JP2010090189A - Resin aqueous dispersion and production method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin aqueous dispersion of a hardly hydrolyzable acid-modified polyolefin/ether block copolymer which cannot be prepared as an aqueous dispersion in the conventional arts. <P>SOLUTION: The resin aqueous dispersion contains the following block copolymer (A), an aqueous medium and a basic compound. The copolymer (A) comprises an acid-modified polyolefin block (a) and a polyether block (b) having surface resistivity of 10<SP>5</SP>to 10<SP>11</SP>Ω, bonded by a mass ratio (a)/(b) ranging from 40/60 to 90/10, and has an acid value of 1 to 50 mgKOH/g. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous resin dispersion containing an acid-modified polyolefin / ether block copolymer, an antistatic coating agent comprising the same, a laminate, and a method for producing an aqueous resin dispersion.

  Various resin materials usually have a high electrical insulation property and are therefore easily charged. As a result, when the resin material is a film or a molded body, there is a problem that dust or dirt in the air is adsorbed to deteriorate the aesthetic appearance or the films stick to each other. Furthermore, when used in electrical equipment and OA equipment, various problems such as malfunction of IC and static electricity failure such as memory destruction may occur.

  In order to solve these problems, a method of kneading a polyolefin / ether block copolymer having antistatic performance into a thermoplastic resin is widely known (Patent Documents 1 and 2).

  The resin composition obtained by these methods and the molded product thereof are characterized in that the antistatic component is not eluted by water and the antistatic property can be maintained permanently. However, it is necessary to add a large amount of polyolefin / ether block copolymer to the resin material in order to fully exhibit the antistatic performance (for example, about 30% by mass with respect to the resin material). In some cases, the excellent physical properties of the resin material were impaired. Furthermore, since a high-molecular type antistatic agent such as a polyolefin / ether block copolymer is expensive, the cost burden is large.

  In contrast to these methods, as a method of imparting antistatic performance while maintaining the excellent physical properties of resin materials, a coating agent containing a polyolefin / ether block copolymer is applied to a film or molded body made of a resin material for charging. A method of laminating a prevention coat layer is conceivable. In this method, since the polymer type antistatic agent can be thinly laminated on the surface of the film or the molded body, a small amount of the polymer type antistatic agent is required and there is an advantage in terms of cost. large. In addition, as such a coating agent, a water-based thing is desired from a viewpoint of environmental conservation.

  Patent Document 3 proposes a method for producing an aqueous dispersion of a resin having a polyolefin / ether graft copolymer structure. However, the antistatic performance of the obtained polyolefin / ether graft copolymer is not described, and the antistatic performance of the aqueous dispersion coating film is not so good. Furthermore, since the polyolefin / ether block copolymer has poor solubility in various organic solvents, it has not been dispersed in an aqueous medium.

On the other hand, Patent Document 4 proposes a special aqueous method for dispersing an acid-modified polyolefin resin in an aqueous medium. However, there has been no research on whether an aqueous solution of an acid-modified polyolefin / ether block copolymer can be formed by this method.
JP 2005-028771 A JP 2002-321314 A JP 2007-246871 A JP 2003-119328 A

  The present invention is intended to provide an aqueous resin dispersion of an acid-modified polyolefin / ether block copolymer capable of obtaining a film having antistatic properties and adhesion to various substrates, in order to solve the above-mentioned problems. Is.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have dispersed an acid-modified polyolefin / ether block copolymer in an aqueous medium to produce a coating film having antistatic performance and adhesion to a substrate. An aqueous resin dispersion that can be obtained has been found and the present invention has been achieved.

That is, the first of the present invention is an aqueous resin dispersion containing a block copolymer (A), an aqueous medium and a basic compound, wherein the block copolymer (A) is an acid-modified polyolefin (a). And a block of a polyether (b) having a surface resistivity of 10 ⁵ to 10 ¹¹ Ω are bonded at a ratio of (a) / (b) = 40/60 to 90/10 (mass ratio). And an aqueous resin dispersion characterized by having an acid value of 1 to 50 mg KOH / g resin. Preferably, the polyether (b) is a polyether diol (b1), a poly It is the said resin aqueous dispersion which is a 1 or more types of compound chosen from the group which consists of etherdiamine (b2) and these modified | denatured products (b3).

  In the second aspect of the present invention, the resin aqueous solution is characterized in that the block copolymer (A), the basic compound, and an aqueous medium are used as raw materials, and these are heated and stirred at a temperature of 80 ° C to 250 ° C. The gist of the manufacturing method of the dispersion.

  The third aspect of the present invention is a gist of an antistatic coating agent comprising the above-described aqueous resin dispersion.

  Furthermore, the fourth aspect of the present invention is a laminate characterized by being obtained by coating the base material with the aqueous resin dispersion described above and then removing the aqueous medium.

  According to the present invention, it is possible to obtain an aqueous dispersion of a polyolefin / ether copolymer that could not be conventionally used as an antistatic coating agent. Furthermore, this resin aqueous dispersion is excellent in antistatic property and adhesion when coated on a substrate.

  Hereinafter, the present invention will be described in detail.

The first aqueous resin dispersion of the present invention is an aqueous resin dispersion containing a block copolymer (A), an aqueous medium and a basic compound, wherein the block copolymer (A) is acid-modified. The block of the polyolefin (a) and the block of the polyether (b) having a surface resistivity of 10 ⁵ to 10 ¹¹ Ω are (a) / (b) = 40/60 to 90/10 (mass ratio). It is bonded at a ratio and has an acid value of 1 to 50 mg KOH / g resin.

First, the block copolymer (A) used in the present invention will be described. In the block copolymer (A), an acid-modified polyolefin (a) block and a polyether (b) block having a volume resistivity of 10 ⁵ to 10 ¹¹ Ω · cm are ester bonds, amide bonds, ethers. It has a structure in which it is alternately and repeatedly bonded through at least one bond selected from the group consisting of a bond, a urethane bond and an imide bond.

  The acid-modified polyolefin resin (a) constituting the block copolymer (A) is modified with an unsaturated carboxylic acid (anhydride) in an appropriate polyolefin (a0), and has a carbonyl group, a carboxyl group, etc. at least at one end. Polyolefin contained.

  The above-mentioned polyolefin (a0) is composed of polyethylene, polypropylene, poly-4-methylpentene-1, polybutene, polyisobutylene, cycloolefin and the like, and may be one or more copolymers. . The polyolefin preferably has 2 to 30 carbon atoms in the olefin monomer, more preferably 2 to 15 carbon atoms, and particularly preferably polypropylene and / or polyethylene.

  As unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid and anhydrides thereof, for example, (meth) acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) And citraconic acid (anhydride). Among these, maleic acid (anhydride) and fumaric acid are preferable, and maleic acid (anhydride) is particularly preferable. The amount of unsaturated carboxylic acid (anhydride) used for modification is usually 0.5 to 40%, preferably 1 to 30%, based on the mass of the polyolefin (a0). Represents mass%).

  The number average molecular weight (hereinafter abbreviated as Mn) of the acid-modified polyolefin resin (a) in the present invention is preferably 800 to 25000, more preferably 1000 to 20000, and particularly preferably 2500 to 10,000. It is preferable that Mn is in the range of 800 to 25000 in terms of reactivity with the polyether (b) described later.

  The acid value of the acid-modified polyolefin resin (a) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described), more preferably 4 to 100, particularly preferably 5 to 80. An acid value within this range is preferable from the viewpoint of reactivity with the polyether (b) described later and aqueous dispersion.

The polyether (b) which is the other component constituting the block copolymer (A) is preferably a polyether diol (b1), a polyether diamine (b2), and a modified product (b3) thereof. Can be used. The surface specific resistance value of the polyether (b) (value measured at 20 ° C. and 60% RH in the method described later) is 10 ⁵ to 10 ¹¹ Ω, preferably 10 ⁵ to 10 ¹⁰ Ω, particularly Preferably, it is 10 ⁵ to 10 ⁹ Ω. When the surface specific resistance value exceeds 1 × 10 ¹¹ Ω · cm, the antistatic performance of the coating film may deteriorate.

The polyether diol (b1) has a structure obtained by addition reaction of an alkylene oxide with a diol, and has a general formula: H- (OA ¹ ) m -O-E ¹ -O- (A ¹ O) What is shown by m'-H is mentioned. In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from a diol, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and m and m ′ represent the number of added alkylene oxides per hydroxyl group of the diol. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used. m and m ′ are usually integers of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. M and m ′ may be the same or different.

  Examples of the diol include dihydric alcohols (for example, aliphatic, alicyclic or aromatic dihydric alcohols having 2 to 12 carbon atoms), dihydric phenols having 6 to 18 carbon atoms, and tertiary amino group-containing diols. Examples of the aliphatic dihydric alcohol include alkylene glycol (ethylene glycol, propylene glycol), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohol include cyclohexane dimethanol, and examples of the aromatic dihydric alcohol include xylylene diol. Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl, etc.) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

  Examples of the tertiary amino group-containing diol include aliphatic or alicyclic primary monoamines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, Hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc. ) And bishydroxyalkylated products of aromatic primary monoamines having 6 to 12 carbon atoms (aniline, benzylamine, etc.). Of these, preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A.

  The alkylene oxide to be added to the diol to produce the polyether diol (b1) is an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more of these are used, but if necessary, other alkylene oxides or substituted alkylene oxides (hereinafter collectively referred to as alkylene oxides), for example, having 5 to 5 carbon atoms. 12 α-olefins, styrene oxide, epihalohydrin (epichlorohydrin, etc.) can be used in a small proportion (for example, 30% or less based on the weight of the total alkylene oxide). Can be random and / or The preferred alkylene oxide is ethylene oxide alone or a combination of ethylene oxide and another alkylene oxide (block and / or random addition) The number of alkylene oxides added is the hydroxyl group of the diol. The number is usually an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100.

  The addition of alkylene oxide can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of oxyalkylene units having 2 to 4 carbon atoms in the polyether diol (b1) is usually 5 to 99.8%, preferably 8 to 99.6%, particularly preferably 10 to 98%. The content of oxyethylene units in the polyoxyalkylene chain is usually 5 to 100%, preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably 60 to 100%.

The polyether diamine (b2) has the general formula: H ₂ N—A ² — (OA ¹ ) m —O—E ¹ —O— (A ¹ O) m′—A ² —NH ₂ (symbol E in the formula ¹ , A ¹ , m and m ′ are the same as described above, and A ² is an alkylene group having 2 to 4 carbon atoms. A ¹ and A ² may be the same or different. Can be used. The polyether diamine (b2) can be obtained by changing the hydroxyl group of the polyether diol (b1) to an amino group by a known method, for example, obtained by cyanoalkylating the hydroxyl group of the polyether diol (b1). The terminal can be reduced to an amino group. Moreover, it can manufacture by making polyether diol (b1) and acrylonitrile react, and hydrogenating the cyanoethylated compound obtained.

  Examples of the modified product (b3) include an aminocarboxylic acid modified product (terminal amino group), an isocyanate modified product (terminal isocyanate group), and an epoxy modified product of the polyether diol (b1) or polyether diamine (b2) ( Terminal epoxy group). The aminocarboxylic acid-modified product can be obtained by reacting polyether diol (b1) or polyether diamine (b2) with aminocarboxylic acid or lactam. The isocyanate-modified product can be obtained by reacting polyether diol (b1) or polyether diamine (b2) with an organic diisocyanate as described below, or reacting polyether diamine (b2) with phosgene. . The epoxy-modified product is obtained by reacting polyether diol (b1) or polyether diamine (b2) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent of 85 to 600). It can be obtained by reacting polyether diol (b1) with epihalohydrin (such as epichlorohydrin).

  The Mn of the polyether (b) is usually 150 to 20,000, and preferably 300 to 20,000, more preferably 1,000 to 2,000 from the viewpoint of heat resistance and reactivity with the acid-modified polyolefin (a). 15,000, particularly preferably 1,200 to 8,000.

The polyether (b) may partially contain a cationic polymer and an anionic polymer. Such cationic polymers include polymers having quaternary ammonium or phosphonium salts, halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ^−. , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{— and the} like. Examples of anionic polymers include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alkali metal sulfonates of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and 3-sulfoisophthalic acid. The sulfonic acid sodium salt.

  The block copolymer (A) used in the present invention is prepared by reacting the polyolefin (a0) with an unsaturated carboxylic acid in a molten state to produce an acid-modified polyolefin (a), and adding a polyether (b) thereto. It can be produced by a method in which the polymerization reaction of (a) and (b) is carried out under high temperature vacuum.

  In the present invention, the compositional mass ratio between the acid-modified polyolefin (a) constituting the block copolymer (A) and the polyether (b) is (a) / (b) = 40/60 to 90 / It is the range of 10, 50 / 50-80 / 20 is more preferable, 55 / 45-80 / 20 is further more preferable, 55 / 45-70 / 30 is especially preferable. When the acid-modified polyolefin (a) is less than 40% by mass, the adhesion of the coating film is deteriorated, and when it exceeds 90% by mass, the antistatic performance is inferior.

  Moreover, in this invention, the acid value of a block copolymer (A) needs to be the range of 1-50, Preferably it is 2-40, Most preferably, it is 3-40. When the acid value is less than 1, aqueous dispersion of the block copolymer (A) becomes difficult, and when it exceeds 50, the adhesion of the coating film may be deteriorated.

  Furthermore, in this invention, as Mn (number average molecular weight) by the gel permeation chromatography of a block copolymer (A), 2000-60000 are preferable, 2500-50000 are more preferable, 3000-40000 are especially preferable, 3000 ˜30000 is most preferred. When the molecular weight exceeds 60,000, it becomes difficult to make the resin water-based, and when it is less than 2,000, the adhesion of the coating film may decrease.

In the present invention, the intrinsic surface resistance value of the block copolymer (A) is preferably 10 ⁵ to 10 ¹⁰ Ω, more preferably 10 ⁵ to 10 ⁹ , and particularly preferably 10 ⁵ to 10 ⁸ .

  As the block copolymer (A) used in the present invention described above, commercially available products can be suitably used. Examples of such commercially available products include Sanyo Kasei Kogyo Co., Ltd .: Pelestat 300, 230, Toho Chemical Industry Co., Ltd .: Anstex FT-P348 etc. are mentioned.

    Next, the aqueous medium used in the present invention will be described. The aqueous medium in the present invention is water or a mixed liquid of water and a water-soluble organic solvent. The water-soluble organic solvent has an effect of promoting aqueous dispersion of the block copolymer (A) and reducing the dispersed particle size. The water-soluble organic solvent in the present invention is one having a solubility in water at 20 ° C. of 50 g / L or more. The amount of the water-soluble organic solvent to be used is preferably 40% by mass or less, more preferably 1 to 40% by mass, and further preferably 2 to 35% by mass of the aqueous medium contained in the resin aqueous dispersion. 3 to 30% by mass is particularly preferable. When the amount of the water-soluble organic solvent exceeds 40% by mass, the viscosity of the obtained aqueous dispersion may become too high.

  Specific examples of the water-soluble organic solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec. -Alcohols such as amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, etc. Ketones, ethers such as tetrahydrofuran and dioxane, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3 Esters such as methoxybutyl, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether Glycols such as acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate Examples of the conductor include 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, and ethyl acetoacetate. Among them, those having a boiling point of 30 to 250 ° C. are preferable. 50 to 200 ° C. is particularly preferable. These water-soluble organic solvents may be used as a mixture of two or more. When the boiling point of the water-soluble organic solvent is less than 30 ° C., the ratio of volatilization during aqueous dispersion of the block copolymer (A) increases, and the efficiency of aqueous dispersion may not be sufficiently increased. When the obtained resin aqueous dispersion is applied to a substrate when the boiling point exceeds 250 ° C., it becomes difficult to scatter the water-soluble organic solvent from the coating film by drying.

  Among the above water-soluble organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, and ethylene are effective because they are highly effective in promoting aqueous dispersion of the block copolymer (A). Glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether are preferable, and ethanol, n-propanol, and isopropanol are particularly preferable from the viewpoint of low temperature drying property.

  Next, the basic compound used in the present invention will be described.

  A basic compound neutralizes the acid component in a block copolymer (A), and produces | generates an acid anion. Aggregation between the fine particles is prevented by the electric repulsion between the anions, and stability is imparted to the aqueous resin dispersion. As the basic compound, ammonia or an organic amine compound that volatilizes during the formation of the coating film is preferable from the viewpoint of adhesion of the coating film. Among them, an organic amine compound having a boiling point of 30 to 250 ° C., more preferably 50 to 200 ° C. is preferable. When the boiling point is lower than 30 ° C., the proportion of volatilization during the aqueous dispersion of the block copolymer (A) increases, and the aqueous dispersion may not proceed completely. When the resin aqueous dispersion obtained when the boiling point exceeds 250 ° C. is applied to a substrate, it becomes difficult to disperse the organic amine compound from the coating film by drying, and the adhesion of the coating film may be deteriorated. .

  Specific examples of the basic compound in the present invention include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3- Examples include ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine.

  The addition amount of the basic compound is preferably 0.5 to 20.0 times equivalent to the acid value of the block copolymer (A), more preferably 1.0 to 15.0 times equivalent, and still more preferably Is 2.0 to 15.0 times equivalent. If it is less than 0.5 times equivalent, the addition effect of a basic compound is not recognized, and if it exceeds 20.0 times equivalent, the adhesiveness of the coating film of a block copolymer (A) may fall.

  The first aqueous resin dispersion of the present invention is obtained by preparing a uniform liquid by dispersing or dissolving the block copolymer (A) in an aqueous medium. Here, the phrase “uniform liquid” means that a part having a solid content concentration locally different from other parts, such as precipitation, is not found in appearance in the aqueous dispersion. In the dispersed state, the number average particle diameter (hereinafter, mn) of the block copolymer (A) can be 1.0 μm or less. It is preferably 0.5 μm or less, more preferably 0.2 μm or less, and particularly preferably 0.1 μm or less. Furthermore, the volume average particle diameter (hereinafter, mv) can be 2 μm or less, preferably 1.0 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.2 μm or less.

  The content of the block copolymer (A) in the aqueous resin dispersion of the present invention can be appropriately selected depending on the film forming conditions, the thickness and performance of the target resin coating film, and is not particularly limited. 1-60 mass% is preferable with respect to 100 mass% of resin aqueous dispersion, and 3-55 mass% is more preferable at the point which maintains the viscosity of a composition moderately and expresses favorable film formation ability. 50 mass% is further more preferable, and 5-45 mass% is especially preferable. The aqueous medium can be appropriately distilled off or diluted with water and / or a water-soluble organic solvent so that the desired viscosity and resin content can be obtained.

  The aqueous resin dispersion of the present invention comprises the above-described components as main components, and the block copolymer (A) can be stably added to an aqueous medium without substantially using a non-volatile aqueous additive. Can be dispersed. The nonvolatile aqueous auxiliary agent remains in the block copolymer (A) even after the coating is formed, and plasticizes the coating, thereby deteriorating the properties of the block copolymer (A). Here, the “aqueous auxiliary” is a drug or compound added for the purpose of promoting aqueousization or stabilizing the aqueous resin dispersion in the production of an aqueous dispersion, and “nonvolatile” means It means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure. “Substantially no non-volatile aqueous solubilizing aid” means that no non-volatile aqueous solubilizing aid is actively added to the system, resulting in the absence of these. Such a nonvolatile aqueous auxiliary agent is particularly preferably zero in content, but is contained in an amount of less than 0.1% by mass with respect to the block copolymer (A) component as long as the effects of the present invention are not impaired. It can be done.

  Examples of the non-volatile aqueous additive include emulsifiers, compounds having a protective colloid effect, high acid value waxes, high acid value acid-modified compounds, and water-soluble polymers.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. 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. Nonionic emulsifiers 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. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

  Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid values, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax and the like, and acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid- Maleic anhydride copolymer and salts thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride male A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 15% by mass or more such as an acid alternating copolymer, a (meth) acrylic acid- (meth) acrylic ester copolymer, and a polyitaconic acid and a salt thereof; Examples thereof include water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, and casein, which are generally used as fine particle dispersion stabilizers.

  The aqueous resin dispersion of the present invention can be mixed with an aqueous resin dispersion other than the block copolymer (A) in order to improve various performances of the coating film. Examples of the aqueous resin dispersion other than the block copolymer (A) include ethylene-acrylic acid ester-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylic acid copolymer. Polyolefin resin, polyester resin, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile resin, chlorinated polypropylene resin, modified nylon resin, urethane resin, phenol resin, Examples thereof include aqueous dispersions such as silicone resins and epoxy resins. You may use these in mixture of 2 or more types. From the viewpoint of improving the adhesion of the coating film, it is preferable to add an aqueous dispersion of a polyolefin resin or a polyester resin. An aqueous dispersion described in JP-A No. 2003-119328 or the like can be used as the aqueous polyolefin resin dispersion, and an aqueous dispersion described in JP-A No. 2000-313793 can be used as the aqueous polyester resin dispersion. From the viewpoint of antistatic properties and adhesion, it is preferable to add 10 to 900 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of the block copolymer (A).

  The aqueous resin dispersion of the present invention may further contain inorganic particles. Examples of such inorganic particles include metal oxides such as magnesium oxide, zinc oxide and tin oxide, inorganic particles such as calcium carbonate and silica, and water-swellable layered inorganic compounds such as vermiculite, montmorillonite, hectorite and synthetic mica. Can be added. The average particle diameter of these inorganic particles is preferably 0.005 to 10 μm, more preferably 0.005 to 5 μm from the viewpoint of the stability of the aqueous dispersion. Inorganic particles may be used as a mixture of two or more. From the viewpoint of improving adhesion and antistatic properties, it is preferable to add tin oxide. For example, the tin oxide sol described in JP2003-81632A can be mentioned. From the viewpoint of antistatic properties and adhesiveness, it is preferable to add 10 parts by mass to 1000 parts by mass in terms of solid content of tin oxide with respect to 100 parts by mass of the solid content of the aqueous polyetheresteramide resin dispersion.

  Furthermore, in the aqueous resin dispersion of the present invention, various agents such as a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersing agent, an ultraviolet absorber, titanium oxide, zinc white, carbon black, etc. Pigments or dyes may be added.

  Next, the manufacturing method of the resin aqueous dispersion which is the 2nd of this invention is demonstrated. The resin aqueous dispersion as described above can be produced by dispersing the block copolymer (A) in an aqueous medium, that is, aqueous dispersion. As the aqueous dispersion method, a method of heating and stirring the block copolymer (A) at a temperature of 80 ° C. to 250 ° C. together with a mixture of the basic compound and the aqueous medium can be used. In aqueous dispersion, it is not necessary to positively add a nonvolatile aqueous auxiliary agent as described above.

  The shape of the block copolymer (A) used in the aqueous dispersion step in the present invention is not particularly limited, but in terms of increasing the aqueousization rate, the particle diameter is 1 cm or less, preferably 0.8 cm or less, or powdery. It is preferable to use those.

  The addition amount of the block copolymer (A) is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and more preferably 5 to 50% by mass with respect to 100% by mass of the total amount of the aqueous medium, the basic compound and the resin. Is more preferable, and 5-45 mass% is especially preferable. When the addition amount is less than 1% by mass, the resin solids concentration of the resulting resin aqueous dispersion is too low to cause the performance of the coating film to be difficult to occur, and when it exceeds 60% by mass, aqueous dispersion tends to be difficult. is there.

  The container for aqueous dispersion is not particularly limited, and a known solid / liquid stirring device, emulsifier, autoclave, or the like can be used. It is preferable if pressurization of 0.1 MPa or more is possible. In such a container for aqueous dispersion, the block copolymer (A), the basic compound, and the aqueous medium are charged, and the temperature in the container is set to 80 to 250 ° C. while stirring. is necessary. More preferably, it is 90-200 degreeC, More preferably, it is 100-190 degreeC. When the temperature in a container is less than 80 degreeC, aqueous dispersion of a block copolymer (A) may become inadequate. When the temperature in a container exceeds 250 degreeC, there exists a possibility that the molecular weight of a block copolymer (A) may fall. In the present invention, the stirring method and the rotation speed of stirring are not particularly limited. Sufficient watering can be achieved even with low-speed stirring that makes the resin float in an aqueous medium, and high-speed stirring (for example, 1000 rpm or more) is not essential.

  The aqueous yield in the method for producing an aqueous resin dispersion of the present invention can be determined from the amount of coarse particles remaining in the obtained aqueous dispersion. Specifically, the aqueous dispersion is subjected to pressure filtration with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the amount of resin remaining on the filter is measured. The aqueous yield is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably 100%.

  Next, the antistatic coating agent which is the third invention and the laminate which is the fourth invention will be described. The antistatic coating agent comprises the above-described aqueous resin dispersion of the present invention, and the laminate is obtained by coating the aqueous resin dispersion on the substrate and then removing the aqueous medium. The coating film formed by removing the aqueous medium from the aqueous resin dispersion of the present invention has good antistatic properties and excellent adhesion to resin substrates such as resin films and resin molded bodies, and substrates such as paper. .

  Examples of the resin film include polyamide resins such as nylon 6, nylon 66 and nylon 46, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and polylactic acid. Examples thereof include a film made of a resin, a polyolefin resin such as polypropylene and polyethylene, a polyimide resin, a polyarylate resin, or a mixture thereof, or a laminate of these films. The resin film may be an unstretched film or a stretched film, and the production method is not limited. The thickness of the resin film is not particularly limited, but is usually 1 to 500 μm.

  The antistatic coating agent of the present invention can be applied to a substrate by a known coating method. As a coating method, various substrate surfaces can be formed by known film forming methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. It is possible to form a uniform coating film in close contact with various substrate surfaces by subjecting it to uniform coating and setting it at around room temperature as necessary, followed by heat treatment for drying or drying and baking. . As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used.

  In addition, the thickness of the resin coating film in the present invention is appropriately selected depending on its use, but is preferably 0.01 to 30 μm, more preferably 0.02 to 10 μm, and further preferably 0.03 to 9 μm. 0.05 to 8 μm is particularly preferable. When the thickness of the resin coating film is less than 0.01 μm, the antistatic property deteriorates. When it exceeds 30 μm, the adhesion of the coating film to the substrate is deteriorated.

The surface resistivity of the coated surface of the substrate coated with the coating film thus obtained is preferably 1 × 10 ¹⁴ Ω or less, more preferably 1 × 10 ¹³ Ω or less, and more preferably 1 × 10 ¹² Ω or less. Further preferred is 1 × 10 ¹¹ Ω or less. Here, the surface specific resistance value was applied to a PET film so that the resin aqueous dispersion was dried to a film thickness of 3 μm and dried at 90 ° C. for 2 minutes. It can obtain | require by measuring the obtained laminated | multilayer film in the atmosphere of temperature 20 degreeC, and humidity 60%.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Various characteristics were measured or evaluated by the following methods.

1. Characteristics of Block Copolymer (A) (1) The weight ratio of polyolefin and polyether of block copolymer (A) was determined by ¹ H-NMR analysis (manufactured by JEOL, 500 MHz). The resin was measured at 120 ° C. using trichlorethylene as a solvent.

(2) Acid value: 0.5 g of a sample is dissolved in 20 ml of o-dichlorobenzene at 150 ° C., cooled to 60 ° C., and 1 ml of ethanol and 2 drops of indicator cresol red are added. And it is the value computed from the consumption of 0.1 mol / L potassium hydroxide by titrating with 0.1 mol / L potassium hydroxide.

(3) Resin surface resistance value: Based on JIS-K6911, a resin molded into a 2 mm thick sheet using a digital ultrahigh resistance / microammeter, R8340 manufactured by Advantest Co., Ltd., at a temperature of 20 ° C. The humidity was measured at 60% for 12 hours.

2. Characteristics of Aqueous Resin Dispersion (1) Aqueous Dispersion Yield After the aqueous dispersion, the resin aqueous dispersion was filtered with pressure through a 300 mesh stainless steel filter (plain weave, wire diameter 35 μm, filtration area 133 cm ² ), then on the filter The remaining resin was dried at 80 ° C. under vacuum for 1 hour, the resin weight was measured, and the yield was calculated from the charged resin weight. When the entire amount could not be filtered at one time, the filter was replaced. In that case, the total residual resin amount was evaluated.

(2) Solid content concentration of resin aqueous dispersion An appropriate amount of resin aqueous dispersion after 300 mesh filtration was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight. Asked.

(3) Average particle diameter of resin aqueous dispersion Number average particle of resin aqueous dispersion after 300 mesh filtration using Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) manufactured by Nikkiso Co., Ltd. The diameter and the weight average particle diameter were determined. Here, the refractive index of the resin used for calculating the particle diameter was set to 1.50.

3. Characteristics of coating film In the following evaluation, as a base material, biaxially stretched polyethylene terephthalate film (Embret PET12 manufactured by Unitika, thickness 12 μm, hereinafter referred to as PET) and L-LDPE (TUX FC-D manufactured by Tosero Co., thickness 50 μm Hereinafter, LLDPE) was used. As the resin aqueous dispersion, a 300-mesh filtered product was used.

(1) Adhesion (tape peeling test)
The aqueous resin dispersion was applied to the above LLDPE and PET films using a Mayer bar so that the film thickness after drying was 1 μm, and then dried at 90 ° C. for 90 seconds. The obtained laminated sheet was evaluated after standing at room temperature for one day. A cellophane tape (TF-12 manufactured by Nichiban Co., Ltd.) was attached to the adhesive surface, and the degree of peeling when the tape was peeled at once was visually evaluated according to the following criteria.

○: No peeling at all △: Some peeling off ×: Most peeling off

(2) Coating film antistatic property The aqueous resin dispersion was applied to a PET film using a Mayer bar so that the film thickness after drying was 1 μm, and then dried at 90 ° C. for 90 seconds. Based on JIS-K6911, the obtained laminated film was subjected to a surface resistance value (Ω) of a coating film of a coated film using a digital ultrahigh resistance / microammeter R83340 manufactured by Advantest Co., Ltd. at a temperature of 20 ° C. and a humidity of 60 % Atmosphere.

Production Example 1
85 parts of low molecular weight polypropylene obtained by the thermal degradation method with Mn of 2500 and density of 0.89 and 15 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere and reacted for 20 hours. . Thereafter, excess maleic anhydride was distilled off under reduced pressure to obtain acid-modified polypropylene (a1). The acid value of (a1) was 39.8.

Production Example 2
95 parts of low molecular weight polypropylene obtained by a thermal degradation method with Mn of 2500 and density of 0.89 and 5 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere and reacted for 20 hours. . Thereafter, excess maleic anhydride was distilled off under reduced pressure to obtain acid-modified polypropylene (a2). The acid value of (a2) was 8.7.

Production Example 3
47 parts of low molecular weight polypropylene obtained by the thermal degradation method with Mn of 500 and density of 0.89, 30 parts of maleic anhydride and 23 parts of glycine were added, and the reaction was carried out at 160 ° C. for 1 hour in a nitrogen gas atmosphere. It was. Then, reaction was performed at 200 degreeC for 20 hours, and the acid-modified polypropylene (a3) was obtained. The acid value of (a3) was 180.6.

Production Example 4
In a stainless steel autoclave, 41 parts of the acid-modified polypropylene (a1) obtained in Production Example 1, 59 parts of polyethylene glycol having a Mn of 2000 (surface resistivity: 5 × 10 ⁷ Ω), an antioxidant (“Irganox”) 1010 ", manufactured by Ciba-Gaiky Co., Ltd., the same shall apply hereinafter)) 0.3 parts and 0.5 parts of zirconyl acetate were added, and polymerization was carried out for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block copolymer (A1). The properties of the block copolymer (A1) are shown in Table 1.

Production Example 5
In a stainless steel autoclave, 64 parts of the acid-modified polypropylene (a1) obtained in Production Example 1, 36 parts of polyethylene glycol having a Mn of 2000 (surface resistivity: 5 × 10 ⁷ Ω), 0.3 parts of an antioxidant And 0.5 parts of zirconyl acetate were added, and polymerization was performed for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block copolymer (A2). The properties of the block copolymer (A2) are shown in Table 1.

Production Example 6
In a stainless steel autoclave, 89 parts of acid-modified polypropylene (a1) obtained in Production Example 1, 11 parts of polyethylene glycol having a Mn of 1000 (surface resistivity: 2 × 10 ⁸ Ω), 0.3 parts of antioxidant And 0.5 parts of zirconyl acetate were added, and polymerization was performed for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block copolymer (A3). The properties of the block copolymer (A3) are shown in Table 1.

Reference production example 7
In a stainless steel autoclave, 95 parts of the acid-modified polypropylene (a1) obtained in Production Example 1, 5 parts of polyethylene glycol having a Mn of 1000 (surface resistivity: 2 × 10 ⁸ Ω), 0.3 parts of an antioxidant And 0.5 parts of zirconyl acetate were added, and polymerization was performed for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out in the form of a strand on the belt and pelletized to obtain a block copolymer (A4). The properties of the block copolymer (A4) are shown in Table 1.

Reference production example 8
In a stainless steel autoclave, 35 parts of the acid-modified polypropylene (a1) obtained in Production Example 1, 65 parts of polyethylene glycol having a Mn of 2000 (surface resistivity: 5 × 10 ⁷ Ω), 0.3 parts of an antioxidant And 0.5 parts of zirconyl acetate were added, and polymerization was performed for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block copolymer (A5). The properties of the block copolymer (A5) are shown in Table 1.

Reference production example 9
In a stainless steel autoclave, the acid-modified polypropylene (a2) obtained in Production Example 2
55 parts, 45 parts of polyethylene glycol with Mn of 2000 (surface resistivity: 5 × 10 ⁷ Ω), 0.3 parts of antioxidant and 0.5 parts of zirconyl acetate are added, and reduced pressure at 230 ° C. and 1 mmHg or less. Polymerization was carried out for 3 hours under the conditions, to obtain a viscous polymer. The polymer was taken out as a strand on the belt and pelletized to obtain a block copolymer (A6). The properties of the block copolymer (A6) are shown in Table 1.

Reference production example 10
In a stainless steel autoclave, 80 parts of the acid-modified polypropylene (a3) obtained in Production Example 3, 20 parts of polyethylene glycol having a Mn of 900 (surface resistivity: 2 × 10 ⁸ Ω), 0.3 parts of an antioxidant And 0.5 parts of zirconyl acetate were added, and polymerization was performed for 3 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block copolymer (A7). The properties of the block copolymer (A7) are shown in Table 1.

Example 1
20.0 g of block copolymer (A1) obtained in Production Example 4, 50.0 g of isopropanol (hereinafter, IPA), 2.0 g (acid) 13.3 times equivalent) of triethylamine (hereinafter referred to as TEA) and 128.5 g of distilled water were charged into a glass container and stirred at a rotating speed of the stirring blade of 300 rpm. No sedimentation was observed, confirming that it was in a floating state. Therefore, while maintaining this state, the power was turned on and heating was performed. Then, the system temperature was maintained at 140 ° C. and further stirred for 2 hours. Cooling to room temperature while stirring at a rotational speed of 300 rpm, pressure filtration through a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and a resinous aqueous dispersion of a milky white uniform block copolymer (A) E-1 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Example 2
Using a commercially available polyolefin / ether block copolymer perestat 300 (manufactured by Sanyo Chemical Co., Ltd., surface resistance value: 1.0 × 10 ⁸ Ω), the amount of TEA was 2.0 g (8. 8 with respect to the acid value). Resin aqueous dispersion E-2 was obtained in the same manner as in Example 1 except for changing to 6 times equivalent). The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Example 3
Using the block copolymer (A2) obtained in Production Example 5, the same method as in Example 1 except that the amount of TEA was changed to 2.0 g (4.9 times equivalent to the acid value). An aqueous resin dispersion E-3 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Example 4
Using the block copolymer (A3) obtained in Production Example 6, the same method as in Example 1 except that the amount of TEA was changed to 2.0 g (3.6 times equivalent to the acid value). An aqueous resin dispersion E-4 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Comparative Example 1
Using the block copolymer (A4) obtained in Reference Production Example 7, the same method as in Example 1 except that the amount of TEA was changed to 2.0 g (3.2 times equivalent to the acid value). Resin aqueous dispersion E-5 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Comparative Example 2
Using the block copolymer (A5) obtained in Reference Production Example 8, the same method as in Example 1 except that the amount of TEA was changed to 2.4 g (19.5 times equivalent to the acid value). Resin aqueous dispersion E-6 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Comparative Example 3
The same method as in Example 1 except that the block copolymer (A6) obtained in Reference Production Example 9 was used and the amount of TEA was changed to 0.65 g (20.0 times equivalent to the acid value). Aqueous dispersion was carried out. The results are shown in Table 2.

Comparative Example 4
The same method as in Example 1 except that the block copolymer (A7) obtained in Reference Production Example 10 was used and the amount of TEA was changed to 1.5 g (0.8 times equivalent to the acid value). Resin aqueous dispersion E-7 was obtained. The properties of the aqueous resin dispersion and the properties of the coating film are shown in Tables 2 and 3, respectively.

Comparative Example 5
Aqueous dispersion was carried out in the same manner as in Example 3 except that TEA was not added. The results are shown in Table 2.

Comparative Example 6
An aqueous resin dispersion E-8 of a graft copolymer obtained by grafting polyetheramine to maleic anhydride-modified polypropylene was obtained (for details, see Example 1 described in JP-A-2007-246871). The properties of the resin aqueous dispersion and the properties of the coating film are shown in Table 3.

Example 5
30 parts by mass of an acid-modified polyolefin resin aqueous dispersion (Arrowbase SB1200, manufactured by Unitika) is added to 100 parts by mass of the solid content of the aqueous resin dispersion E-3 obtained in Example 3, Table 3 shows the adhesion and surface resistivity of the coating film obtained from the mixed solution with PET.

Example 6
30 parts by mass of a polyester resin aqueous dispersion (Elitel KT9204, manufactured by Unitika Ltd.) in terms of solid content is added to 100 parts by mass of the solid content of the aqueous resin dispersion E-3 obtained in Example 3, and from the mixture Table 3 shows the adhesion and surface resistivity of the obtained coating film with PET.

Example 7
50 parts by mass of tin oxide sol (AS11T, manufactured by Unitika Co., Ltd.) in terms of solid content was added to 100 parts by mass of the solid content of the aqueous resin dispersion E-3 obtained in Example 3, and obtained from the mixed solution. Table 3 shows the adhesion and surface resistivity of the coating film with PET.

Comparative Example 7
30 parts by mass of an acid-modified polyolefin resin aqueous dispersion (Arrowbase SB1200, manufactured by Unitika) is added to 100 parts by mass of the solid content of the aqueous resin dispersion E-7 obtained in Comparative Example 4, Table 3 shows the adhesion and surface resistivity of the coating film obtained from the mixed solution with PET.

Comparative Example 8
30 parts by mass of a polyester resin aqueous dispersion (Elitel KT9204, manufactured by Unitika Co., Ltd.) in terms of solid content is added to 100 parts by mass of the solid content of the resin aqueous dispersion E-7 obtained in Comparative Example 4, and from the mixed solution Table 3 shows the adhesion and surface resistivity of the obtained coating film with PET.

Comparative Example 9
50 parts by mass of tin oxide sol (AS11T, manufactured by Unitika Co., Ltd.) in terms of solid content was added to 100 parts by mass of the solid content of the aqueous resin dispersion E-7 obtained in Comparative Example 4 and obtained from the mixed solution. Table 3 shows the adhesion and surface resistivity of the coating film with PET.

  The results of Examples 1 to 4 show that the hardly water-decomposable polyolefin / ether block copolymer can be made aqueous by the aqueous dispersion method of the present invention. Moreover, the coating film obtained from this resin aqueous dispersion had antistatic performance and was further excellent in adhesion to various substrates.

  From the results of Example 2, even a commercial product satisfying the provisions of the present invention can be made water-based, and the coating film obtained from the aqueous dispersion also has antistatic properties, and further adheres to various substrates. It was excellent in nature.

  From the results of Examples 1 to 4, as the mass ratio of the polyolefin (a) and the polyether (b) constituting the block copolymer (A) increases, the surface resistivity of the obtained coating film increases. It was. This is considered that the polyether (b) works as an antistatic component.

  In Comparative Example 1, the mass ratio of the polyolefin (a) and the polyether (b) constituting the block copolymer (A) is within the upper limit of the ratio of (a) with respect to the range defined in the present invention. Although the adhesion of the aqueous dispersion coating film to the substrate was improved, the surface resistivity increased and the antistatic performance deteriorated. In Comparative Example 2, the ratio of (a) is outside the lower limit of the mass ratio of (a) and (b) defined in the present invention, and the antistatic performance of the coating film of the aqueous resin dispersion is good. However, the adhesion with the base material deteriorated.

  From the result of Comparative Example 3, the acid value of the block copolymer (A) deviated downward from the range defined in the present invention, and the resin could not be dispersed in water. In Comparative Example 4, the acid value of the block copolymer (A) deviated from the upper limit of the present invention, and the aqueous dispersion of the resin could be achieved. Worsened.

  From the comparison between Examples 1 to 4 and Comparative Example 5, it can be seen that the resin cannot be dispersed in water without using a basic compound.

  From the results of Comparative Example 6, the aqueous dispersion of the acid-modified polyolefin / ether graft copolymer has improved adhesion to the base material of the coating film, but has a high surface resistivity and antistatic performance. It wasn't.

  From the results of Examples 5 and 6, when an aqueous resin dispersion such as polyolefin or polyester is added to the aqueous resin dispersion of the block copolymer (A), the adhesion to the substrate is maintained while maintaining the antistatic performance. I was able to improve.

  From the results of Example 7, when tin oxide sol as inorganic particles was added to the aqueous dispersion of the block copolymer (A), adhesion with PET could be improved while maintaining antistatic performance.

From the results of Comparative Examples 7 to 9, an acid-modified polyolefin resin was obtained in the same manner as in Examples 5 to 7 in the resin aqueous dispersion E-7 in which the acid value of the block copolymer (A) deviated upward from the range specified in the present invention Even when the aqueous dispersion, the polyester resin aqueous dispersion, and the tin oxide sol were added, the adhesion could not be improved.

Claims (5)

An aqueous resin dispersion containing a block copolymer (A), an aqueous medium and a basic compound, wherein the block copolymer (A) comprises a block of acid-modified polyolefin (a) and a surface resistivity value The block of the polyether (b) having a ratio of 10 ⁵ to 10 ¹¹ Ω is bonded at a ratio of (a) / (b) = 40/60 to 90/10 (mass ratio), and the acid value is 1 Resin aqueous dispersion, characterized in that it is ˜50 mg KOH / g resin.   The aqueous resin dispersion according to claim 1, wherein the polyether (b) is one or more compounds selected from the group consisting of polyether diol (b1), polyether diamine (b2), and modified products thereof (b3). .   3. The aqueous resin dispersion according to claim 1, wherein the block copolymer (A), the basic compound and the aqueous medium are used as raw materials, and these are heated and stirred at a temperature of 80 ° C. to 250 ° C. 3. Production method.   An antistatic coating agent comprising the aqueous resin dispersion according to claim 1.   A laminate obtained by coating the substrate with the aqueous resin dispersion according to claim 1 or 2 and then removing the aqueous medium.