WO2015079919A1

WO2015079919A1 - Aqueous dispersion composition containing modified polyolefin

Info

Publication number: WO2015079919A1
Application number: PCT/JP2014/080013
Authority: WO
Inventors: 将史中島; 健二柏原
Original assignee: 東洋紡株式会社
Priority date: 2013-11-26
Filing date: 2014-11-13
Publication date: 2015-06-04
Also published as: JP6662040B2; TW201529676A; JPWO2015079919A1

Abstract

　To provide an aqueous dispersion composition containing a modified polyolefin, having good adhesive properties and water resistance, and the viscosity of the aqueous dispersion composition being in a range of 500 mPa∙s or less and fixed. An aqueous dispersion composition containing a modified polyolefin (A), a basic substance (B), and an emulsifier (E), and further containing an electrolyte (D) and/or an anionic-group-containing water-soluble polymer (C) having an acid value of 150-500 mg/KOH/g-resin.

Description

Modified polyolefin-containing aqueous dispersion composition

The present invention relates to an aqueous dispersion composition containing a modified polyolefin. More specifically, it contains a modified polyolefin, a basic substance and an emulsifier suitable for use in paints, inks, sealants, primers or adhesives, and further contains at least one of an anionic group-containing water-soluble polymer and an electrolyte. It relates to a dispersion composition.

Polyolefin resins such as polypropylene are excellent in properties and inexpensive, and are therefore used in large quantities in automobile parts, various films, various molded products, and the like. However, the polyolefin-based resin has a problem that it is difficult to paint and adhere because it is crystalline and the surface is nonpolar.

For this reason, modified polyolefins such as acid-modified polyolefins and acid-modified chlorinated polyolefins have been developed for painting, printing, and laminating and adhering polyolefin resins. Dispersion compositions have been proposed (for example, Patent Documents 1 and 2).

JP-A-8-176374 JP-A-1-256549

However, in the above method, the viscosity of the aqueous dispersion composition may not be stable. When the viscosity is unstable, there is a problem that handling during production becomes poor and production efficiency is lowered. Furthermore, when preparing paints, inks, etc., additives such as various viscosity modifiers are blended in addition to the modified polyolefin-containing aqueous dispersion composition.

The present invention has been made in view of the above problems, and as a result of intensive studies, the present inventors have found that an aqueous dispersion composition containing a modified polyolefin has an anionic group-containing water-soluble polymer and / or electrolyte. It has been found that the aqueous dispersion composition can be stabilized at a low viscosity by containing the water, and the present invention has been completed.

In order to achieve the above-mentioned problems, the present inventors have intensively studied and have come up with the following inventions.

An anionic group-containing water-soluble polymer (C) and an electrolyte (D) containing a modified polyolefin (A), a basic substance (B) and an emulsifier (E), and having an acid value of 150 to 500 mg KOH / -resin An aqueous dispersion composition containing at least one.

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

The aqueous dispersion composition contains 0.5 to 10 parts by mass of the basic substance (B) and 1 to 30 parts by mass of the emulsifier (E) with respect to 100 parts by mass of the modified polyolefin (A). The total amount of the group-containing water-soluble polymer (C) and the electrolyte (D) is preferably contained in an amount of 0.1 to 20 parts by mass.

A paint, ink, sealant, primer or adhesive containing the aqueous dispersion composition.

A laminate of a polyolefin substrate bonded with the adhesive and a resin substrate or a metal substrate.

ポリオレフィン Polyolefin substrate painted with the paint.

Since the aqueous dispersion composition according to the present invention contains an anionic group-containing water-soluble polymer and / or electrolyte, the viscosity when the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass is 500 mPa · s. It can be made constant in the following range. Furthermore, the coating film produced using the aqueous dispersion composition according to the present invention is free from unevenness and has good adhesion and water resistance.

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

<Modified polyolefin (A)>
The modified polyolefin (A) used in the present invention is not particularly limited, but is preferably acid-modified polyolefin (A1) and / or acid-modified chlorinated polyolefin (A2).

<Acid-modified polyolefin (A1)>
The acid-modified polyolefin (A1) used in the present invention is not limited, but at least one of polyethylene, polypropylene and propylene-α-olefin copolymer includes at least α, β-unsaturated carboxylic acid and its acid anhydride. What is obtained by grafting 1 type is preferable.

The propylene-α-olefin copolymer is a copolymer in which α-olefin is copolymerized mainly with propylene. As the α-olefin, for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.

Examples of at least one of α, β-unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof. Among these, acid anhydrides are preferable, and maleic anhydride is more preferable. Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like. These acid-modified polyolefins can be used alone or in combination of two or more.

The method for producing the acid-modified polyolefin (A1) is not particularly limited, and for example, radical graft reaction (that is, a radical species is generated for a polymer to be a main chain, and the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride).

Although it does not specifically limit as a radical generator, It is preferable to use an organic peroxide. The organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.

The acid-modified chlorinated polyolefin (A2) used in the present invention is not limited, but is preferably obtained by chlorinating the acid-modified polyolefin (A1).

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

The acid-modified amount of the modified polyolefin (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more. 1% by mass or more is most preferable. 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 especially preferable, and 5 mass% or less is the most preferable. If the amount is too small, it may be difficult to disperse sufficiently. If the amount is too large, the water resistance of the coating film may be adversely affected.

The amount of acid modification when acid-modified with maleic anhydride can be determined by FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC). First, a calibration curve solution is prepared by dissolving maleic anhydride at an arbitrary concentration. The calibration curve solution is subjected to FT-IR measurement, and a calibration curve is prepared from 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 calibration curve, the acid-modified amount of maleic anhydride was determined from the absorbance of the stretching peak (1780 cm ⁻¹ ) of the carbonyl bond of maleic anhydride. Ask.

The weight average molecular weight (Mw) of the modified polyolefin (A) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is too small, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when too large, solubility may fall and a problem may arise in preparation of an aqueous dispersion composition.

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

The modified polyolefin (A) is preferably crystalline. The crystallinity is advantageous because it has higher cohesion than amorphous and has excellent adhesion, water resistance, heat resistance, and chemical resistance.

The crystallinity referred to in the present invention means a differential scanning calorimeter (hereinafter also referred to as DSC, manufactured by TA Instruments Japan, Q-2000) at a temperature of 10 ° C./100° C. to 250 ° C. min. The temperature is raised at a temperature of 1 and a clear melting peak is indicated in the temperature raising process. The melting point and the heat of fusion were measured at 10 ° C./min. Using DSC. It is a value measured from the top temperature and the area of the melting peak when the temperature is melted at a rate of temperature, the resin is cooled, and the temperature is melted again.

The melting point (Tm) of the modified polyolefin (A) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the cohesive force derived from the crystal becomes weak, and the adhesiveness, water resistance, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solubility may be lowered and a problem may occur in the production of the aqueous dispersion composition.

When the modified polyolefin (A) is an acid-modified chlorinated polyolefin (A2), the chlorine content of the acid-modified chlorinated polyolefin (A2) depends on the solution stability and the polyolefin substrate and the resin substrate or metal substrate. From the viewpoint of adhesiveness, the lower limit is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably. Is 14% by mass or more. If it is less than the above value, the solution stability may be lowered and emulsification may not be possible. The upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, still more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. is there. When the above value is exceeded, the crystallinity of the acid-modified chlorinated polyolefin may decrease, and the adhesive strength may decrease.

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

<Basic substance (B)>
The basic substance (B) used in the present invention can neutralize the acidic group (carboxyl group) of the modified polyolefin (A) and improve the dispersibility of the modified polyolefin (A).

The basic substance (B) is not particularly limited, but a volatile basic substance is preferable, and among them, ammonia and amines are preferable. The amines are not particularly limited, but monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine , N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, and the like are particularly preferable. Triethylamine, N, N-dimethylethanolamine. These volatile amines can be used alone or in combination of two or more.

The basic substance (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). Is more preferable, and 3 parts by mass or more is particularly preferable. Further, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 7 parts by mass or less. If the amount is too small, the particle size of the dispersed particles of the resulting aqueous dispersion composition is large, and the storage stability may be lowered. If the amount is too large, the water resistance of the coating film may be lowered.

<Anionic group-containing water-soluble polymer (C)>
The anionic group-containing water-soluble polymer (C) used in the present invention can reduce the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition. Thereby, the viscosity when the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass can be made constant within a range of 500 mPa · s or less.

Further, by using the anionic group-containing water-soluble polymer (C), the viscosity of the aqueous dispersion composition is lowered, and the excellent effect of not inhibiting the effect of the viscosity modifier at the time of coating is obtained. Demonstrated. Viscosity modifiers exhibit the desired viscosity by hydration and association between polar groups in the paint, but when low-molecular compounds such as electrolytes are used as charge reducing agents, these hydration and association between polar groups In order to inhibit this, the viscosity modifier may not function. On the other hand, since the anionic group-containing water-soluble polymer (C) is a polymer compound, the flow in the paint is suppressed, the interaction with the viscosity modifier is small, and the effect of the viscosity modifier is not affected. Conceivable. That is, when preparing paints, inks, sealants, primers, adhesives, etc., it is necessary to mix various additives such as viscosity modifiers in addition to the aqueous dispersion composition to prevent dripping during coating. There is. The anionic group-containing water-soluble polymer (C) does not hinder the effects of viscosity modifiers, so there is no dripping during coating, and good paints, inks, sealants, primers and adhesion An agent or the like can be obtained.

The anionic group-containing water-soluble polymer (C) refers to a polymer compound that dissolves in water and reduces the charge on the particle surface of the modified polyolefin (A). Specific examples include, but are not limited to, an acrylic resin, a urethane resin, an epoxy resin, and the like containing a carboxyl group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group, and more specifically, polystyrene sulfonic acid. And an anionic group-containing water-soluble polymer mainly composed of polyacrylic acid, styrene-maleic anhydride copolymer, styrene-acrylic monomer copolymer, styrene-methacrylic monomer copolymer, and the like. These anionic group-containing water-soluble polymers (C) can be used alone or in combination of two or more.

The acid value of the anionic group-containing water-soluble polymer (C) needs to be 150 mgKOH / g-resin or more, preferably 160 mgKOH / g-resin or more, more preferably 170 mgKOH / g-resin or more. More preferably, it is 180 mgKOH / g-resin or more, particularly preferably 190 mgKOH / g-resin or more, and most preferably 200 mgKOH / g-resin or more. If it is too low, the effect of lowering the viscosity of the aqueous dispersion composition may be reduced. Further, it is necessary to be 500 mgKOH / g-resin or less, preferably 490 mgKOH / g-resin or less, more preferably 480 mgKOH / g-resin or less, further preferably 470 mgKOH / g-resin or less, particularly Preferably it is 460 mgKOH / g-resin or less, most preferably 450 mgKOH / g-resin or less. If it is too high, the water resistance of the coating film may be lowered, and the effect of the viscosity modifier during coating may be impaired. If it is in the said range, since the viscosity of an aqueous dispersion composition and the physical property of a coating film become favorable, it is preferable. The acid value of the anionic group-containing water-soluble polymer (C) can be measured according to JIS K-0070-1992.

The weight average molecular weight (Mw) of the anionic group-containing water-soluble polymer (C) is preferably 1,500 or more, more preferably 2,000 or more, more preferably 3,000 or more, More preferably, it is 5,000 or more, Especially preferably, it is 7,000 or more, Most preferably, it is 9,000 or more. When too small, the effect of the viscosity modifier at the time of coating may be inhibited. Further, it is preferably 30,000 or less, more preferably 29,000 or less, more preferably 28,000 or less, further preferably 27,000 or less, and particularly preferably 26,000 or less. Yes, most preferably 25,000 or less. When too large, the solubility to water may fall and the effect of a viscosity fall may become small. If it is in the said range, since the viscosity of an aqueous dispersion composition and the physical property of a coating film become favorable, it is preferable. The weight average molecular weight of the anionic group-containing water-soluble polymer (C) is a value measured by GPC under an atmosphere of 40 ° C.

The solubility of the anionic group-containing water-soluble polymer (C) in water (20 ° C.) is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. Is more preferable, and more preferably 30% by mass or more. Although an upper limit is not specifically limited, Practically, it is 50 mass% or less.

The anionic group-containing water-soluble polymer (C) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the modified polyolefin (A). The amount is more preferably 5 parts by mass or more, and particularly preferably 2 parts by mass or more. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be reduced. If the amount is too large, the water resistance of the coating film may be decreased, and the effect of the viscosity modifier at the time of coating may be impaired.

<Electrolyte (D)>
The electrolyte (D) used in the present invention is one that dissolves in water and ionizes cations and anions to show conductivity. By using the electrolyte, the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition can be reduced, whereby the solid content of the modified polyolefin in the aqueous dispersion composition is 30% by mass. The viscosity can be made constant in the range of 500 mPa · s or less. The electrolyte (D) is not particularly limited. Aliphatic hydroxy acids such as citramalic acid, hydroxybutyric acid, glycolic acid, tartronic acid, glyceric acid; salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orthoric acid, gallic acid , Aromatic acids such as mandelic acid, benzic acid, atrolactic acid, mellilotic acid, furoletic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapinic acid; lithium chloride, sodium chloride, potassium chloride, magnesium chloride, Calcium chloride, sodium bromide, bromide Potassium, magnesium bromide, calcium bromide, sodium iodide, alkali halides (earth) or calcium metal iodide salt; and the like. Among these, citric acid, isocitric acid, and sodium chloride are preferable. These electrolytes (D) can be used alone or in combination of two or more.

The electrolyte (D) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 1.5 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). Is more preferable and 2 parts by mass or more is particularly preferable. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be small, and if it is too large, the water resistance of the coating film may be decreased.

The total amount of the anionic group-containing water-soluble polymer (C) and the electrolyte (D) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A), and is 1 part by mass or more. More preferably, it is more preferably 1.5 parts by mass or more, and particularly preferably 2 parts by mass or more. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be reduced. If the amount is too large, the water resistance of the coating film may be decreased, and the effect of the viscosity modifier at the time of coating may be impaired.

<Emulsifier (E)>
The emulsifier (E) used in the present invention is not particularly limited, and examples thereof include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers. In addition to those generally used for emulsion polymerization, surfactants are also included. . For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. And the like. Nonionic emulsifiers include polyoxyalkylene alkyl ether type such as polyoxyethylene lauryl ether, polyoxyalkylene styrenated phenyl ether type such as polyoxyethylene styrenated phenyl ether, and polyoxyalkylene alkyl such as polyoxyethylene nonylphenyl ether. Phenyl ether type, polyoxyalkylene alkylamine type such as polyoxyethylene stearylamine, polyoxyalkyleneamine type such as polyoxyethylene polyoxypropylene monoamine, polyoxyalkylene alkylamide type such as polyoxyethylene oleylamide, polyoxyethylene Polyoxyalkylene fatty acid ester type such as monolaurate, polyoxyethylene polyoxypropylene glycol, polyoxyethylene Ethylene oxide and propylene oxide block polymer type and ethylene oxide propylene oxide random polymerization type polyoxypropylene tridecyl ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, and the like. Examples of amphoteric emulsifiers include lauryl betaine and lauryl dimethylamine oxide. These emulsifiers (E) can be used alone or in combination of two or more.

The emulsifier (E) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, relative to 100 parts by mass of the modified polyolefin (A). It is particularly preferably at least 5 parts by mass, and most preferably at least 5 parts by mass. Further, it is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, further preferably 25 parts by mass or less, particularly preferably 22 parts by mass or less, and 20 parts by mass or less. Most preferably it is. If the amount is too small, the stability may decrease, and if the amount is too large, the water resistance of the coating film may decrease.

The method of blending the emulsifier is not particularly limited. For example, the emulsifier may be blended without being diluted with water or the like, or may be blended in the form of an aqueous solution diluted to 1 to 50% by mass. In order to rapidly mix with the aqueous dispersion composition, it is preferably blended in the form of an aqueous solution diluted to 1 to 50% by mass. By blending the aqueous dispersion composition with an aqueous emulsifier, the emulsifier is quickly adsorbed onto the particles.

<Aqueous dispersion composition>
The aqueous dispersion composition of the present invention contains the modified polyolefin (A), the basic substance (B) and the emulsifier (E), and further contains an anionic group-containing water-soluble polymer (C) and an electrolyte (D). It is a mixture containing at least one.

The aqueous dispersion composition has a viscosity at 25 ° C. of 500 mPa · s or less measured using a Brookfield viscometer (rotor rotation speed: 60 rpm) when the solid content of the modified polyolefin (A) is 30% by mass. Preferably there is. More preferably, it is 400 mPa · s or less, further preferably 300 mPa · sPa · s or less, and particularly preferably 200 mPa · s or less. If it is too large, the operability and the like during production of the aqueous dispersion composition and preparation of the paint may be poor. Further, the lower the viscosity is, the better the handling property is, so there is no particular lower limit, but practically it is 5 mPa · s or more.

The solid content concentration of the modified polyolefin (A) in the aqueous dispersion composition according to the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, still more preferably 15 to 40% by mass, Most preferably, it is in the range of 20 to 35% by mass. If the solid content concentration of the modified polyolefin (A) is too high, the viscosity becomes high and aggregation between the modified polyolefin particles tends to occur, so that the dispersion stability may be significantly lowered. On the other hand, if it is too low, it is difficult to say that it is practical in terms of both production and application.

The particle size of the modified polyolefin (A) contained in the aqueous dispersion composition is preferably 5 to 500 nm, more preferably 10 to 400 nm, and even more preferably 15 to 300 nm. If the particle size is too small, the film formability tends to be improved. For this reason, fusion and aggregation between the dispersed particles are likely to occur, and as a result, the dispersion stability is lowered, which is not preferable. On the other hand, if it is too large, not only the dispersion stability is greatly lowered but also the film formability is lowered, so that the appearance and performance of the resulting film may be deteriorated.

The particle size of the modified polyolefin (A) contained in the aqueous dispersion composition can be measured using a laser diffraction / scattering particle size distribution analyzer (Zetasizer Nano manufactured by Malvern).

Although it does not specifically limit as a manufacturing method of an aqueous dispersion composition, For example, the following manufacturing methods are mentioned. That is, the modified polyolefin (A) is heated and dissolved in one or more solvents selected from the group consisting of ether solvents, alcohol solvents and aromatic solvents, and water, after adding a basic substance and cooling. It can be obtained by removing these solvents. The composition of the emulsifier (E), the anionic group-containing water-soluble polymer (C) and / or the electrolyte (D) is not particularly limited, but can be arbitrarily selected during emulsification, before solvent concentration, after solvent concentration, and the like. . In particular, the emulsifier (E) is preferably added after the solvent concentration because foaming during the solvent concentration can be suppressed.

Although it does not specifically limit as an ether solvent, Tetrahydrofuran (henceforth THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. are mentioned, These are single 1 type or 2 types. A combination of the above can be used. Of these, tetrahydrofuran is preferred.

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

Examples of the aromatic solvent include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, solvent naphtha and the like, and these can be used alone or in combination of two or more. Of these, toluene is preferable.

The amount of the solvent and water used can be arbitrarily selected, but is preferably modified polyolefin (A): water: solvent = 100: 50 to 800: 11 to 900 (mass ratio), and 100: 200 to More preferably, it is 400: 43 to 233 (mass ratio). When the amount of water or solvent is large, the modified polyolefin is more easily dispersed in water. However, it takes time for concentration and the volumetric efficiency is lowered, which is economically disadvantageous and impractical. Dispersion may not be possible when there is little water. When the amount of the solvent is small, the viscosity is remarkably increased at the time of dissolution by heating, so that uniform dissolution cannot be achieved and eventually uniform dispersion may not be possible.

The temperature at the time of melting by heating is not particularly limited, but is preferably 50 ° C. or higher. Moreover, if it is 75 degrees C or less, it is below the boiling point of the organic solvent to be used, and a pressure vessel is unnecessary for melt | dissolving with heating, and it is preferable. The dissolution time is not particularly limited, but can be completely dissolved usually in 1 to 2 hours.

The aqueous dispersion composition according to the present invention includes the modified polyolefin (A), the basic substance (B), the emulsifier (E), and an anionic group-containing water-soluble composition as long as the performance of the present invention is not impaired as required. In addition to the polymer (C) and / or the electrolyte (D), various additives can be blended and used. Although it does not specifically limit as an additive, It is preferable to use a viscosity modifier, a film-forming auxiliary | assistance, a wetting agent, a flame retardant, a pigment, an antiblocking agent, etc. Aqueous dispersion compositions containing these various additives can be used for paints, inks, sealants, primers or adhesives.

The viscosity modifier is not particularly limited, and examples thereof include alkali swelling viscosity modifiers, alkali swelling association viscosity modifiers, urethane association viscosity modifiers, and the like. Specific examples of the alkali swelling type viscosity modifier are not particularly limited, but specific examples of the Primal (registered trademark) ASE 60 and the alkali swelling association type viscosity modifier are not particularly limited, but include Primal DR-72, urethane association type. Specific examples of the viscosity modifier are not particularly limited, and examples include Adecanol (registered trademark) UH-752.

<Laminate>
The laminate of the present invention refers to a laminate of a polyolefin substrate bonded with the adhesive of the present invention and a resin substrate, metal substrate or wood substrate. Although it does not specifically limit as a resin base material, Resin sheets or resin films, such as polyvinyl chloride, polyester, polyolefin, polyamide, a poval, or a polyurethane, are mentioned. Moreover, it does not specifically limit as a metal base material, Various metals, such as aluminum, SUS, copper, iron, zinc, metal plates, such as each alloy and a plating product, and metal foil are mentioned.

<Viscosity of aqueous dispersion composition>
The viscosity when the solid content of the modified polyolefin in the aqueous dispersion composition of the present invention is 30% by mass is evaluated by measuring the viscosity of the solution at 25 ° C. at a rotor rotational speed of 60 rpm using a Brookfield viscometer.
(Evaluation criteria)
◎ (particularly excellent in practical use): 200 mPa · s or less ○ (excellent in practical use): over 200 mPa · s to 300 mPa · s or less Δ (practical use): over 300 mPa · s to 500 mPa · s × (impractical) ): Over 500 mPa · s, or viscosity cannot be measured due to gelation

<Evaluation of effects on viscosity modifier>
In order to apply the coating material, ink, sealant, primer or adhesive containing the aqueous dispersion composition to a substrate or the like, it is necessary to add a viscosity modifier to develop a certain viscosity. At this time, a charge reducing agent such as an electrolyte may inhibit the effect of the viscosity adjusting agent. Therefore, the influence of the charge reducing agent on the viscosity modifier was evaluated. Specifically, a viscosity modifier is added to the aqueous dispersion composition before and after the addition of the anionic group-containing water-soluble polymer and / or electrolyte (charge reducing agent), the viscosity is measured, and evaluation is performed according to the following formula.
(Evaluation criteria)
η _d = viscosity after addition of charge reducing agent / viscosity before addition of charge reducing agent ◎ (particularly excellent in practical use): η _d = 0.9 or more ○ (excellent in practical use): η _d = 0.7 or more, 0. Less than 9 △ (practical): η _d = 0.5 or more, less than 0.7 × (impractical): η _d = less than 0.5

<Evaluation as paint, ink, sealant, primer>
Evaluation as a paint, ink, sealant or primer containing the aqueous dispersion composition of the present invention was performed by preparing a coating film sample and evaluating its adhesion and water resistance.

<Preparation of paint film sample>
A film forming aid and a wetting agent are added to the aqueous dispersion composition to prepare a primer paint simulation liquid (also called a flash primer). The flash primer is applied to the substrate 1 (polypropylene plate) so that the film thickness after drying with a bar coater is 10 μm. After pre-drying the coated surface with a warm air dryer for 10 minutes in an 80 ° C atmosphere, a two-component urethane paint is applied with a spray gun and dried with a warm air dryer for about 35 minutes in an atmosphere of about 80 ° C for a coating sample Get.

<Evaluation of adhesiveness of coating film>
The coating film sample is allowed to stand for 36 hours in an atmosphere of 25 ° C., and 100 grids are made on the painted surface with a cutter knife at intervals of 1 mm, and a cellophane adhesive tape is closely attached on the coated surface and pulled at an angle of 60 °. Remove. Repeat the stripping 10 times using new cellophane adhesive tape. 10 points when the coating surface did not change after 10 repetitions, 9 points when peeling occurred at the 10th time, and 8 points below, 7, 6 points, and 0 points when peeling occurred at the first time .
(Evaluation criteria)
○ (Excellent for practical use): 10 points △ (Practical use): 9 points × (Practical use impossible): 8 points or less

<Evaluation of water resistance of coating film>
The coating film sample was allowed to stand for 36 hours in a 25 ° C. atmosphere, and then immersed in warm water of 40 ° C. for 10 days. After confirming the change of the coating film sample, the adhesiveness was evaluated. The case where there was no change in the coating film sample and the adhesive evaluation was 10 points was evaluated as good and good. The case where there was no change in the coating film sample and the adhesion evaluation was 9 points was evaluated as Δ. The case where blister was generated in the coating film sample or the adhesion evaluation was 8 points or less was evaluated as x.

<Evaluation as an adhesive>
Evaluation as an adhesive containing the aqueous dispersion composition of the present invention was performed by preparing a laminate sample and evaluating the adhesiveness.

<Preparation of laminate sample>
The aqueous dispersion composition is applied to a polyolefin substrate using a bar coater so that the thickness of the dried aqueous dispersion composition layer is adjusted to 3 μm. The coated surface is dried for about 10 minutes in an atmosphere of about 80 ° C. with a warm air dryer. A metal substrate is superimposed on the surface of the aqueous dispersion composition layer, and a laminate is obtained by thermocompression bonding at about 120 ° C. and about 0.1 MPa for about 2 minutes.

<Evaluation of adhesiveness of laminate>
Based on the test method of ASTM-D1876-61, the peel strength at a tensile speed of 50 mm / min is measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation. The peel strength (N / cm) between the metal substrate / polyolefin substrate is the average of five test values.
(Evaluation criteria)
◎ (particularly excellent in practical use): 8 N / cm or more ○ (excellent in practical use): 7 N / cm or more and less than 8 N / cm Δ (practical): 6 N / cm or more and less than 7 N / cm × (impractical): 6 N / less than cm

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples. In the examples and comparative examples, “parts” simply means “parts by mass”.

Production Example 1
A 1 L autoclave was charged with 100 parts by weight of a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals), 300 parts by weight of toluene and 25 parts by weight of maleic anhydride, and the temperature was raised to 120 ° 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 poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the resin-containing liquid was centrifuged to separate and purify the acid-modified propylene-butene copolymer grafted with maleic anhydride and the ungrafted maleic anhydride and low molecular weight substances. Thereafter, it is dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, modified amount of maleic anhydride is 2.0 mass%, weight average molecular weight is 50,000). It was.

Production Example 2
A maleic anhydride modified propylene-butene copolymer (PO-2, modified amount of maleic anhydride 1.0 mass), except that the amount of maleic anhydride charged was changed to 15 parts by mass. %, Weight average molecular weight 80,000).

Production Example 3
A maleic anhydride-modified propylene-butene copolymer (PO-3, modified amount of maleic anhydride: 1.5 mass), except that the amount of maleic anhydride charged was changed to 21 parts by mass. %, Weight average molecular weight 70,000).

Production Example 4
In a 1 L autoclave equipped with a stirrer, 100 parts by mass of propylene-ethylene copolymer (MFR = 5 g / 10 min at 230 ° C. atmosphere), 150 parts by mass of toluene and 20 parts by mass of maleic anhydride, di-tert-butyl per After 5 parts by mass of oxide was added and the temperature was raised to 140 ° C., the mixture was further stirred for 3 hours. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-ethylene copolymer grafted with maleic anhydride, (poly) maleic anhydride and low molecular weight substances. Thereafter, it was dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer. Next, 100 parts by mass of maleic anhydride-modified propylene-ethylene copolymer and 1700 parts by mass of chloroform were sealed in a 2 L glass-lined reaction can and sealed. The solution in the reaction can was heated while being stirred and dispersed, and dissolved in the can at a temperature of 120 ° C. for 1 hour. After cooling the internal temperature to 110 ° C., 0.5 parts by mass of t-butylperoxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. The temperature inside the can was cooled to 60 ° C., 1400 parts by mass of chloroform was distilled off, and 4 parts by mass of pt-butylphenylglycidyl ether was added as a stabilizer. Thereafter, by drying, maleic anhydride modified chlorinated propylene-ethylene copolymer (CPO-1, modified amount of maleic anhydride 2.5% by mass, chlorine content 20% by mass, weight average molecular weight 80,000) Got.

Production Example 5
By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 160 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-2, maleic anhydride modification amount 0.8 mass%, chlorine content 40 mass%, weight average molecular weight 100,000) was obtained.

Production Example 6
By changing the amount of maleic anhydride charged to 35 parts by mass, the amount of di-tert-butyl peroxide charged to 6 parts by mass and the amount of chlorine introduced to 10 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-3, modified amount of maleic anhydride 3.0% by mass, chlorine content 15% by mass, weight average molecular weight 70,000) was obtained.

Example 1
After 210 parts by weight of ion-exchanged water, 100 parts by weight of PO-1, 110 parts by weight of tetrahydrofuran, 45 parts by weight of isopropyl alcohol, and 55 parts by weight of toluene were placed in a flask equipped with a stirrer and heated to 70 ° C. The solution was heated and dissolved at the same temperature for 1 hour. Next, 3.6 parts by mass (2 chemical equivalents) of N, N-dimethylethanolamine was added, and after gradually cooling to 40 ° C. over 1 hour, the organic solvent was removed at a reduced pressure of about 10 kPa (absolute pressure). Distilled off. Thereafter, 40 parts by mass of a 25% by mass aqueous solution of polyoxyethylene lauryl ether was added to obtain a cloudy aqueous dispersion composition (a1-1). To this aqueous dispersion composition, 5 parts by mass (solid content) of Jonkrill (registered trademark) PDX-6137A was added to obtain an aqueous dispersion composition (a2-1). The aqueous dispersion composition (a2-1) had a solid content concentration of 30% by mass, a viscosity at 25 ° C. of 58 mPa · s, a pH of 9.0, and an average particle size of 85 nm.

Examples 2 to 22, Comparative Examples 1 to 6
Similarly to the aqueous dispersion compositions (a1-1) and (a2-1), the aqueous dispersion compositions (a1-1) to (a1-28), (a2- 1) to (a2-28) were obtained. The physical properties are shown in Tables 1 to 4.

Evaluation of effect on viscosity modifier (measurement of viscosity of aqueous dispersion composition)
100 parts by weight of the aqueous dispersion composition (a1-1) was collected in a beaker, and 8 parts by weight of an alkali swelling viscosity modifier (Primal (registered trademark) ASE 60, manufactured by Rohm and Haas) while stirring with a homodisper. Was gradually added dropwise and stirred for 10 minutes. After stirring, it was left overnight in a thermostatic bath at 25 ° C., stirred again with a homodisper, and the viscosity was measured with a Brookfield viscometer. The aqueous dispersion compositions (a1-2) to (a1-28) and (a2-1) to (a2-28) were also measured in the same manner as (a-1). The results are shown in Tables 1 to 4.

Preparation of coating film sample: 100 parts by weight of aqueous dispersion composition (a2-1), 10 parts by weight of film-forming aid (butyl cellosolve) and wetting agent (Enviromem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) A flash primer was prepared by adding 1 part by weight. The flash primer was applied to a polypropylene plate (manufactured by Yajima Seisakusho Co., Ltd.) using a bar coater. The coated surface was pre-dried for 10 minutes in an 80 ° C. atmosphere with a warm air dryer, and then a two-component urethane coating was applied with a spray gun, and dried for 35 minutes in an 80 ° C. atmosphere with a warm air dryer to form a coating sample 1 Obtained. Coating film samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the coating film sample 1.

Adhesiveness of coating film The coating film sample 1 was allowed to stand for 36 hours in an atmosphere of 25 ° C., and 100 grids were made on the painted surface with a cutter knife at intervals of 1 mm, and a cellophane adhesive tape was adhered thereon. Peel off at an angle of 60 °. Repeat the stripping 10 times using new cellophane adhesive tape. 10 points when the coating surface did not change after 10 repetitions, 9 points when peeling occurred at the 10th time, 8 points below, 7, 6 points, and 0 points when peeling occurs at the first time did. Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.

Water resistance of coating film The coating film sample 1 was allowed to stand for 36 hours in a 25 ° C. atmosphere and then immersed in warm water at 40 ° C. for 10 days. After confirming the change of the coating film, the adhesiveness was evaluated. The case where there was no change in the coating film and the adhesive evaluation was 10 points was evaluated as good and good. The case where there was no change in the coating film and the adhesive evaluation was 9 points was evaluated as Δ. A case where blisters were generated in the coating film or the adhesive evaluation was 8 points or less was evaluated as x. Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.

Preparation of Laminate Sample Aqueous dispersion composition (a2-1) 100 parts by weight 10 parts by weight of a film-forming aid (butyl cellosolve) and a wetting agent (Envirogem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) 1 part by weight was added to produce an adhesive 1. Adhesive 1 was applied to an unstretched polypropylene film (Toyobo Pyrene (registered trademark) film CT, thickness 40 μm) using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 μm. . The coated surface was dried with a hot air dryer for 10 minutes in an atmosphere at 80 ° C., and an aluminum foil (8079-0, 40 μm in thickness) was superimposed on the surface of the adhesive layer. Laminate sample 1 was obtained by thermocompression bonding at 1 MPa for 2 minutes. Laminate samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the laminate sample 1.

<Evaluation of adhesiveness of laminate>
In accordance with the test method of ASTM-D1876-61, the peel strength of the laminate sample 1 at a tensile speed of 50 mm / min was measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation. The laminate samples 2 to 28 were measured in the same manner as the laminate sample 1. The results are shown in Tables 1 to 4.

The anionic group-containing water-soluble polymer (C) used in Tables 1 to 4 is as follows.
Anionic group-containing water-soluble polymer (c-1): Joncryl (registered trademark) PDX-6137A (styrene-acrylic monomer copolymer), nonvolatile content 28.0 wt%, solid content acid value 240 mgKOH / g-resin , Weight average molecular weight 16,500, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-2): Joncryl (registered trademark) 57J (styrene-acrylic monomer copolymer), non-volatile content 37.0% by weight, solid content acid value 215 mg KOH / g-resin, weight Average molecular weight 4,900, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-3): Joncryl (registered trademark) HPD-196 (styrene-acrylic monomer copolymer), non-volatile content 36.0% by weight, solid content acid value 200 mgKOH / g-resin , Weight average molecular weight 9,200, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-4): Joncryl (registered trademark) 52J (styrene-acrylic monomer copolymer), non-volatile content 60.0% by weight, solid content acid value 238 mgKOH / g-resin, weight Average molecular weight 1,700, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-5): Joncrill (registered trademark) JDX-6500 (styrene-acrylic monomer copolymer), non-volatile content 29.5 wt%, solid content acid value 85 mgKOH / g-resin , Weight average molecular weight 10,000, manufactured by BASF.

Since the aqueous dispersion composition according to the present invention contains a modified polyolefin, a basic substance and an emulsifier, and further contains at least one of an anionic group-containing water-soluble polymer and an electrolyte, the modification in the aqueous dispersion composition The viscosity at a polyolefin solid content of 30% by mass is constant within a range of 500 mPa · s or less. Furthermore, if an anionic group-containing water-soluble polymer is used, the effects of additives used at the time of coating, particularly the viscosity modifier, are not hindered. Therefore, it is suitable for fields such as automotive exterior paint applications, automotive interior paint applications, and home appliance adhesive applications.

Claims

An anionic group-containing water-soluble polymer (C) and electrolyte (D) containing a modified polyolefin (A), a basic substance (B) and an emulsifier (E), and having an acid value of 150 to 500 mgKOH / g-resin An aqueous dispersion composition containing at least one of the following.
The aquatic dispersion composition according to claim 1, wherein the modified polyolefin (A) is an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).
Containing 100 to 10 parts by mass of the modified polyolefin (A), 0.5 to 10 parts by mass of the basic substance (B), 1 to 30 parts by mass of the emulsifier (E), and an anionic group-containing water-soluble polymer (C 2) The aqueous dispersion composition according to claim 1, comprising 0.1 to 20 parts by mass of a total amount of the electrolyte (D).
A paint, ink, sealant, primer or adhesive containing the aqueous dispersion composition according to any one of claims 1 to 3.
A laminate of a polyolefin substrate bonded with the adhesive according to claim 4 and a resin substrate or a metal substrate.
A polyolefin substrate coated with the paint according to claim 4.