is not specifically limited, The following manufacturing methods are mentioned. That is, by dissolving the modified polyolefin (A) in one or more solvents selected from the group consisting of ether solvents, alcohol solvents, and aromatic solvents, and water, and adding alkali It can be obtained by removing these solvents after cooling.

The ether-based solvent is not particularly limited, and examples thereof include tetrahydrofuran (hereinafter referred to as THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like. These can be used singly or in combination of two or more. Among them, tetrahydrofuran is particularly ideal.

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

Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, cumene, mineral spirits, etc., and these can be used singly or in combination of two or more. Among them, toluene is particularly desirable.

The amount of solvent and water used can be selected arbitrarily, modified polyolefin (A): water: solvent=100: 50~800: 11~900 (mass ratio) is ideal, 100: 200~400: 43~233 (mass It is more ideal than).

The alkaline substance is not particularly limited, and volatile alkaline substances are preferable, and ammonia and amines are particularly preferable. The amines are not particularly limited, and examples include monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, mono Ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N -Dimethylethanolamine and N,N-dimethylpropanolamine, etc., especially triethylamine and N,N-dimethylethanolamine. These volatile amines can be used individually or in combination of 2 or more types.

The basic substance is preferably 0.5 parts 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 particularly preferably 3 parts by mass or more. In addition, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably 7 parts by mass or less. If it is 0.5 parts by mass or more and 10 parts by mass or less, the particle size of the dispersed particles does not become too large, and the storage stability becomes particularly good. If it is too much, the water resistance of the coating film may decrease.

The temperature at the time of heating and dissolving is not particularly limited, but it is preferably 50°C or higher. In addition, if it is 75°C or lower, which is lower than the boiling point of the organic solvent used, a pressure vessel for heating and dissolving is not required, so it is preferable. The dissolution time is also not particularly limited, and it usually dissolves completely within 1 to 2 hours.

The aqueous dispersion of the modified polyolefin (A) may be blended with an emulsifier as needed within the range that does not impair the performance of the present invention.

The emulsifier blended in the aqueous dispersion of the modified polyolefin (A) is not particularly limited, and examples include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, or amphoteric emulsifiers, except for general use In addition to emulsion polymerization, it also contains surfactants. As for anionic emulsifiers, for example, sulfate ester salt of higher alcohol, higher alkyl sulfonate, higher carboxylate, alkylbenzene sulfonate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl Phenyl ether sulfate, vinyl sulfonate succinate, etc. Nonionic emulsifiers include polyoxyalkylene alkyl ether types such as polyoxyethylene lauryl ether, and polyoxyalkylene styrenated phenyl ether types such as polyoxyethylene styrenated phenyl ether. , Polyoxyethylene nonyl phenyl ether and other polyoxyalkylene alkyl phenyl ether type, polyoxyethylene stearyl amine and other polyoxyalkylene alkyl amine type, polyoxyethylene polyoxypropylene monoamine and other poly Polyoxyalkylene amine type, polyoxyalkylene alkyl amide type such as polyoxyethylene oleamide, polyoxyalkylene fatty acid ester type such as polyoxyethylene monolaurate, polyoxyethylene polyoxypropylene glycol , Polyoxyethylene polyoxypropylene tridecyl ether and other ethylene oxide propylene oxide block polymerization type, ethylene oxide propylene oxide random polymerization type, polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan anhydride Fatty acid esters and so on. As for the amphoteric emulsifier, for example, lauryl betaine, lauryl dimethyl amine oxide and the like can be mentioned. These can be used alone or in combination of two or more kinds.

The emulsifier is preferably 1 part by mass or more relative to 100 parts by mass of the modified polyolefin (A), more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, particularly preferably 4 parts by mass or more, and most preferably 5 parts by mass or more 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 particularly preferable, and 20 parts by mass or less is most preferable. If it is 1 part by mass or more, it tends to be easy to emulsify, and if it is 30 parts by mass or less, the water resistance of the coating film is likely to be improved.

The method of blending the emulsifier is not particularly limited. For example, it may be blended without being diluted in water or the like, or it may be blended in the form of an aqueous solution diluted to 1-50% by mass. In order to be quickly mixed into the aqueous dispersion composition, it is preferable to blend in the form of an aqueous solution diluted to 1-50% by mass. By blending the emulsifier in an aqueous solution state in the aqueous dispersion composition, the emulsifier will be quickly adsorbed on the particles.

In addition, in the aqueous dispersion composition of the present invention, in order to further improve the properties such as water resistance and solvent resistance, a hardener may be blended as necessary. The hardener is not particularly limited, and examples include water-based polyfunctional carbodiimide resins, water dispersions of polyfunctional isocyanate compounds, water-based polyfunctional oxazoline resins, and water-soluble silane couplings containing polyfunctional silyl groups. Coupling agent, water-based melamine compound, etc. With respect to 100 parts by mass of the resin in the aqueous dispersion composition of the present invention, it is preferable to blend 2 to 30 parts by mass of these hardeners.

Then, in the aqueous dispersion composition of the present invention, various additives such as fillers, pigments, colorants, and antioxidants can be blended within a range that does not reduce the effects of the present invention. The blending amount of these additives is preferably 150 parts by mass or less relative to 100 parts by mass of the resin in the aqueous dispersion composition, more preferably 140 parts by mass or less, and more preferably 130 parts by mass or less. It is more preferably 5 parts by mass or more, and more preferably 2 parts by mass or more. If it falls within the above range, the excellent effects of the present invention can be exerted.

The aqueous dispersion composition of the present invention has excellent adhesion to various plastic substrates, especially the adhesion strength, so it is suitable for coating, printing, bonding, primers, coatings, inks, and coating agents during coating, printing, bonding, and coating. , The use of adhesive is helpful.

The present invention will be specifically described below based on examples, but the present invention should not be limited to these examples. The simple description of "parts" in the examples and comparative examples means parts by mass. In addition, the measurement and evaluation methods used in the present invention are as follows.

1) Determination of solid content concentration of aqueous dispersion Take a sample and accurately weigh about 1g of the aqueous dispersion of the sample in a 50ml glass weighing bottle. Then dry the weighing bottle after loading the sample with a hot air dryer at 120°C for 2 hours, and then put the weighing bottle taken out in a desiccator, and place and cool it at room temperature for 30 minutes. The weighing bottle is taken out from the desiccator, its mass is precisely weighed, and the mass% of the solid content concentration of the aqueous dispersion is calculated from the weight change before and after the hot air drying (the following formula). Aqueous dispersion solid content concentration (mass%)=100-[(mass of sample before hot air drying)-(mass of sample after hot air drying)]/(mass of sample before hot air drying)×100

2) Determination of viscosity of aqueous dispersion Using the "ViscometerTV-22" (E-type viscometer) manufactured by Toki Sangyo Co., Ltd., place a 0.6g sample on a rotor No. 0.8°(=48')×R24, range H, rotation speed 5rpm, 25°C Measure under the conditions.

3) Determination of pH of aqueous dispersion The value at 25°C was measured using "pH meter F-52" manufactured by Horiba Manufacturing Co., Ltd. In addition, the calibration of the measuring instrument uses the phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The liquid (pH 9.18) was measured at three points.

4) Determination of the average particle size of the aqueous dispersion Using "Zetasizer Nano-ZS Model ZEN3600" manufactured by Malvern Corporation, the average particle diameter (Z average particle diameter) was measured from the intensity distribution by dynamic light scattering. The solid content of the aqueous dispersion composition was adjusted to a concentration of 0.05 g/L, the sample was measured 3 times at 25°C, and the average value was taken.

5) Measurement of the amount of acid modification The amount of acid modification when acid modification is performed with maleic anhydride can be obtained by FT-IR (FT-IR8200PC manufactured by Shimadzu Corporation). First, maleic anhydride is dissolved in an arbitrary concentration to prepare a calibration curve solution. Perform the FT-IR measurement of the calibration curve solution, and create the calibration curve based on the absorbance ^{of the stretching peak (1780 cm -1) of the carbonyl (C=O) bond of maleic anhydride.} The modified polyolefin (A) was dissolved in chloroform and subjected to FT-IR measurement. Based on the above calibration curve, ^{the absorbance of maleic anhydride's carbonyl bond stretching peak (1780 cm -1} ) was obtained. The amount of acid modification.

6) Determination of melting point The melting point and the heat of fusion of the present invention are measured by using a differential scanning calorimeter (hereinafter referred to as DSC, Q-2000 manufactured by TA Instruments Japan) at a rate of 10°C/min for heating and melting, cooling the resin, and then heating and melting. The value measured at the highest temperature of the melting peak. 7) Measurement of glass transition temperature The glass transition temperature (Tg) (°C) of the resin is defined by DSC under the same conditions as the melting point measurement, defined as the straight line from the longitudinal axis direction to the extension of each baseline during the reheating process. The straight line is equidistant from the glass The temperature at the point where the curves of the step-like part of the transition intersect.

The compositions of the water dispersions used in the following examples and comparative examples are shown in Tables 1 and 2.

Manufacturing example 1 100 parts by mass of propylene-butene copolymer ("TAFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals Co., Ltd., 75% by mass of propylene, 25% by mass of butene) as a polyolefin, 300 parts by mass of toluene, and Malay 10 parts by mass of acid anhydride was placed in a 1 L autoclave, and after the temperature was raised to 130° C., 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. Then, after cooling the obtained reaction liquid, it was poured into a container containing a large amount of methyl ethyl ketone to precipitate the resin. Afterwards, the liquid containing the resin is centrifuged to separate and refine the acid-modified propylene-butene copolymer obtained by graft polymerization of maleic anhydride from the ungrafted maleic anhydride and low molecular weight substances. After that, it was dried at 70°C for 5 hours under reduced pressure to obtain a maleic anhydride modified propylene-butene copolymer (A-1, maleic anhydride with a modified amount of 1.0% by mass and a weight average molecular weight of 90,000 , Melting point 82℃).

Manufacturing example 2 Put 100 parts by mass of polypropylene (Prime Polypro (registered trademark) J105G" made by Prime Polymer Co., Ltd., 100% by mass of propylene), 300 parts by mass of toluene, and 10 parts by mass of maleic anhydride, which are polyolefins, into a 1L autoclave After the temperature was raised to 130°C, 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. Then, after cooling the obtained reaction liquid, it was poured into a container filled with a large amount of methyl ethyl ketone to precipitate the resin. Afterwards, the liquid containing the resin is centrifuged to separate and refine the acid-modified polypropylene obtained by graft polymerization of maleic anhydride from the ungrafted maleic anhydride and low molecular weight substances. After that, it was dried at 70° C. for 5 hours under reduced pressure to obtain maleic anhydride-modified polypropylene. Then, 100 parts by mass of maleic anhydride modified polypropylene and 1,700 parts by mass of chloroform were put into a 2L reaction tank made of glass lining and sealed. While stirring and dispersing the liquid in the reaction tank, it was heated and dissolved at 120°C in the tank for 1 hour. After the temperature in the tank was cooled to 110°C, 0.5 parts by mass of tert-butyl peroxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. After the temperature in the tank was cooled to 60°C and 1,400 parts by mass of chloroform was distilled off, 4 parts by mass of p-tert-butylphenyl glycidyl ether was added as a stabilizer. Afterwards, it was dried to obtain maleic anhydride modified chlorinated polypropylene (A-2, the modified amount of maleic anhydride was 1.0% by mass, the chlorine content was 17% by mass, the weight average molecular weight was 110,000, and the melting point was 96°C).

Manufacturing example 3 Except that the maleic anhydride was changed to 15 parts by mass, the acid modification was carried out in the same manner as in Production Example 1, to obtain a maleic anhydride modified propylene-butene copolymer (A-3, the modified amount of maleic anhydride was 1.5% by mass , Weight average molecular weight 70,000, melting point 80°C).

Manufacturing example 4 In addition to changing polyolefin to propylene-butene copolymer ("TAFMER (registered trademark) XM7070" manufactured by Mitsui Chemicals Co., Ltd., 70% by mass of propylene, 30% by mass of butene), and maleic anhydride to 20% by mass Except for parts, the acid modification was carried out in the same manner as in Production Example 1, to obtain a maleic anhydride modified propylene-butene copolymer (A-4, maleic anhydride modified amount of 2.0% by mass, weight average molecular weight 60,000, melting point 70 ℃).

Manufacturing example 5 100 parts by mass of modified polyolefin (A-1), 210 parts by mass of ion-exchange water, 110 parts by mass of tetrahydrofuran, 45 parts by mass of isopropyl alcohol, and 55 parts by mass of toluene were put into a flask with a mixer, and the temperature was raised to 70 After ℃, heat and dissolve at the same temperature for 1 hour. Then, 3.6 parts by mass (2 chemical equivalents) of N,N-dimethylethanolamine was added, and after slowly cooling to 40°C over 1 hour, the organic solvent was distilled off at a reduced pressure of 91 kPa. Obtained a cloudy maleic anhydride modified polyolefin aqueous dispersion (a-1). The solid content concentration of the aqueous dispersion (a-1) was 30% by mass, the viscosity at 25°C was 48 mPa·s, the pH was 8.1, and the average particle size was 128 nm.

Manufacturing example 6 The modified polyolefin was changed to (A-2), and 10 parts by mass of polyoxyethylene lauryl ether was added at the same time as A-2, except that water dispersion was carried out in the same manner as in Production Example 5 to obtain white turbid maleic anhydride Modified chlorinated polyolefin aqueous dispersion (a-2). The solid content concentration of the aqueous dispersion (a-2) was 30% by mass, the viscosity at 25°C was 13 mPa·s, the pH was 7.8, and the average particle size was 106 nm.

Manufacturing example 7 The modified polyolefin was changed to (A-3), and N,N-dimethylethanolamine was changed to 5.4 parts by mass (2 chemical equivalents), except that the water dispersion was carried out in the same manner as in Production Example 5 to obtain white turbidity The aqueous dispersion of maleic anhydride modified chlorinated polyolefin (a-3). The solid content concentration of the aqueous dispersion (a-3) was 30% by mass, the viscosity at 25°C was 16 mPa·s, the pH was 8.0, and the average particle size was 120 nm.

Manufacturing example 8 The modified polyolefin was changed to (A-4), and N,N-dimethylethanolamine was changed to 7.2 parts by mass (2 stoichiometric weight), except that the water dispersion was carried out in the same manner as in Production Example 5 to obtain white turbidity The aqueous dispersion of maleic anhydride modified chlorinated polyolefin (a-4). The solid content concentration of the aqueous dispersion (a-4) was 30% by mass, the viscosity at 25°C was 146 mPa·s, the pH was 8.1, and the average particle size was 82 nm.

For the aqueous dispersion of the conjugated diene copolymer (B), the following are used. b-1: Acrylonitrile-butadiene copolymer ("Nipol (registered trademark) 1562" manufactured by ZEON Co., Ltd., Japan, high nitrile NBR latex, acrylonitrile content of 36% by mass or more and less than 43% by mass, Tg- 26℃) b-2: Acrylonitrile-butadiene copolymer ("Nipol (registered trademark) 1571H" manufactured by ZEON, Japan, carboxyl modified high nitrile modified NBR latex, with an acrylonitrile content of 36% by mass or more and no Up to 43% by mass, Tg-14°C) b-3: Styrene-butadiene copolymer ("Nipol (registered trademark) LX-112" manufactured by ZEON (Stock), Japan, Tg-49°C) b-4: Styrene-butadiene copolymer ("Nipol (registered trademark) SX-1105A" manufactured by ZEON (Stock), Japan" , Tg-4℃)

[Example 1] <Preparation of aqueous dispersion composition> Mix 70 parts by mass of (a-1) as component (A) (21 parts by mass in solid content) and 24 parts by mass (b-1) as component (B) (in terms of solid content as 9) in a container. Parts by mass) and uniformly stirred for 30 minutes with a disperser to obtain an aqueous dispersion composition.

＜Pigment dispersion liquid＞ After adding 4 parts by mass of water-soluble acrylic resin, 2 parts by mass of conductive carbon black, 36 parts by mass of rutile-type titanium oxide, and 70 parts by mass of ion-exchanged water and stirring for 30 minutes, dispersion was performed for 30 minutes with a bead mill. After that, 5 parts by mass of a urethane-associated thickener and 2 parts by mass of a leveling agent were added to obtain a pigment dispersion.

＜Paint＞ 94 parts by mass of the aqueous dispersion composition obtained above and 119 parts by mass of the pigment dispersion were mixed and uniformly stirred to obtain coating material 1.

＜Evaluation＞ (Making of test coated board) The polypropylene substrate, ABS substrate, and FRP (unsaturated polyester) substrate were degreased with isopropyl alcohol and used as test panels. The paint 1 prepared as described above was applied by air spray coating on the test plate so that the dry coating film was 10 μm, and dried in an oven at 80° C. for 5 minutes. On the coating composition surface of the test panel, RETAN (registered trademark) PG80III WHITE (trade name, manufactured by Kansai Paint Co., Ltd.) as a coloring base coating was applied by air spraying so as to have a dry film thickness of 50 μm. Then, it was heated in an oven at 80°C for 30 minutes to form a laminated coating film. Then, it was allowed to stand still for 36 hours in an environment of 25° C. to obtain a test coated plate. Perform various coating film performance tests as shown below on this test coated board.

(Evaluation of Adhesion) Cut a gap with a width of 2mm on each test coated plate with a sharp cutter to form a 10×10 checkerboard pattern, and glue cellophane tape (manufactured by NICHIBAN) to the checkerboard-like part, and repeat 10 times sharply at an angle of 60° Stripping operation. Even if it is repeated 10 times, there is no change on the coated surface. 10 points are counted. If peeling occurs at the 10th time, 9 points are counted. The following are 8, 7, and 6 points in order. When peeling occurs, it is counted as 0 points. The results are shown in Table 1 and Table 2.

(Evaluation of water resistance) Each test coated plate was immersed in warm water at 40°C for 10 days. After immersion, the external appearance of the coating film surface was confirmed, and the adhesion evaluation mentioned above was implemented. The results are shown in Table 1 and Table 2. Evaluation criteria ◎: There is no abnormal appearance such as blistering, and the adhesion evaluation is 10 points ○: There is no abnormal appearance such as blistering, and the adhesion evaluation is 4-9 points △: There is no abnormal appearance such as blistering, and the adhesion evaluation is 1 to 3 points ×: The appearance of blistering or adhesion is evaluated as 0 points

(Evaluation of Peel Strength) Adhesion strength was evaluated by peel strength. After making a 130μm test coating coated with a colored base paint under the above-mentioned test coating production conditions, cut the test coating to a width of 1cm, and use a Tensilon universal material testing machine (manufactured by A&D) at a speed of 5mm per second. Stretch it by 50mm and calculate the average strength after 5 measurements. Evaluation criteria ◎: The value of peeling strength is above 1000gf/cm ○: The value of peeling strength is above 800gf/cm and less than 1000gf/cm △: The value of peeling strength is 500gf/cm or more and less than 800gf/cm ×: The value of peeling strength does not reach 500gf/cm

[Examples 2 to 14 and Comparative Examples 1 to 8] Except having changed to the modified polyolefin and conjugated diene-based copolymer shown in Table 1 and Table 2, the paint was produced in the same manner as in Example 1, and each test was performed.

[Table 1]

[產業利用性][Table 2]

[Industrial Utilization]

The aqueous dispersion composition of the present invention has excellent adhesion and adhesion strength not only to polyolefin substrates, but also to other plastic substrates. Therefore, it is helpful for the application of primers, paints, inks, coating agents, and adhesives during coating, printing, bonding, and coating, and can be used in common for various different substrates.

Claims (7)

An aqueous dispersion composition containing modified polyolefin (A) and conjugated diene copolymer (B), the conjugated diene copolymer (B) has a cyano group, and (A)/(B) The mass ratio is 70/30~30/70. The aqueous dispersion composition according to claim 1, wherein the modified polyolefin (A) has a melting point of 50°C or more and 120°C or less, and is an acid-modified or chlorinated acid-modified polyolefin. The aqueous dispersion composition according to claim 1 or 2, wherein the cyano group of the conjugated diene copolymer (B) is derived from an acrylonitrile component. The aqueous dispersion composition according to claim 1 or 2, wherein the weight average molecular weight of the modified polyolefin (A) is 40,000 to 120,000. The aqueous dispersion composition according to claim 1 or 2, wherein the conjugated diene copolymer (B) contains 10% by mass or more and 60% by mass or less of the cyano group-containing monomer component. A paint containing the aqueous dispersion composition according to any one of claims 1 to 5. An adhesive comprising the aqueous dispersion composition according to any one of claims 1 to 5.