KR20160091817A - Aqueous dispersion composition containing modified polyolefin - Google Patents

Abstract

An aqueous dispersion containing a modified polyolefin having good adhesion and water resistance and having an aqueous dispersion composition having a viscosity of 500 mPa s or less. (A) and a basic substance (B) and further containing at least one of an anionic polymer-containing water-soluble polymer (C) having an acid value of 150 to 500 mgKOH / g resin and an electrolyte (D) Composition.

Description

AQUEOUS DISPERSION COMPOSITION CONTAINING MODIFIED POLYOLEFIN [0001] The present invention relates to a modified polyolefin-

The present invention relates to an aqueous dispersion composition containing a modified polyolefin. More particularly, the invention relates to an aqueous dispersion composition containing a modified polyolefin and a basic substance, which is suitable for use as a paint, an ink, a sealant, a primer or an adhesive, and further contains at least one of an anionic polymer containing an anionic group and an electrolyte.

Polyolefin-based resins such as polypropylene have excellent properties and are inexpensive and are used in large quantities in automobile parts, various films, various molded articles, and the like. However, since the polyolefin resin is crystalline and the surface is non-polar, it has a problem that it is difficult to coat and adhere.

For this reason, modified polyolefins such as acid-denatured polyolefins and acid-denatured chlorinated polyolefins have been developed for coating, printing, and bonding or adhering a polyolefin resin, and among them, an aqueous dispersion of a modified polyolefin (For example, Patent Documents 1 and 2). Since the aqueous dispersion composition of this modified polyolefin does not substantially use an emulsifier, there is no occurrence of unevenness of the coating film, and the coating film has good physical properties such as low solubility, water resistance and blocking resistance It is an excellent method.

Patent Document 1: JP-A-2009-079078 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-18659

However, in the above method, the viscosity of the aqueous dispersion composition may not be stable. If the viscosity is unstable, the handling at the time of production becomes defective and the production efficiency is lowered. In addition, when preparing paints and inks, additives such as various viscosity adjusting agents are added in addition to the modified polyolefin-containing aqueous dispersion composition, there is a problem that the handling becomes poor even then.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and the present inventors have intensively studied and, as a result, have found that the aqueous dispersion composition containing the modified polyolefin contains an aqueous polymer containing an anionic group and / And that the present invention has been completed.

Means for Solving the Problem In order to achieve the above object, the present inventors have made extensive studies and have proposed the following inventions.

(A) and a basic substance (B) and further containing at least one of an anionic polymer-containing water-soluble polymer (C) having an acid value of 150 to 500 mgKOH / g resin and an electrolyte (D) Composition.

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) relative to 100 parts by mass of the modified polyolefin (A), 0.1 to 10 parts by mass of the total amount of the anionic group-containing water-soluble polymer (C) By mass to 20% by mass.

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

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

A polyolefin substrate coated with the paint.

Since the aqueous dispersion composition according to the present invention contains an anionic group-containing water-soluble polymer and / or an electrolyte, the viscosity of the water-based dispersion composition at 30% by mass of the solid content of the modified polyolefin is controlled in the range of 500 mPa s or less . Further, since no emulsifier is practically used, the coating film produced by using the aqueous dispersion composition has no occurrence of stain and the like, and the adhesive property and the water resistance are good.

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 an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).

The acid-modified polyolefin (A1) used in the present invention is not limited, but it is preferable that at least one of an alpha, beta -unsaturated carboxylic acid and an acid anhydride thereof is added to at least one of polyethylene, polypropylene and propylene- It is preferably obtained by grafting.

The propylene-? -Olefin copolymer is obtained by copolymerizing? -Olefin with propylene as a main component. As the? -olefin, for example, one kind or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene and vinyl acetate can be used. Of these? -Olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the -olefin component in the propylene-? -Olefin copolymer is not limited, but is preferably 50 mol% or more, more preferably 70 mol% or more.

Examples of the at least one of the?,? - unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Of these, acid anhydrides are preferable, and maleic anhydride is more preferable. Specific examples thereof include a maleic anhydride-modified polypropylene, a maleic anhydride-modified propylene-ethylene copolymer, a maleic anhydride-modified propylene-butene copolymer and a maleic anhydride-modified propylene-ethylene-butene copolymer. One or more modified polyolefins may be used in combination.

The production method of the acid-modified polyolefin (A1) is not particularly limited, and for example, a radical graft reaction (that is, a method in which a radical species is generated for a polymer as a main chain and an unsaturated carboxylic acid and an acid A reaction in which an anhydride is graft-polymerized).

The radical generator is not particularly limited, but it is preferable to use an organic peroxide. Examples of the organic peroxide include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, Peroxides such as hexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; And azonitriles such as azobisisobutylonitrile, azobisisopropionitrile, and the like.

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 modified polyolefin (A) preferably has an acid modification amount of not less than 0.1% by mass, more preferably not less than 0.3% by mass, more preferably not less than 0.5% by mass, particularly preferably not less than 0.8% by mass, more preferably not less than 1% Is most preferable. Further, it is preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 7 mass% or less, particularly preferably 6 mass% or less, most preferably 5 mass% or less. If it is too small, it may be difficult to sufficiently disperse it, and if it is too large, water resistance of the coating film may be adversely affected.

The amount of acid modification in the case of acid modification with maleic anhydride can be determined by FT-IR (FT-IR8200PC, manufactured by Shimadzu Corporation). First, maleic anhydride is dissolved at an arbitrary concentration to prepare a calibration curve solution. Subjected to FT-IR measurement of the calibration solution of maleic anhydride of a carbonyl (C = O) stretching peak (1780 ㎝ ^{- 1)} of the combination creates a calibration curve from the absorbance. Dissolving the modified polyolefin (A) in chloroform was subjected to FT-IR measurement, new peaks (1780 ㎝ ^{- 1)} of a carbonyl bond of the maleic anhydride on the basis of the calibration curve is obtained by acid-modified amount of maleic anhydride from the absorbance of the .

The weight average molecular weight (Mw) of the modified polyolefin (A) is preferably in the range of 40,000 to 170,000. More preferably 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 in the range of 80,000 to 130,000. If it is too small, the cohesive force is weakened and the adhesiveness may be poor. On the other hand, if it is too large, the solubility decreases and a problem may arise in production of the aqueous dispersion composition.

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

The modified polyolefin (A) is preferably crystalline. Because of its crystallinity, it is advantageous because it has strong cohesive strength and is excellent in adhesiveness, water resistance, heat resistance and chemical resistance as compared with amorphous.

The crystallinity referred to in the present invention is obtained by raising the temperature to -100 deg. C to 250 deg. C at a rate of 10 deg. C / min using a differential scanning calorimeter (hereinafter also referred to as DSC, manufactured by T.A. Instrument Co., , Indicating a clear melting peak during the heating process. The melting point and the heat of fusion are measured from the top temperature and the area of the melting peak when they are heated and melted at a rate of 10 ° C / min using a DSC, cooled to a resin, and then reheated to melt.

The melting point (Tm) of the modified polyolefin (A) is preferably in the range of 50 占 폚 to 120 占 폚. More preferably in the range of 60 占 폚 to 100 占 폚, and most preferably in the range of 70 占 폚 to 90 占 폚. If it is less than the above-mentioned range, the cohesive force derived from the crystal is weakened, and the adhesion, water resistance, heat resistance and chemical resistance may be poor. On the other hand, when the amount exceeds the above-mentioned range, the solubility decreases and a problem may arise in 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) is preferably 5% by mass or less, More preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably 14% by mass or more. If the amount is less than the above-mentioned range, the solution stability may deteriorate and the emulsion can not be emulsified. The upper limit is preferably 40 mass% or less, more preferably 38 mass% or less, further preferably 35 mass% or less, particularly preferably 32 mass% or less, and most preferably 30 mass% or less. When the value is exceeded, the crystallinity of the acid-modified chlorinated polyolefin is lowered, and the bonding strength may be lowered.

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) to improve the dispersibility of the modified polyolefin (A).

The basic substance (B) is not particularly limited, but is preferably a volatile basic substance, and among these, ammonia and amines are preferable. Examples of the amines include, but are not limited to, monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dimethylpropanolamine, and the like can be given. , Particularly preferred are triethylamine and N, N-dimethylethanolamine. These volatile amines may be used alone or in combination of two or more.

The amount of the basic substance (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more based on 100 parts by mass of the modified polyolefin (A) desirable. It is more preferably 10 parts by mass or less, more preferably 9 parts by mass or less, further preferably 8 parts by mass or less, particularly preferably 7 parts by mass or less. If the amount is too small, the particle size of the dispersed particles of the obtained aqueous dispersion composition may be large and the storage stability may be deteriorated. If too large, the water resistance of the coating film may be deteriorated.

<Water-soluble polymer containing anionic group (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 of the aqueous dispersion composition when the solid content of the modified polyolefin is 30% by mass can be kept constant within a range of 500 mPa s or less.

Further, by using the anionic polymer (C) containing an anionic group, not only the viscosity of the aqueous dispersion composition is lowered, but also the effect of preventing the effect of the viscosity adjuster at the time of coating is exerted. The viscosifying agent exhibits a desired viscosity by hydration and association between polar groups in the coating material. However, when a low molecular compound such as an electrolyte is used as the charge reducing agent, the viscosity adjusting agent does not function to inhibit the association between the hydration and polar groups . On the other hand, it is considered that the water-soluble polymer (C) containing an anionic group is a polymer compound, so the flow in the coating is suppressed, and the interaction with the viscosity adjuster is small, thereby not affecting the effect of the viscosity adjuster. That is, when preparing paints, inks, sealants, primers and adhesives, it is necessary to incorporate various additives such as a viscosity adjusting agent in addition to the aqueous dispersion composition to prevent dripping during coating. If the water-soluble polymer (C) containing an anionic group is not deteriorated by the effect of the viscosity adjusting agent or the like, good coatings, inks, sealants, primers and adhesives can be obtained without the occurrence of droplet upon coating.

The anionic polymer-containing water-soluble polymer (C) refers to a polymer compound that dissolves in water to reduce the charge on the particle surface of the modified polyolefin (A). Specific examples include, but are not limited to, acrylic resins, urethane resins, and epoxy resins containing carboxyl groups, sulfonic acid groups, sulfuric acid ester groups and phosphate ester groups, and more specifically polystyrene sulfonic acid, polyacrylic acid, styrene- A water-soluble polymer containing an anionic group whose main component is a maleic anhydride copolymer, a styrene-acrylic monomer copolymer, a styrene-methacrylic monomer copolymer and the like. These anionic group-containing water-soluble polymers (C) may be used singly or in combination of two or more.

The acid value of the anionic polymer-containing water-soluble polymer (C) should be 150 mgKOH / g or more, preferably 160 mgKOH / g or more, more preferably 170 mgKOH / g or more More preferably not less than 180 mgKOH / g-resin, particularly preferably not less than 190 mgKOH / g-resin, and most preferably not less than 200 mgKOH / g-resin. If it is too low, the effect of lowering the viscosity of the aqueous dispersion composition may be reduced. Further, it is required to be not more than 500 mgKOH / g resin, preferably not more than 490 mgKOH / g resin, more preferably not more than 480 mgKOH / g resin, still more preferably not more than 470 mgKOH / g resin -Resin, particularly preferably not more than 460 mgKOH / g-resin, and most preferably not more than 450 mgKOH / g-resin. If it is too high, the water resistance of the coating film may be lowered, and the effect of the viscosity adjusting agent at the time of coating may be deteriorated. Within the above range, the viscosity of the aqueous dispersion composition and the physical properties of the coating film become favorable. The acid value of the anionic polymer-containing water-soluble polymer (C) can be measured in accordance with 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, still more preferably 3,000 or more, still more preferably 5,000 or more, Is at least 7,000, and most preferably at least 9,000. If it is too small, the effect of the viscosity adjusting agent at the time of coating may be deteriorated. It is preferably 30,000 or less, more preferably 29,000 or less, more preferably 28,000 or less, still more preferably 27,000 or less, particularly preferably 26,000 or less, and most preferably 25,000 or less. If it is too large, the solubility in water may be lowered and the effect of lowering the viscosity may be decreased. Within the above range, the viscosity of the aqueous dispersion composition and the physical properties of the coating film become favorable. The weight average molecular weight of the anionic group-containing water-soluble polymer (C) is a value measured by GPC in an atmosphere at 40 캜.

The solubility of the anionic group-containing water-soluble polymer (C) in water (20 캜) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 30% More preferable. The upper limit is not particularly limited, but practically, it is 50 mass% or less.

The amount of the anionic group-containing water-soluble polymer (C) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, and 2 parts by mass or less, relative to 100 parts by mass of the modified polyolefin (A) Or more. It is more preferably 20 parts by mass or less, more preferably 19 parts by mass or less, even more preferably 18 parts by mass or less, particularly preferably 17 parts by mass or less. If the amount is too small, the effect of lowering the viscosity may be small. If the amount is too large, the water resistance of the coating film may decrease, and the effect of the viscosity adjusting agent at the time of coating may be deteriorated.

&Lt; Electrolyte (D) >

The electrolyte (D) used in the present invention refers to a material that dissolves in water and is converted to positive ions and anions to exhibit conductivity. By using an electrolyte, the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition can be reduced, whereby the viscosity when the solid content of the modified polyolefin is 30% by mass in the aqueous dispersion composition is 500 mPa s And can be made constant in the following range. The electrolyte (D) is not particularly limited and includes, for example, citric acid, isocitric acid, malic acid, leucic acid, mevalonic acid, fic acid, ricinolic acid, ricinelidic acid, cresolic acid, Aliphatic hydroxy acids such as malic acid, malic acid, malic acid, malic acid, malic acid, malic acid, malic acid, But are not limited to, salicylic acid, creosotic acid, vanillic acid, sicric acid, pyrocatechuic acid, resorcinol, protocatechuic acid, gentisilic acid, orsellic acid, gallic acid, mandelic acid, benzylic acid, atrolactic acid, Aromatic hydroxycarboxylic acids such as cumaric acid, umbellic acid, caffeic acid, ferulic acid and cinnamic acid; Halogenated alkali (earth) metal salts such as lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, sodium iodide and calcium iodide. Among these, citric acid, isocitric acid, and sodium chloride are preferable. These electrolytes (D) may be used alone or in combination of two or more.

The amount of the electrolyte (D) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, particularly preferably 2 parts by mass or more, per 100 parts by mass of the modified polyolefin (A) Do. It is more preferably 20 parts by mass or less, more preferably 19 parts by mass or less, even more preferably 18 parts by mass or less, particularly preferably 17 parts by mass or less. If the amount is too small, the effect of lowering the viscosity may be small. If the amount is too large, the water resistance of the coating film may decrease.

The total amount of the anionic group-containing water-soluble polymer (C) and the electrolyte (D) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and 1.5 parts by mass or more based on 100 parts by mass of the modified polyolefin (A) And still more preferably 2 parts by mass or more. It is more preferably 20 parts by mass or less, more preferably 19 parts by mass or less, even more preferably 18 parts by mass or less, particularly preferably 17 parts by mass or less. If the amount is too small, the effect of lowering the viscosity may be small. If the amount is too large, the water resistance of the coating film may decrease, and the effect of the viscosity adjusting agent at the time of coating may be deteriorated.

&Lt; Aqueous Dispersion Composition >

The aqueous dispersion composition of the present invention is a mixture containing the modified polyolefin (A) and the basic substance (B) and further containing at least one of the anionic group-containing water-soluble polymer (C) and the electrolyte (D).

When the solid content of the modified polyolefin (A) is 30% by mass, the aqueous dispersion composition preferably has a viscosity at 25 占 폚 of 500 mPa 占 퐏 or less as measured using a Brookfield viscometer (rotor speed: 60 rpm) desirable. More preferably, it is 400 mPa.s or less, more preferably 300 mPa.s or less, and particularly preferably 200 mPa.s or less. If it is excessively large, the processability and the like at the time of production of the aqueous dispersion composition and at the time of producing the paint may become defective. The lower the viscosity is, the better the handling property is. Therefore, the lower limit is not particularly limited, but it is practically 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 from 5 to 50 mass%, more preferably from 10 to 45 mass%, still more preferably from 15 to 40 mass% And preferably from 20 to 35 mass%. When the solid content concentration of the modified polyolefin (A) is too high, the viscosity becomes high and cohesion easily occurs between the modified polyolefin particles, so that the dispersion stability may be considerably lowered. On the other hand, if it is too low, it is difficult to say that it is practical from both the manufacturing side and the use side.

The modified polyolefin (A) contained in the aqueous dispersion composition preferably has a particle diameter of 5 to 500 nm, more preferably 10 to 400 nm, and further preferably 15 to 300 nm. If it is too small, the film-forming property tends to be improved. However, this is not preferable because fusion and agglomeration between dispersed particles tend to occur, resulting in a decrease in dispersion stability. On the other hand, if it is too large, not only the dispersion stability is greatly lowered but also the film-forming property is lowered, so that the appearance and performance of the obtained coating film may deteriorate.

The measurement of the particle diameter of the modified polyolefin (A) contained in the aqueous dispersion composition can be carried out using a laser diffraction / scattering method particle size distribution measuring apparatus (Zetaizer Nano, Maru Reflection).

Since the aqueous dispersion composition of the present invention contains substantially no emulsifier, the coating film produced by using the aqueous dispersion composition has no occurrence of stain and the like, and the adhesive property and the water resistance are good. Specifically, it is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, further preferably 0.1 parts by mass or less, based on 100 parts by mass of the modified polyolefin (A) , And 0 parts by mass are particularly preferable. The total amount of the modified polyolefin (A), the basic substance (B), the anionic group-containing water-soluble polymer (C), the electrolyte (D) and water in the aqueous dispersion composition is preferably 99.85% by mass or more, more preferably 99.94% More preferably 99.97% by mass or more, and particularly preferably 100% by mass.

Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier, and surfactants are generally used in addition to emulsion polymerization. Examples of the anionic emulsifier include sulfuric acid ester salts of higher alcohols, higher alkylsulfonates, higher carboxylates, alkylbenzenesulfonates, polyoxyethylene alkylsulfate salts, polyoxyethylene alkylphenylether sulfate salts, vinylsulfosuccinates Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer , And sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters. Examples of amphoteric emulsifiers include lauryl betaine and lauryldimethylamine oxide.

The method for producing the aqueous dispersion composition is not particularly limited, and for example, the following production methods can be mentioned. That is, the modified polyolefin (A) is heated and dissolved in at least one solvent selected from the group consisting of an ether solvent, an alcohol solvent and an aromatic solvent, and water, and a basic material is added. After cooling, . The blend of the anionic polymer-containing water-soluble polymer (C) and / or the electrolyte (D) is not particularly limited, but may be arbitrarily selected during emulsification, before solvent concentration, and after solvent concentration.

Examples of the ether solvent include, but are not limited to, tetrahydrofuran (hereinafter also referred to as THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc., Two or more species may be used in combination. Among them, tetrahydrofuran is preferable.

The alcoholic solvent is not particularly limited, and examples thereof include aliphatic alcohols having 1 to 7 carbon atoms, aromatic alcohols, alicyclic alcohols, etc. These solvents can be used singly or in combination of two or more kinds. Among them, 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 solvents include benzene, toluene, xylene, ethylbenzene, isopropylbenzene and solvent naphtha. These solvents may be used alone or in combination of two or more. Among them, toluene is preferable.

The amount of the solvent and the amount of water to be used may be selected arbitrarily, but it is preferable that the amount of the modified polyolefin (A): water: solvent is 100: 50 to 800: 11 to 900 (mass ratio), 100: 200 to 400: 43 to 233 Is more preferable. When water or a large amount of solvent is used, the modified polyolefin is more easily dispersed in water, but it takes time to concentrate or the volume efficiency is lowered, which is economically disadvantageous and is not practical. When water is small, dispersion may not be possible in some cases. When the amount of the solvent is small, the viscosity increases remarkably at the time of heating and dissolution, and uniform dissolution can not be performed, and as a result, uniform dispersion can not be achieved in some cases.

The temperature at the time of heating and dissolving is not particularly limited, but is preferably 50 ° C or more. When the temperature is not higher than 75 캜, it is preferable that the boiling point of the organic solvent to be used is less than or equal to the boiling point, and a pressure vessel is not required for heating and dissolving. The dissolving time is not particularly limited, but is usually completely dissolved in 1 to 2 hours.

The aqueous dispersion composition according to the present invention may contain the modified polyolefin (A), the basic substance (B), the anionic group-containing water-soluble polymer (C) and / or the electrolyte D), various additives may be used in combination. The additive is not particularly limited, but it is preferable to use a viscosity adjusting agent, a film forming auxiliary, a wetting agent, a flame retardant, a pigment, an antiblocking agent and the like. An aqueous dispersion composition containing these various additives may be used in paints, inks, sealants, primers or adhesives.

The viscosifying agent is not particularly limited, and examples thereof include an alkali swelling viscosity adjusting agent, an alkaline swelling associating viscosity adjusting agent, and a urethane associating viscosity adjusting agent. Specific examples of the alkali swellable viscosity adjustor include, but are not particularly limited to, specific examples of Primer (registered trademark) ASE60 and alkali swell associative viscosity adjustor include, but are not limited to, Primer DR-72, spheres of urethane associative viscosity regulator Examples include, but are not limited to, adecanol (registered trademark) UH-752 and the like.

<Laminate>

The laminate of the present invention refers to a laminate of a polyolefin substrate adhered with the adhesive of the present invention and a resin substrate, a metal substrate or a wood substrate. The resin substrate is not particularly limited, and resin sheets or resin films such as polyvinyl chloride, polyester, polyolefin, polyamide, polyurethane, or polyurethane can be given. The metal substrate is not particularly limited, and examples thereof include various metals such as aluminum, SUS, copper, iron and zinc, and metal plates and metal foils such as alloys and plated products.

&Lt; Viscosity of aqueous dispersion composition >

When the solid content of the modified polyolefin in the aqueous dispersion composition of the present invention is 30% by mass, the viscosity of the solution at 25 캜 is measured and measured by using a Brookfield viscometer at a rotor rotation number of 60 rpm.

(Evaluation standard)

◎ (Practically excellent): 200 mPa · s or less

○ (Practically excellent): Above 200 mPa · s and below 300 mPa · s

△ (practical): Above 300 mPa · s and below 500 mPa · s

× (practically impossible): viscosity exceeding 500 mPa · s or gelation is not measurable

&Lt; Evaluation of influence on viscosity control agent >

In order to apply a coating material, an ink, a sealant, a primer or an adhesive containing the aqueous dispersion composition to a substrate or the like, it is necessary to form a viscous adjustment agent to exhibit a certain viscosity. At this time, the charge reducing agent such as an electrolyte may hinder the effect of the viscosity adjusting agent. Therefore, the influence of the charge reducing agent on the viscosity adjusting agent was evaluated. Concretely, the viscosity adjusting agent is added to the aqueous dispersion composition before and after the addition of the anionic group-containing water-soluble polymer and / or the electrolyte (charge-reducing agent) and viscosity is measured and evaluated by the following formula.

(Evaluation standard)

η _d = viscosity after addition of charge reducing agent / viscosity before addition of charge reducing agent

? (Practically excellent):? _D = 0.9 or more

? (Practically excellent):? _D = 0.7 or more, less than 0.9

? (Practicable):? _D = 0.5 or more and less than 0.7

× (practically impossible): η _d = less than 0.5

&Lt; Evaluation as paint, ink, sealant, primer >

The evaluation as a paint, an ink, a sealant or a primer containing the aqueous dispersion composition of the present invention was carried out by preparing samples of coating films and evaluating them according to their adhesiveness and water resistance.

&Lt; Preparation of coating film sample >

A film forming aid and a wetting agent are added to the aqueous dispersion composition to prepare a primer coating solution (also referred to as a flash primer). The flash primer is coated on the substrate 1 (polypropylene plate) with a bar coater so as to have a thickness of 10 mu m after drying. The coated surface is preliminarily dried with a hot air dryer in an atmosphere at 80 캜 for 10 minutes, and then applied with a spray gun in a two-pack urethane paint and dried for about 35 minutes under a temperature of about 80 캜 in a hot air dryer to obtain a coated film sample.

&Lt; Evaluation of adhesiveness of coated film &

After the coated film sample was allowed to stand in an atmosphere at 25 캜 for 36 hours, 100 scissors scales were formed at intervals of 1 mm with a cutter knife on the coated surface, and a cellophane adhesive tape was closely adhered thereon and peeled at an angle of 60 °. Peeling is repeated 10 times using a new cellophane adhesive tape. 10 points, 10 points, 10 points, 9 points, 8 points, 7 points, 6 points, and no peeling at the first time.

(Evaluation standard)

○ (Excellent in practice): 10 points

△ (practical): 9 points

× (practically impossible): 8 points or less

<Evaluation of Water Resistance of Coating Film>

The coated film sample was allowed to stand in an atmosphere at 25 캜 for 36 hours, and then immersed in hot water at 40 캜 for 10 days. After confirming the change of the sample of the coating film, the adhesion was evaluated. The case where there was no change in the sample of the coating film and the evaluation of the adhesiveness was 10 points was evaluated as good. A case in which there was no change in the sample of the coating film and 9 points in the evaluation of the adhesiveness was evaluated as?. A case where a blister occurred in the sample of the coating film, or a case where the blister was 8 points or less in the evaluation of the adhesion property was evaluated as &quot; Bad &quot;

&Lt; Evaluation as adhesive >

The evaluation as an adhesive containing the aqueous dispersion composition of the present invention was carried out by preparing a sample of a layered product and evaluating the adhesiveness.

&Lt; Preparation of laminated sample &

The aqueous dispersion composition is coated on the polyolefin substrate so that the film thickness of the aqueous dispersion composition layer after drying using a bar coater is adjusted to 3 占 퐉. The coated surface is dried in a hot air dryer at about 80 ° C for about 10 minutes. The metal substrate is superimposed on the surface of the aqueous dispersion composition layer and thermocompression-bonded at about 120 DEG C and about 0.1 MPa for about 2 minutes to obtain a laminate.

&Lt; Evaluation of adhesiveness of laminate &

The peel strength at a tensile speed of 50 mm / min is measured at 25 占 폚 using Tensilon RTM-100 manufactured by Orientech Corporation according to the test method of ASTM-D1876-61. The peel strength (N / cm) between the metal substrate and the polyolefin substrate is an average value of five test values.

(Evaluation standard)

◎ (Practically excellent): 8 N / cm or more

○ (practically excellent): 7 N / cm or more and less than 8 N / cm

? (Practicable): 6 N / cm or more and less than 7 N / cm

× (practically impossible): less than 6 N / cm

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments. In the examples and the comparative examples, the description simply refers to parts by mass.

Manufacturing example  One

A 1 L autoclave was charged with 100 parts by mass of propylene-butene copolymer ("TFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals, Inc.), 300 parts by mass of toluene and 25 parts by mass of maleic anhydride, And 8 parts by mass of di-tert-butyl peroxide were added, followed by stirring for 1 hour. Thereafter, the obtained reaction solution was cooled and then poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Thereafter, the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer obtained by graft-polymerizing maleic anhydride and a maleic anhydride and a low molecular weight without graft. Thereafter, the resultant was dried under reduced pressure at 70 占 폚 for 5 hours to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, a modified amount of maleic anhydride of 2.0 mass%, weight average molecular weight of 50,000).

Manufacturing example  2

Maleic anhydride-modified propylene-butene copolymer (PO-2, a modified amount of maleic anhydride of 1.0% by mass, a weight average molecular weight of 80,000) was obtained in the same manner as in Production Example 1 except that the content of maleic anhydride was changed to 15 parts by mass, .

Manufacturing example  3

Maleic anhydride-modified propylene-butene copolymer (PO-3, a modified amount of maleic anhydride of 1.5% by mass, a weight average molecular weight of 70,000) was obtained in the same manner as in Production Example 1 except that the content of maleic anhydride was changed to 21 parts by mass, .

Manufacturing example  4

100 parts by mass of a propylene-ethylene copolymer (MFR = 5 g / 10 min in an atmosphere at 230 캜), 150 parts by mass of toluene and 20 parts by mass of maleic anhydride were charged in a 1 L autoclave equipped with a stirrer, 5 parts by mass of oxide were added, the temperature was raised to 140 占 폚, and the mixture was further stirred for 3 hours. Thereafter, the obtained reaction solution was cooled and then poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Thereafter, the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-ethylene copolymer obtained by graft-polymerizing maleic anhydride, (poly) maleic anhydride and a low molecular weight. Thereafter, the resultant was dried under reduced pressure at 70 DEG C for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer. Subsequently, 100 parts by mass of a maleic anhydride-modified propylene-ethylene copolymer and 1700 parts by mass of chloroform were put in a 2 L glass-lined reaction tube and sealed. The solution in the reaction tube was heated while being stirred and dispersed, and the solution was melted at 120 캜 for 1 hour. After the internal temperature of the tube was cooled to 110 캜, 0.5 part by mass of t-butylperoxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. The internal temperature of the tube was cooled to 60 占 폚, and 1400 parts by mass of chloroform was distilled off. Then, 4 parts by mass of p-t-butylphenylglycidyl ether was added as a stabilizer. Thereafter, by drying, a maleic anhydride-modified chlorinated propylene-ethylene copolymer (CPO-1, a modified amount of maleic anhydride of 2.5 mass%, a chlorine content of 20 mass%, and a weight average molecular weight of 80,000) was obtained.

Manufacturing example  5

Except that the content of maleic anhydride was changed to 9 parts by mass, the content of di-tert-butyl peroxide was changed to 3 parts by mass, and the amount of chlorine introduced was changed to 160 parts by mass, Ethylene copolymer (CPO-2, a modification amount of maleic anhydride of 0.8 mass%, a chlorine content of 40 mass%, and a weight average molecular weight of 100,000).

Manufacturing example  6

Except that the content of maleic anhydride was changed to 35 parts by mass, the content of di-tert-butyl peroxide was changed to 6 parts by mass, and the amount of chlorine introduced was changed to 10 parts by mass, whereby a maleic anhydride-modified chlorinated propylene- Ethylene copolymer (CPO-3, a modified amount of maleic anhydride of 3.0% by mass, a chlorine content of 15% by mass, and a weight average molecular weight of 70,000).

Example  One

210 parts by mass of ion-exchanged water, 100 parts by mass of PO-1, 110 parts by mass of tetrahydrofuran, 45 parts by mass of isopropyl alcohol and 55 parts by mass of toluene were placed in a flask equipped with a stirrer, And then heated and melted at the same temperature for 1 hour. Subsequently, 3.6 parts by mass (2 chemical equivalents) of N, N-dimethylethanolamine was added and the mixture was gradually cooled to 40 占 폚 over 1 hour, and then the organic solvent was distilled off at a reduced pressure of about 10 ㎪ To obtain a cloudy aqueous dispersion composition (a1-1). 5 parts by mass (solid content) of Zoncryl (registered trademark) PDX-6137A was added to this aqueous dispersion composition to obtain an aqueous dispersion composition (a2-1). The solid content concentration of the aqueous dispersion composition (a2-1) was 30 mass%, the viscosity at 25 占 폚 was 64 mPa 占 퐏, the pH was 9.0, and the average particle diameter was 92 nm.

Example  2 to 22, Comparative Example  1 to 6

(A1-1) to (a1-28), (a2-1) to (a2-2) shown in Tables 1 to 4 were prepared in the same manner as in the aqueous dispersion compositions (a1-1) (a2-28). Physical properties and the like are shown in Tables 1 to 4.

Evaluation of the effect on the viscosity adjusting agent Dispersant  Viscosity measurement of the composition)

100 parts by mass of the aqueous dispersion composition (a1-1) was sampled in a beaker, and 8 parts by mass of an alkali swelling viscosity control agent (Prima (registered trademark) ASE60, manufactured by Rohm and Haas Company) And stirred for 10 minutes. After stirring, the mixture was allowed to stand overnight in a constant temperature bath at 25 캜, stirred again with a homodisperser, and the viscosity was measured with a Brookfield viscometer. The aqueous dispersion compositions (a1-2) to (a1-28), (a2-1) to (a2-28) were measured in the same manner as in (a-1). The results are shown in Tables 1 to 4.

Coating film  Production of samples

10 parts by weight of a film forming auxiliary (butyl cellosolve) and 1 part by weight of a wetting agent (Envirozem (registered trademark) AD01, manufactured by Nisshinka Chemical Co., Ltd.) were added to 100 parts by weight of the aqueous dispersion composition (a2-1) To prepare a flash primer. The flash primer was applied to a polypropylene plate (manufactured by Yajima Seisakusho Co., Ltd.) using a bar coater. The coated surface was preliminarily dried with a hot air dryer in an atmosphere at 80 캜 for 10 minutes, and then a two-pack urethane paint was applied by a spray gun and dried in a hot air drier at 80 캜 for 35 minutes to obtain Coating Film Sample 1. Coating film samples 2 to 28 were also produced using aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as Coating film sample 1.

Of the coated film  Adhesiveness

After the coated film sample 1 was allowed to stand in an atmosphere of 25 ° C for 36 hours, 100 grid squares were formed at intervals of 1 mm with a cutter knife on the coated surface, and a cellophane adhesive tape was closely adhered thereon and peeled at an angle of 60 °. Peeling is repeated 10 times using a new cellophane adhesive tape. 10 points when there was no change on the coated surface even after 10 repetitions, and 9 points when the peeling occurred at 10th, 8 points, 7 points, and 6 points at the 10th peeling, and 0 point when peeling occurred at the first peeling Respectively. 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.

Of the coated film  Water resistance

The Coating Sample 1 was allowed to stand in an atmosphere at 25 캜 for 36 hours, and then immersed in hot water at 40 캜 for 10 days. After confirming the change of the coating film, the evaluation of adhesion was carried out. The case where there was no change in the coating film and the evaluation of the adhesiveness was 10 points was evaluated as good. &Quot; DELTA &quot; was defined as a case where there was no change in the coating film, and the evaluation of adhesion was 9 points. A case where blisters were generated in the coating film or the number of points was 8 or less in the evaluation of the adhesion property was evaluated as &quot; poor &quot;. 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.

The laminate  Production of samples

10 parts by weight of a film forming auxiliary (butyl cellosolve) and 1 part by weight of a wetting agent (Envirozem (registered trademark) AD01, manufactured by Nisshinka Chemical Co., Ltd.) were added to 100 parts by weight of the aqueous dispersion composition (a2-1) To prepare an adhesive 1. Adhesive 1 was coated on an unstretched polypropylene film (Pyrene (registered trademark) film CT manufactured by Toyobo Co., Ltd., thickness: 40 占 퐉) using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 占 퐉. The coated surface was dried with a hot-air dryer for 10 minutes in an atmosphere of 80 ° C, and an aluminum foil (8079-0, thickness: 40 μm) was laminated on the surface of the adhesive layer and dried at 120 ° C. and 0.1 MPa for 2 minutes The laminate sample 1 was obtained by thermocompression bonding. The laminate samples 2 to 28 were also produced using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the laminate sample 1.

&Lt; Evaluation of adhesiveness of laminate &

According to the test method of ASTM-D1876-61, the peel strength of the laminated sample 1 at a tensile speed of 50 mm / min was measured under the environment of 25 캜 using Tensilon RTM-100 manufactured by Orientech Corporation Respectively. The laminate samples 2 to 28 were also 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.

(Styrene-acrylic monomer copolymer), non-volatile matter content of 28.0% by weight, solid acid value of 240 mgKOH / g-resin, weight average molecular weight of 16,500, Manufactured by BASF.

(Styrene-acrylic monomer copolymer), non-volatile matter content 37.0% by weight, solid acid value 215 mgKOH / g-resin, weight average molecular weight 4,900, manufactured by BASF .

(Styrene-acrylic monomer copolymer), 36.0% by weight of nonvolatile matter, a solid acid value of 200 mgKOH / g-resin, a weight average molecular weight of 9,200, and an anionic group-containing water-soluble polymer (c-3): John Krill TM HPD- Manufactured by BASF.

(Styrene-acrylic monomer copolymer), nonvolatile matter 60.0% by weight, solid acid value 238 mgKOH / g-resin, weight average molecular weight 1,700, manufactured by BASF .

Water-soluble polymer containing anionic group (c-5): John Krill 占 JDX-6500 (styrene-acrylic monomer copolymer), nonvolatile matter 29.5% by weight, solid acid value 85 mgKOH / g- Manufactured by BASF.

Since the aqueous dispersion composition according to the present invention contains a modified polyolefin, a basic substance and an anionic group-containing water-soluble polymer and / or an electrolyte, the viscosity of the aqueous dispersion composition at a solid content of modified polyolefin of 30 mass% · It is constant in the range of s or less. When the water-soluble polymer containing an anionic group is used, there is no case where the effect of the additive used in painting, in particular, the viscosity adjusting agent is not hindered. Therefore, it is suitable for applications such as automotive exterior paint, interior paint for automobiles, and home electric appliance adhesives.

Claims (6)

(A) and a basic substance (B) and further containing at least one of an anionic polymer-containing water-soluble polymer (C) having an acid value of 150 to 500 mgKOH / g resin and an electrolyte (D) Composition. The aqueous 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). The electrolyte membrane according to claim 1, wherein the basic polyolefin (B) is contained in an amount of 0.5 to 10 parts by mass and the total amount of the anionic group-containing water-soluble polymer (C) and the electrolyte (D) is 0.1 to 20 parts by mass relative to 100 parts by mass of the modified polyolefin (A) By mass of the water-based dispersion composition. 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 and a resin substrate or a metal substrate adhered with the adhesive according to claim 4. A polyolefin substrate coated with a paint as described in claim 4.