JP5728327B2 - Water-based acrylic urethane resin composition and coating film formed by applying and drying the same - Google Patents

Description

  The present invention relates to a water-based acrylic urethane resin composition, and a coating film formed by applying and drying the composition to at least one surface of a synthetic resin film. Specifically, the film is formed using a specific isocyanate compound. The present invention relates to a water-based acrylic urethane resin composition excellent in water resistance at the time, and a coating film formed by applying and drying the composition, which is excellent in dust resistance and can be suitably used particularly for an agricultural film.

  Polyurethane resins are widely used as paints, adhesives, binders, and coating agents because they can form coatings and molded articles having wear resistance, adhesion, non-tackiness, and rubber elasticity. Conventionally, water-based polyurethane resin compositions have been frequently used from the viewpoint of safety against environmental pollution and occupational health. However, since the water-based polyurethane resin composition is inferior in the physical properties of the formed coating film as compared with the solvent-based or solvent-free type, improvement is demanded particularly from the viewpoint of water resistance.

  On the other hand, synthetic resins such as vinyl chloride resins, polyolefin resins, and polyester resins have excellent physical properties such as mechanical strength, chemical resistance, and weather resistance, and are relatively inexpensive, so they are used in various applications. For example, these synthetic resins are used for agricultural films such as tunnel cultivation and house cultivation. However, in the case of these synthetic resin films, additives such as plasticizers, anti-fogging agents, and stabilizers blended bleed to the film surface over time, so that dust adheres to the film surface. The light transmittance was significantly lowered after a year, and there were drawbacks such as inhibiting the cultivation and growth of crops. Thus, development of agricultural films having excellent dust resistance has been desired.

  As means for improving the performance of agricultural films such as dust resistance, a method of applying an acrylic resin to the surface of an inexpensive synthetic resin film as described above (Patent Documents 1 to 4), a method of applying a fluororesin (Patent) Documents 5 to 8), a method of applying a mixture of a fluororesin and an acrylic resin (Patent Documents 9 to 11), a method of applying an acrylic urethane resin (Patent Documents 12 and 13), and the like have already been disclosed. However, even if an acrylic resin is applied, it is not possible to sufficiently prevent the plasticizer in the base material from bleeding out on the surface of the molded product. When used in combination, it was not satisfactory in terms of adhesion between the base resin and the coating layer, product cost, and the like. Also, when acrylic urethane resin is used, the adhesion between the base resin and the coating layer is good and the dust resistance is improved, but the required high dust resistance has not yet been achieved. It was.

Japanese Patent Publication No.46-29639 Japanese Patent Publication No. 50-28117 Japanese Patent Publication No. 50-31195 Japanese Patent Publication No. 55-52052 JP 56-86748 A JP 57-8155 A JP-A-57-12646 Japanese Patent Laid-Open No. 03-51121 JP 63-21143 A Japanese Patent Laid-Open No. 46-65161 Japanese Patent Publication No. 63-236 JP 07-298791 A Japanese Patent Laid-Open No. 10-16169

As a result of various investigations in view of such circumstances, the present inventors have used a specific isocyanate compound as an essential component, and the water-based acrylic urethane resin composition formed has remarkable coating water resistance, the water-based The present inventors have found that a coating film in which an acrylic urethane resin composition is applied on one or both surfaces of a synthetic resin is excellent in dustproof property and suitable as an agricultural film, and have reached the present invention.
Accordingly, a first object of the present invention is to provide a water-based acrylic urethane resin composition excellent in water resistance of a coating film.
The second object of the present invention is to provide a coating film which is excellent in dustproof property and suitable as an agricultural film.

但し、上式中のＲ^１は炭素原子数１０〜３０のアルキル基を表し、Ｒ^２は−Ｎ＝Ｃ＝Ｏ、又は下記の基を表し、Ａはジイソシアネート化合物から２個の−Ｎ＝Ｃ＝Ｏを除いた残基を表す。

但し、上式中のＲ ^１ は炭素原子数１０〜３０のアルキル基を表す。 That is, the present invention is an aqueous acrylic urethane resin composition containing 2 to 70% by mass of a resin containing 20 to 80% by mass of a polyurethane resin and 80 to 20% by mass of an acrylic resin in terms of solid content. At least one polyol component (a) wherein the resin is selected from the group consisting of polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline polycarbonate polyols and non-crystalline polycarbonate polyols; Isocyanate component (b) essentially comprising an isocyanate compound represented by formula (1), and water-based polyurethane resin obtained using water as an essential component, wherein the acrylic resin comprises (meth) acrylic acid and (meth) acrylate At least one selected from Polymerizing the unsaturated monomer (c) with an aqueous acrylic resin obtained, the proportion of the isocyanate compound represented by the general formula (1) is, at a content in the aqueous polyurethane resin solid content, 2 to 35 A water-based acrylic urethane resin composition characterized by being in mass%, and a coating film formed by applying the water-based acrylic urethane resin composition to one side or both sides of a synthetic resin film.
General formula (1)

However, R ¹ in the above formula represents an alkyl group having 10 to 30 carbon atoms, R ² represents —N═C═O, or the following group, and A represents two —N═C from the diisocyanate compound. = represents the excluding O residues.

However, R ¹ in the above formula represents an alkyl group having 10 to 30 carbon atoms.

  In the present invention, A in the general formula (1) is preferably a residue obtained by removing two —N═C═O from 1,6-hexamethylene diisocyanate, and the isocyanate component (b) However, it is preferable to further contain dicyclohexylmethane-4,4′-diisocyanate and / or isophorone diisocyanate together with the isocyanate compound represented by the general formula (1). Further, as an essential component, it is preferable to further contain an ionic group-introducing compound as the component (d) and an ionic group neutralizing agent as the component (e), and the synthetic resin film used for the coating film is A vinyl chloride resin film, a polyolefin resin film, or a polyester resin film is preferred.

Wherein component (a) to be used in an aqueous acrylic urethane resin composition of the invention Po Li ether polyols, polyester polyols, polyester polycarbonate polyols, of a crystalline polycarbonate polyols and non-crystalline polycarbonate polyols At least one polyol selected from the group .
The component (a) can be used in combination with a low molecular polyol having a number average molecular weight of less than 200, which will be described later .

  Examples of the polyether polyols include, for example, 1,2-propanediol, 1,3-propanediol; low molecular polyols such as trimethylolpropane, glycerin, polyglycerin, pentaerythritol, bisphenol A, ethylenediamine, and the like. Examples include ethylene oxide and / or propylene oxide adducts to amine compounds and the like; polytetramethylene ether glycol and the like.

  Examples of the polyester polyols include a polyol such as a low molecular polyol having a number average molecular weight of less than 200, which will be described later, and a polyvalent carboxylic acid in an amount less than the stoichiometric amount of the polyol, or its ester, anhydride, carboxylic acid A polyester polyol obtained by a direct esterification reaction or transesterification reaction with an ester-forming derivative such as a halide; and a direct esterification of the polyol with a lactone or a hydroxycarboxylic acid obtained by a hydrolytic ring-opening reaction thereof. The polyester polyol obtained by reaction is mentioned.

  Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipine. Fats such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid, and castor oil fatty acid trimer A tetravalent or higher carboxylic acid such as pyromellitic acid.

  Examples of the ester-forming derivative of the polyvalent carboxylic acid include the anhydrides of the polyvalent carboxylic acid described above, or carboxylic acid halides such as chloride and bromide; methyl ester, ethyl ester, propyl ester of the polyvalent carboxylic acid, Examples include lower aliphatic esters such as isopropyl ester, butyl ester, isobutyl ester, and amyl ester.

  Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

  Examples of the polyester polycarbonate polyol include a reaction product obtained by reacting a reaction product of a polyester glycol such as polycaprolactone polyol and alkylene carbonate with an alkylene carbonate, and a reaction product of ethylene carbonate and a polyhydric alcohol with an organic dicarboxylic acid. Thing etc. are mentioned.

  Examples of the crystalline or non-crystalline polycarbonate polyol include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polypropylene glycol, and / or polytetramethylene glycol. And the reaction product of phosgene, phosgene, diallyl carbonate (for example, diphenyl carbonate) or cyclic carbonate (for example, propylene carbonate).

The number average molecular weight of the polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline polycarbonate polyols or non-crystalline polycarbonate polyols is preferably 300 to 5,000, more preferably 500 to 3,000. More preferred. In the present invention, among these polyols, it is particularly preferable to use polycarbonate polyols because the adhesiveness of the aqueous acrylic urethane resin composition of the present invention under wet heat is improved.

The said number average molecular weight of the low molecular polyols of less than 200, d Ji glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9 Nonanjio Le, cyclohexanedimethanol, at least one diol and / or trimethylol ethane is selected from cyclohexanediol, trimethylolpropane, hexitols such, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, tetramethylol Ru trivalent or more polyols der such as propane.

  In the present invention, the isocyanate compound represented by the general formula (1) used as the component (b) can be obtained by adding a long-chain alcohol to a nurate (trimer) of a diisocyanate compound.

  Examples of the diisocyanate compound that can form the nurate body include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, and 3,3′-dimethyl. Aromatic diisocyanates such as diphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans and / or cis-1,4-cyclohexane diisocyanate , Cycloaliphatic diisocyanates such as norbornene diisocyanate; 1,6-hexamethylene diisocyanate, (2,2,4) and / or (2,4,4) ) - trimethyl hexamethylene diisocyanate, aliphatic diisocyanates such as lysine diisocyanate; and mixtures thereof. Among these diisocyanate compounds, the use of at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate and isophorone diisocyanate, in particular, at least 1,6-hexa It is preferable to use methylene diisocyanate from the viewpoint of availability of raw materials and synthesis workability.

  Here, the nurate of the diisocyanate compound is, for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, or diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, carbon of an alkyl group. Phthalates such as mixed alkyl phthalates, butyl benzyl phthalates and hexanol benzyl phthalates having 7 to 11 atoms (hereinafter referred to as C7 to C11), phosphate esters such as tris-resyl phosphate and trisphenyl phosphate, In plasticizers such as adipic acid esters such as di-2-ethylhexyl adipate or trimellitic acid esters such as mixed alkyl trimellitates of C7 to C11, well-known catalysts such as tertiary amines, quaternary ammonium compounds, Mannich It can be obtained by polymerizing by a known method using a base, an alkali metal of a fatty acid, an alcoholate or the like. When the polymerization reaction is performed in a highly volatile solvent, it is preferable to finally perform a solvent replacement treatment using a suitable high boiling point solvent such as a plasticizer.

  Examples of the long-chain alcohols to be added to the nurate include decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneico Examples thereof include linear or branched alcohols having 10 to 30 carbon atoms such as sanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, and triacontanol. Among these long-chain alcohols, the use of a long-chain alcohol having 15 to 25 carbon atoms, in particular, the use of n-octadecanol, is a water-based acrylic urethane resin composition that is more excellent in water resistance and the like. Is preferable.

  The method for producing the isocyanate compound represented by the general formula (1) using these nurate bodies and long-chain alcohols is not particularly limited, but for example, per 1 mole of the nurate body of the diisocyanate compound. 1 to 2 mol of long-chain alcohols can be easily produced by adding them in a batch or stepwise and allowing them to react under heating.

  The content of the isocyanate compound represented by the general formula (1) used in the present invention is 2 to 35% by mass in the solid content of the aqueous polyurethane resin, but preferably 3 to 30% by mass. 5 to 25% by mass is more preferable. When the content of the isocyanate compound of the general formula (1) is less than 2% by mass, the effects such as water resistance of the resin coating film and dust resistance of the water-based acrylic urethane resin coating film are small. There is a tendency that the dispersibility of the polymer in water and the storage stability of the aqueous resin are poor.

  The isocyanate used as the component (b) of the present invention may be the isocyanate compound represented by the general formula (1) alone, but is used in combination with the isocyanate compound represented by the general formula (1) and the diisocyanate compound. It is preferable to do.

  Examples of the diisocyanate compound include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4 ′. -Aromatic diisocyanates such as diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; fats such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans and / or cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate Cyclic diisocyanates; 1,6-hexamethylene diisocyanate, (2,2,4) and / or (2,4,4) -trimethylhexa Ji diisocyanate, aliphatic diisocyanates such as lysine diisocyanate; and mixtures thereof. These diisocyanate compounds may be used in the form of modified products such as carbodiimide modification and biuret modification, or may be used in the form of blocked isocyanates blocked with various blocking agents. Among these, dicyclohexylmethane-4,4'-diisocyanate and isophorone diisocyanate are preferably used.

  Furthermore, as the isocyanate of the component (b), a polyisocyanate compound having three or more isocyanate groups can be used in combination as necessary. Examples of such a polyisocyanate compound include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and mixtures thereof. Carbodiimide modification of these tri- or higher functional isocyanates; Isocyanurate modification; Modified products such as biuret modification; Block isocyanates in which these are blocked with various blocking agents; Isocyanurate trimers of diisocyanate compounds and biuret 3 quantities Examples include the body.

  The water-based polyurethane resin used in the present invention is obtained by dispersing polyurethane using water as the essential component (a) and component (b) in water. The water dispersion method of the polyurethane is not particularly limited, and further, a self-emulsification method using the ionic group-introducing compound (d) and the ionic group neutralizing agent (e) as essential components, or the main chain or side chain of the polyurethane. Any of a self-emulsification method in which polyethylene oxide units are introduced and dispersed in water, a forced emulsification method using a reactive or non-reactive emulsifier, or an emulsification method combining these self-emulsification and forced emulsification may be used.

  Examples of the ionic group-introducing compound (d) include a compound that introduces an anionic group and a compound that introduces a cationic group. Examples of the compound that introduces an anionic group include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid, etc. These polyols containing sulfonic acid groups of Examples of the cationic group to be introduced include N, N-dialkylalkanolamines, N-methyl-N, N-diethanolamine, N-alkyl-N, N-, such as N-butyl-N, N-diethanolamine. Examples include dialkanolamines and trialkanolamines.

  Moreover, the compounding quantity of the said ionic group introduction | transduction compound (d) may be the quantity used as the range which is 0-30 mass% in the urethane prepolymer which consists of said (a), (b) and (d) component. The amount is preferably 0 to 20% by mass, more preferably 0 to 10% by mass. When the content of the ionic group-introducing component exceeds 30% by mass, the viscosity of the urethane prepolymer increases as the cohesive energy of urethane bonds increases, causing problems such as difficulty in water dispersibility.

  Examples of the ionic group neutralizer component (e) used in the present invention include an anionic group neutralizer and a cationic group neutralizer. Examples of the neutralizing agent for the anionic group include trialkylamines such as trimethylamine, triethylamine, and tributylamine; N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1 -N, N-dialkylalkanolamines such as dimethylamino-2-methyl-2-propanol; N-alkyl-N, N-dialkanolamines; tertiary amine compounds of trialkanolamines such as triethanolamine; Examples include basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of the cationic group neutralizing agent include organic carboxylic acids such as formic acid, acetic acid, lactic acid, succinic acid, glutaric acid, and citric acid; organic sulfonic acids such as paratoluenesulfonic acid and alkyl sulfonate; hydrochloric acid, phosphoric acid, In addition to inorganic acids such as nitric acid and sulfonic acid; epoxy compounds such as epihalohydrin, quaternizing agents such as dialkyl sulfuric acid and alkyl halides can be mentioned.

  The amount of the ionic group neutralizing agent component (e) used is preferably 0.5 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents per 1 equivalent of ionic groups. More preferred. If the amount of the ionic group neutralizing agent used is too large or insufficient, not only the storage stability of the water-based acrylic urethane resin composition, but also the mechanical properties such as strength and elongation of the water-based acrylic urethane resin film, water resistance, etc. There is a risk that the physical properties will deteriorate.

The method for producing the water-based polyurethane resin used in the present invention is not particularly limited, and if necessary, using a solvent that is inert to the reaction and has a large affinity for water, the polyol component (a), It can be suitably produced by a known method using the isocyanate component (b) and the water essentially comprising the isocyanate compound represented by the general formula (1). In this case, it is preferable to further use an ionic group-introducing compound (d) and an ionic group neutralizing agent component (e), and if necessary, introducing a polyethylene oxide unit into the main chain or side chain of the polyurethane, An emulsifier component can be blended.
In the present invention, (1) after synthesizing a urethane prepolymer, an ionic group neutralizing agent is added to the prepolymer and / or water, and the water contains an ionic group neutralizing agent component and / or an emulsifier component. (2) Water dispersion was performed by a phase inversion method in which water containing an ionic group neutralizing agent component and / or an emulsifier component was added and dispersed in a urethane prepolymer. Any method of chain extending a urethane resin in water using a chain extender component may be used, and the water dispersion method and the like are not particularly limited.

  Examples of suitable solvents that are inert to the reaction and have a high affinity for water include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone. These solvents are usually used in an amount of 3 to 200 parts by mass with respect to 100 parts by mass of the urethane prepolymer (total amount of components (a), (b) and (d), (e)). When a solvent having a boiling point of 100 ° C. or lower is used as these solvents, it is preferable to synthesize the aqueous polyurethane resin and then remove the solvent by distillation under reduced pressure or the like.

  As a compound for introducing a polyethylene oxide unit into the main chain or side chain of the polyurethane (hereinafter also referred to as a nonionic group-introducing compound), an ethylene oxide polyaddition product or an ethylene oxide / propylene oxide copolyaddition product of the low molecular polyols, Ammonia and ethylene oxide polyadducts of low molecular weight amine compounds having two or more active hydrogens such as methylamine, ethylamine, aniline, phenylenediamine, isophoronediamine, or ethylene oxide / propylene oxide coadducts; Trimer) polyethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ester, and the like.

  The amount of the nonionic group-introducing compound used is preferably an amount such that the content of polyethylene oxide units in the polyurethane is 1 to 30% by mass, and more preferably 3 to 20% by mass. When the content of the polyethylene oxide unit in the polyurethane is less than 1% by mass, the effect of improving the water dispersion stability of the aqueous polyurethane is small. When the content is more than 30% by mass, the polyurethane is obtained from the aqueous acrylic urethane resin composition of the present invention. The water resistance of the coating film may deteriorate.

  Examples of the emulsifier component include ordinary anionic surfactants and nonionic surfactants; primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, and the like. Further, known surfactants such as cationic surfactants; amphoteric surfactants such as betaine type, sulfate type and sulfonic acid type;

  Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; sodium Sulfolicinolate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate and tolethanolamine abiates; Sodium benzene sulfonate, Alkaline phenol hydroxyethylene Alkyl aryl sulfonates such as alkali metal sulfate High alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkyl aryl sulfate salt; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate N-acyl amino acid salt; N-acyl methyl taurine salt and the like.

  Examples of the nonionic surfactant include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; and alcohols having 1 to 18 carbon atoms. Examples include ethylene oxide and / or propylene oxide adduct; ethylene oxide and / or propylene oxide adduct of alkylphenol; ethylene glycol and / or propylene oxide adduct of alkylene glycol and / or alkylene diamine. Examples of the alcohol having 1 to 18 carbon atoms constituting these nonionic surfactants include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol. Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.

  Examples of the alkylphenol include phenol, methylphenol, 2,4-ditertiarybutylphenol, 2,5-ditertiarybutylphenol, 3,5-ditertiarybutylphenol, 4- (1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F etc. are mentioned.

  Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. It is done. Moreover, as alkylenediamine, what substituted the alcoholic hydroxyl group of these alkylene glycol by the amino group etc. are mentioned. Further, the ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

  Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazolinium. Examples thereof include laurate.

  Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethyl Examples include betaine types such as metal salts of carboxymethyl betaine and hydroxypropyl phosphate, amino acid types such as metal salts of β-laurylaminopropionic acid, sulfate ester types, and sulfonic acid types.

  Although the amount of the emulsifier component used is not particularly limited, from the viewpoint of mechanical properties such as strength and elongation of the coating film obtained by applying the aqueous acrylic urethane resin composition, and coating film water resistance, It is preferably 0 to 30 parts by mass and more preferably 0 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the polyurethane resin. When it exceeds 30 mass parts, there exists a possibility that the physical property of an above-mentioned water-based acrylic urethane resin film may fall.

As the chain extender component, for example, the chain extender can be appropriately selected from conventionally used chain extenders such as the low molecular weight polyol compound having a number average molecular weight of less than 200 and the low molecular polyamine compound. Examples of such chain extender components include low molecular diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, tolylene diamine, piperazine, and 2-methylpiperazine in addition to the low molecular diols described above; polyoxypropylene Polyether diamines such as diamine and polyoxyethylene diamine; mensen diamine, isophorone diamine, norbornene diamine, aminoethylaminoethanol, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane Alicyclic diamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; m-xylenediamine, α- (m / pamino) Phenyl) Ruamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene, etc. Of the aromatic diamines of : succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, hydrazine hydrate, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′ , 1'-tetramethyl-4,4 '-(methylene-di-para-phenylene) disemicarbazide and other hydrazines; and water.

  The amount of the chain extender component used is such that the equivalent ratio of the isocyanate reactive group of the chain extender to 1 equivalent of the isocyanate group in the urethane prepolymer before the chain extension reaction is from the viewpoint of the film properties of the aqueous acrylic urethane resin. The amount is preferably in the range of 0.1 to 1.0.

  The (meth) acrylate related to the unsaturated monomer of the component (c) used in the present invention is not particularly limited. For example, a (meth) acrylalkyl ester compound having an alkyl group having 1 to 18 carbon atoms It is. As the alkyl group of the alkyl ester, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, cyclohexyl, benzyl, n-octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl Alkyl groups such as octadecyl, methoxyethyl, ethoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-3-chloropropyl, dimethylaminoethyl, diethylaminoethyl, glycidyl or tetrahydrofurfuryl and substituted alkyl Groups. In the present invention, among these, alkyl esters having 1 to 8 carbon atoms are preferable, and alkyl esters having 1 to 4 carbon atoms are more preferable from the viewpoints of reactivity, water dispersibility, and availability. .

  Moreover, another unsaturated monomer can also be copolymerized with the said unsaturated monomer (c) of this invention. Examples of these other unsaturated monomers include aliphatic unsaturated hydrocarbons such as ethylene, propylene, butene, isobutene, and butadiene, halogenated aliphatic unsaturated hydrocarbons such as vinyl chloride and vinylidene chloride, styrene, and α-methyl. Aromatic unsaturated hydrocarbons such as styrene and vinyltoluene, unsaturated carboxylic acids such as crotonic acid, itaconic acid, fumaric acid and maleic acid, or esters thereof (the alcohol component constituting the ester includes the (meth) acrylate described above. Are included), and vinyl esters such as vinyl benzoate and vinyl acetate; nitrogen-containing vinyl monomers such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and acrylonitrile; and the like.

  In addition, the content of the unsaturated monomer selected from (meth) acrylic acid or (meth) acrylate used in the present invention in the total unsaturated monomer can be arbitrarily set, but the total unsaturated monomer It is preferably 30% by mass or more, and more preferably 50% by mass or more. If it is less than 30% by mass, the effect of using (meth) acrylic acid or (meth) acrylate is hardly exhibited.

  In addition, by using unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and maleic acid and using a neutralizing agent, water-solubility may be imparted to the acrylic resin itself. it can. Examples of the neutralizing agent include those that can be used in the case of the water-based polyurethane resin described above.

  These unsaturated monomers can be charged all at the beginning of the reaction, or dividedly or continuously, and a chain transfer agent such as a mercaptan is added as necessary. You can also.

  The polymerization initiator used for producing the acrylic resin is not particularly limited, and not only a water-soluble initiator used in ordinary emulsion polymerization but also an oil-soluble initiator can be used. . Examples of these polymerization initiators include potassium persulfate, ammonium persulfate, azobiscyanovaleric acid, azobisisobutyronitrile, tert-butyl hydroperoxide, dicumyl peroxide, and benzoyl peroxide. Moreover, what is called a redox catalyst which consists of a combination of these polymerization initiators, sulfite, and a sulfoxylate can also be used.

  The amount of the polymerization initiator used varies depending on the type, concentration, reaction temperature, and the like of the unsaturated monomer, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 10% by mass with respect to the total unsaturated monomers. 5% by mass. These polymerization initiators can be added not only in a batch but also in portions or continuously.

  Although the reaction temperature at the time of superposing | polymerizing the said unsaturated monomer changes according to the kind and quantity of the unsaturated monomer and polymerization initiator to be used, it is preferable that it is 0-100 degreeC.

  Moreover, the emulsifier that can be used when the acrylic resin is produced (polymerized) alone in advance is not particularly limited. Specific examples thereof include a reactive emulsifier and an emulsifier that can be used in the above-described aqueous polyurethane resin. Is mentioned.

  Moreover, as said reactive emulsifier, if it has an unsaturated bond which can be copolymerized with the said unsaturated monomer in a molecule | numerator, it can be used regardless of being a nonionic type, an anionic type, or a cationic type. .

  The reactive emulsifier is a compound having at least one hydrophobic group, hydrophilic group and reactive group in the molecule. The hydrophobic group is a group comprising an aliphatic or aromatic hydrocarbon group, and the hydrophilic group is represented by a nonionic group represented by a polyoxyalkylene ether group, a sulfonate, a carboxylate or a phosphate. Including an anionic group or a cationic group typified by a quaternary ammonium salt, the reactive group is a vinyl ether group, an allyl ether group, a vinyl phenyl group, an allyl phenyl group; an ester group or an amide of (meth) acrylic acid Group; or a group containing an ester group or an amide group of an unsaturated dibasic acid such as maleic acid.

  Examples of the reactive emulsifier include, for example, JP-A-62-22803, JP-A-62-2104802, JP-A-62-2104803, JP-A-62-221431, JP-A-62-221432, and JP-A-62-2225237. Nos. 62-244430, 62-286528, 62-289228, 62-289229, 63-12334, 63-54930, 63-77530 Gazette, 63-77531, 63-77532, 63-84624, 63-84625, 63-126535, 63-126536, 63-147530 63-139035, JP-A-1-11630, 1-222338, 1 No. 22627, No. 1-2628, No. 1-33062, No. 1-334430, No. 1-33441, No. 1-34342, No. 1-99638, No. 1-99639 No. 4-50204, No. 4-53802, and No. 4-55401.

  Specific examples of the reactive emulsifier include, for example, 1- (meth) allyloxy-2-hydroxyalkane, 1- (meth) allyloxy-3-alkylphenoxy-2-hydroxyalkane, 1- (meth) acryloyloxy-2 -Hydroxyalkane, 1- (meth) acryloyloxy-3-alkylphenoxy-2-hydroxyalkane, 1- (meth) allyloxy-3-alkyloxy-2-hydroxyalkane, 1- (meth) acryloyloxy-3-alkyloxy- An alkylene oxide adduct of 2-hydroxyalkane and 4-alkyl-2- (2-propenyl) phenol, or a sulfate ester alkali, a phosphate ester alkali, or an ammonium salt thereof can be used.

  It is preferable that the usage-amount of the said reactive emulsifier is 0.1-20 mass% in all the unsaturated monomers. When the amount used is less than 0.1% by mass, the emulsion stability becomes insufficient, and when it exceeds 20% by mass, the properties of the film formed from the resulting aqueous resin may be adversely affected.

  The water-based acrylic urethane resin composition of the present invention contains a polyurethane resin and an acrylic resin, but the adjustment method is not particularly limited, and is a method of mixing a separately manufactured water-based polyurethane resin and a water-based acrylic resin, or Any method of adding an acrylic unsaturated monomer mixture and an emulsifier to a water-based polyurethane resin for polymerization can be employed. In the present invention, a method of polymerizing an unsaturated monomer in an aqueous polyurethane resin is more preferable from the viewpoint of improving various performances such as coating film transparency.

  In the water-based acrylic urethane resin composition of the present invention, the polyurethane resin and the acrylic resin are contained so as to have a mass ratio of 20:80 to 80:20, and the total resin solid content is 2 to 2 in the previous solid content. It is contained so that it may become 70 mass%, Preferably 5-60 mass%. If the total solid content of the polyurethane resin and the acrylic resin is less than 2% by mass, it takes a long time to dry, and if the solid content exceeds 70% by mass, the viscosity becomes high and the handling becomes inconvenient. And storage stability decreases.

  Various additives usually used can be added to the water-based acrylic urethane resin composition of the present invention as necessary. Specific examples of the additive include, for example, a crosslinking agent, various weathering agents (hindered amine light stabilizers, ultraviolet absorbers and antioxidants), a silane coupling agent that particularly enhances adhesion to the substrate, and colloidal silica. Or inorganic colloidal sol such as colloidal alumina, tetraalkoxysilane and its condensation polymer, chelating agent, epoxy compound, pigment, dye, film-forming aid, curing agent, external cross-linking agent, viscosity modifier, leveling agent, antifoaming agent, Anti-gelling agent, radical scavenger, heat resistance imparting agent, inorganic or organic filler, plasticizer, lubricant, fluorine-based or siloxane-based antistatic agent, reinforcing agent, catalyst, thixotropic agent, wax, prevention Examples thereof include a clouding agent, an antibacterial agent, an antifungal agent, an antiseptic and an antirust agent.

  The cross-linking agent can be added as an internal cross-linking agent during the synthesis of the urethane prepolymer, or can be added as an external cross-linking agent to the aqueous acrylic urethane resin composition.

  Examples of the internal crosslinking agent include melamine compounds such as melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine, And low molecular polyol compounds having three hydroxyl groups such as trimethylolpropane. In the present invention, among these, melamine is particularly preferable because it hardly inhibits the water dispersibility of the urethane prepolymer.

  As the external cross-linking agent, urea, melamine, benzoguanamine and the like and adducts of formaldehyde, amino resins such as alkyl ether compounds composed of these adducts and alcohols having 1 to 6 carbon atoms, polyfunctional epoxy compounds, A polyfunctional isocyanate compound, a block isocyanate compound, a polyfunctional aziridine compound, etc. are mentioned. Moreover, when an aqueous polyurethane resin is anionic, the compound which can react with an anionic group (specifically a carboxyl group or a sulfonic acid group) can be used as a crosslinking agent.

  Examples of the compound that can react with the anionic group include an oxazoline compound, an epoxy compound, a carbodiimide compound, an aziridine compound, a melamine compound, and a zinc complex. In the present invention, among these, it is preferable to use an oxazoline compound, an epoxy compound, and a carbodiimide compound that easily react with an anionic group.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6- Tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracar Xylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) .Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidi Amino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8 , 12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8 , 12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] -1,5,8,1 2-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy] ) Butyl Ruboniruokishi] ethyl] -2,4,8,10-spiro [5.5] undecane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-C13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylpheny ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 1,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5 -Di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di) Benzoates such as 3 butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metals Examples thereof include salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of the antioxidant include phosphorus-based, phenol-based, and sulfur-based antioxidants. Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl phosphite, Diphenyl decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (mixed alkyl of C ₁₂ alkyl to C ₁₅ alkyl) -4,4′-isopropylidene diphenyl phosphite, bis [2,2′-methylenebis ( 4,6-diamy Ruphenyl)]-isopropylidene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl -5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis) 3-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) ) Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, 2-butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol Monophosphite etc. are mentioned.

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditertiarybutyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyl) Oxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) pro Onato], tocopherol and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic esters of polyols.

  The amount of the weathering agent (hindered amine light stabilizer, ultraviolet absorber and antioxidant) used is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the solid content of the aqueous acrylic urethane resin composition. In particular, the content is more preferably 0.01 to 5 parts by mass. When the amount is less than 0.001 part by mass, a sufficient addition effect may not be obtained. When the amount is more than 10 parts by mass, water dispersion stability and physical properties of the coating film may be adversely affected.

  As a method of adding these weathering agents, a method of adding to a polyol of a urethane raw material, a method of adding to a urethane prepolymer, a method of adding to a water phase at the time of water dispersion of urethane or acrylic resin, a method of adding after water dispersion However, from the viewpoint of easy operation, a method of adding to the raw material polyol and a method of adding to the urethane prepolymer are preferable.

  The synthetic resin that can form the synthetic resin film before coating used in the present invention is not particularly limited, but in the present invention, in particular, vinyl chloride resin, polyolefin resin, polyester resin, etc. Can be preferably used.

  The vinyl chloride resin is not particularly limited by the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. In the present invention, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile little ternary copolymer Polymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer Polymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer Vinyl chloride resins such as polymers, vinyl chloride-various vinyl ether copolymers, and blends thereof, or other synthetic resins not containing chlorine, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers Examples thereof include blends, block copolymers, graft copolymers, and the like with polymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, and polyesters.

  Examples of the polyolefin resin include high density, low density or linear low density polyethylene; single weight of α-olefin such as polypropylene, polybutene-1, poly-3-methylpentene, and ethylene-propylene copolymer. Examples thereof include copolymers or copolymers, copolymers of these α-olefins with polyunsaturated compounds such as conjugated dienes or nonconjugated dienes, acrylic acid, methacrylic acid, or vinyl acetate.

  Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyether polyester.

  As a method of forming a film from the synthetic resin, a normal synthetic resin processing method is used. For example, calendar processing, roll processing, extrusion molding processing, blow molding, inflation molding, melt casting, pressure molding processing. A method such as paste processing or powder molding can be preferably used.

  The thickness of the synthetic resin film is preferably 0.001 to 1 mm, more preferably 0.01 to 0.5 mm.

  Further, when forming the synthetic resin film, additives used in ordinary synthetic resins, such as plasticizers, organic carboxylic acids, phenols and organic phosphoric acid metal salts, organic tin compounds, epoxy compounds, β -Diketone compounds, polyhydric alcohols, phosphorus-based, phenol-based or sulfur-based antioxidants, ultraviolet absorbers, light stabilizers, hydrotalcite compounds, zeolite compounds, perchlorates, other inorganic metal compounds, crosslinking Agents, fillers, antistatic agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, pigments, processing aids, antifogging agents and antifoggants An agent or the like can be used.

  Examples of the method for coating the aqueous acrylic urethane resin composition of the present invention on the synthetic resin film include, for example, a gravure coating method, a reverse roll coating method, an air knife coating method, a bar coating method, a doctor blade coating method, and a curtain roll coating method. And coating methods such as dip coating, spray coating, and rod coating. For example, the aqueous acrylic urethane resin composition of the present invention is applied to one or both sides of a vinyl chloride resin film so that the dry film thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm. And dry.

  Applications of the water-based acrylic urethane resin composition of the present invention include paints, adhesives, surface modifiers, organic powder and / or inorganic powder binders and molded articles, and the like. Specifically, paints for inorganic structural materials such as glass, slate or concrete, coatings for agricultural films, wood coatings, steel plate coatings, thermal paper coatings, inkjet paper coatings, printing inks Examples thereof include a binder and a coating agent for electronic material parts. Among these uses, the water-dispersed polyurethane composition of the present invention is particularly suitable as a coating agent for agricultural films, steel sheet, glass or wood paints, and paper, fiber or electronic material parts. It is particularly suitable as a coating agent for agricultural films.

  In addition, the use of the coating film according to the present invention is not particularly limited, but for agricultural films such as house, tunnel and mulch (so-called agricultural bi, agricultural poly, agricultural sacbi, agricultural PO, hard film, etc.) It can be particularly preferably used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by these Examples. In addition, the part in an Example and a comparative example represents a mass part unless there is particular notice.

[Production Example-1]
<Synthesis of General Formula (1) Isocyanate Compound Solution NOD-1>
1,6-hexamethylene diisocyanate nurate (193 g / NCO equivalent) 579 g (NCO equivalent: 3.0), stearyl alcohol (n-octadecanol) 270 g (OH equivalent: 1.0) and N-methyl-2 -849 g of pyrrolidone was charged into a reaction flask, reacted at 115-120 ° C for 2 hours under a nitrogen stream, and confirmed that NCO% was 5.0%, and a solution of an isocyanate compound of general formula (1) NOD-1 was obtained.

<Synthesis of water-based acrylic urethane resin composition PAU-1>
<Urethane prepolymer production process>
As a polyol (a) component, 49 g (0.049 mol) of a polyester diol (manufactured by ADEKA, product name Y9-10) having a number average molecular weight of 1000 obtained from adipic acid and neopentyl glycol, and trimethylolpropane As the isocyanate component (b), 2 g (0.038 mol), 56 g (0.033 mol) of the above-mentioned isocyanate compound solution NOD-1, and 87 g (0. 0.3M) of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI). 33 mol), 17.9 g (0.134 mol) of dimethylolpropionic acid as the ionic group-introducing compound (d), and 64 g of N-methyl-pyrrolidone as the solvent were charged in a reaction flask, and the temperature was 100 to 120 ° C. under a nitrogen stream. For 2.5-3.0 hours and confirm that the NCO% is 3.8%. . After cooling to 50 to 60 ° C., 16.2 g (0.14 mol) of triethylamine is added as an ionic group neutralizing agent (e), and the mixture is reacted at 50 to 60 ° C. for 30 minutes. Obtained.

<Latex and urethane high molecular weight process>
As unsaturated monomer component (c), 162 g (1.62 mol) of methyl methacrylate, 25 g (0.19 mol) of butyl acrylate and 2.5 g (0.029 mol) of methacrylic acid were added, and urethane prepolymer / An acrylic monomer mixture was obtained.
Next, 0.3 g of an antifoaming agent (manufactured by ADEKA, B1016) is added to 519 g of water, and 441 g of the urethane prepolymer / acrylic monomer mixture is added to prepare an aqueous solution, followed by stirring at 20-40 ° C. for 15 minutes. Then, 16.0 g (0.067 mol) of an ethylenediamine / water (1/3) mixture was added dropwise as a chain extender, and the mixture was stirred at 20 to 40 ° C. for 10 minutes. Furthermore, 11.6 g (0.017 mol) of adipic acid dihydrazide / water (1/3) mixed solution was added as a chain extender, and stirring was continued at 20 to 40 ° C. until disappearance of NCO group (1 to 2 hours). An aqueous polyurethane / acrylic monomer mixture was obtained.

<Acrylic polymerization process>
To the obtained aqueous polyurethane / acrylic monomer mixture, 10.3 g (0.0013 mol) of a 3% by weight aqueous solution of potassium persulfate was added, and an acrylic polymerization reaction was carried out at 50 to 60 ° C. for 2 hours to obtain an aqueous acrylic urethane resin. Composition PAU-1 was obtained.

[Production Examples-2 and -3]
<Synthesis of aqueous acrylic urethane resin compositions PAU-2 and PAU-3>
Based on the formulation described in Table 1 below, it was produced under the same production conditions as the PAU-1.

[Comparative Production Example-1]
<Synthesis of water-based polyurethane resin PUD-1>
A water-based polyurethane resin PUD-1 was obtained in the same manner as in Production Example-1, except that the unsaturated monomer (c) used in Production Example-1 was not blended.

[Comparative Production Examples-2 to 5]
<Synthesis of water-based acrylic urethane resins PAU-4 to PAU-7>
Based on the formulation described in Table 1 below, aqueous acrylic urethane resins PAU-4 to PAU-7 were produced in the same manner as in Production Example-1. However, for PAU-7, the water dispersibility of the urethane prepolymer was inferior, and an aqueous resin could not be obtained.

＊１：Ｙ９−１０：ポリエステルポリオール（ネオペンチルグリコール／アジピン酸Ｍｗ１０００）
＊２：ＰＴＧ−１０００：ポリテトラメチレンエーテルグリコールＭｗ１０００（（株）保土ヶ谷化学製）
＊３：Ｃ１０９０：ポリカーボネートジオールＭｗ１０００（（株）クラレ製）
＊４：ＴＭＰ：トリメチロールプロパン
＊５：ＮＯＤ−１：ヘキサメチレンジイソシアネート三量体／ステアリルアルコール反応物
＊６：Ｈ_１２ＭＤＩ：ジシクロヘキシルメタン−４，４’−ジイソシアネート
＊７：ＩＰＤＩ：イソホロンジイソシアネート
＊８：ＭＭＡ：メタクリル酸メチル
＊９：ＢＡ：アクリル酸ブチル
＊１０：ＭＡ：メタクリル酸
＊１１：ＤＭＰＡ：ジメチロールプロピオン酸
＊１２：ＴＥＡ：トリエチルアミン
＊１３：ＮＭＰ：Ｎ−メチル−２−ピロリドン
＊１３：UPP／AC混合物：ウレタンプレポリマー／アクリルモノマー混合物
＊１４：EDA／水：エチレンジアミン／水（1／３）混合液
＊１５：ADH／水：アジピン酸ジヒドラジド／水（1／３）混合液
＊１６：KPS／水：過硫酸カリウム３wt％水溶液
＊１７：ＮＣＯeq：ウレタンプレポリマー／アクリルモノマー混合物のイソシアネート当量

* 1: Y9-10: Polyester polyol (neopentyl glycol / adipic acid Mw1000)
* 2: PTG-1000: Polytetramethylene ether glycol Mw1000 (manufactured by Hodogaya Chemical Co., Ltd.)
* 3: C1090: Polycarbonate diol Mw1000 (manufactured by Kuraray Co., Ltd.)
* 4: TMP: Trimethylolpropane * 5: NOD-1: Hexamethylene diisocyanate trimer / stearyl alcohol reactant * _6: H 12 _MDI: dicyclohexylmethane-4,4'-diisocyanate * 7: IPDI: isophorone diisocyanate * 8: MMA: methyl methacrylate * 9: BA: butyl acrylate * 10: MA: methacrylic acid * 11: DMPA: dimethylolpropionic acid * 12: TEA: triethylamine * 13: NMP: N-methyl-2-pyrrolidone * 13: UPP / AC mixture: urethane prepolymer / acrylic monomer mixture * 14: EDA / water: ethylenediamine / water (1/3) mixture * 15: ADH / water: adipic acid dihydrazide / water (1/3) mixture * 16: KPS / water: potassium persulfate 3wt% aqueous solution * 17: N Oeq: isocyanate equivalent of the urethane prepolymer / acrylic monomer mixture

[Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2]
<Water resistance evaluation>
<Preparation of coating film>
On the glass plate, the water-based acrylic polyurethane resin or water-based polyurethane resin already prepared in Table 2 was applied using a bar coater so as to have a thickness of 100 μm in a dry state, and dried at room temperature for 24 hours. The coating film was obtained by drying at 120 ° C. for 2 hours.

<Water resistance evaluation of coating film>
The water-based acrylic urethane resin or water-based polyurethane resin coating film obtained above was immersed in water at 25 ° C. for 1 week, and then the degree of whitening was observed by visual observation, and the water resistance was evaluated according to the following criteria.
<Evaluation criteria>
◎: No whitening at all ○: Little whitening
Δ: Slight whitening is observed
×: Fair whitening is observed

[Examples 2-1 to 2-3 and Comparative examples 2-1 to 2-5]
<Dustproof and adhesive evaluation>
<Production of vinyl chloride resin film>
100 parts by weight of vinyl chloride resin (degree of polymerization 1300), 50 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, 2 parts by weight of bisphenol A type epoxy resin, 1.5 parts by weight of sorbitan monopalmitate, methylene bis stearamide 0.5 parts by mass, 0.5 parts by mass of hydrotalcite, 0.5 parts by mass of zinc stearate, 0.5 parts by mass of barium stearyl phosphate, octadecyl-3- (3,5-ditert-butyl-4- 0.1 part by weight of hydroxyphenyl) propionate and tetra (1,2,2,6,6-pentamethyl-4-
Piperidyl) butanetetracarboxylate 0.1 parts by mass was blended and calendered at 180 ° C. to prepare a 0.1 mm thick vinyl chloride resin film.

[Production of coating film]
<Vinyl chloride resin>
On one side of the vinyl chloride resin film obtained above, the aqueous resin composition obtained in the production example described in Table 3 below was applied using a 130 mesh gravure coater, and a 2 μm thick coating film was applied. A coating film was obtained.

<Dustproof evaluation>
The coated surface of the coating film obtained above is exposed to the outside (Urawa City, Saitama Prefecture), and the dust resistance is evaluated visually based on the following criteria for the film before exposure and after 12 months of exposure. did.
(Dust-proof evaluation criteria)
A: Almost no dust is attached
○: Slightly attached dust
Δ: Some dust is attached
×: Dust adheres remarkably

<Bend resistance evaluation>
The coating film obtained above was subjected to 180 ° bending 10 times and then visually evaluated for bending resistance based on the following evaluation criteria.
(Bend resistance evaluation criteria)
○: No cracking or peeling
Δ: Slight cracks occur
X: Cracking and peeling occur [Example 3]

<Production of polyethylene film>
100 parts by mass of low density polyethylene (density 0.923 g / cm ³ , MFR = 2.0), 0.2 parts by mass of tris (2,4-ditert-butylphenyl) phosphite and 0.2 parts by mass of methylene bisamide And a film having a thickness of 0.1 mm was obtained by an inflation processing method.

<Preparation of coating film>
<Polyethylene film>
The water-based acrylic urethane resin composition (PAU-1) obtained in the above production example was applied to one side of the polyethylene film obtained above with a 130 mesh gravure coater to form a coating film having a thickness of 2 μm.

The same test as in Example 2 was performed using the coating film obtained above. The results are shown in Table 3 below.
[Example 4]

<Preparation of polyester film>
100 parts by mass of polyethylene terephthalate and 0.2 parts by mass of tris (2,4-ditert-butylphenyl) phosphite were blended, and a 0.1 mm thick film was produced by melt extrusion.

<Preparation of coating film>
<Polyester film>
The water-based acrylic urethane resin composition (PAU-1) obtained in the above production example was applied to one side of the polyester film obtained above with a 130 mesh gravure coater to form a coating film having a thickness of 2 μm.

  The same test as in Example 2 was performed using the coating film obtained above. The results are shown in Table 3 below.

  As is clear from the results in Table 2, in the case of Comparative Example 1-2 in which the amount of the specific isocyanate compound used in the present invention is small, the water resistance is inferior, and the acrylic resin as in Comparative Example 1-1. It can be seen that the water resistance is good only in the case of the acrylic urethane resin composition of the present invention in which a specific amount of a specific isocyanate is blended, even though the urethane resin alone system not compounding is poor. Therefore, the acrylic urethane resin composition of the present invention is useful as a paint / coating agent having excellent water resistance.

  Further, as is clear from the results of Table 3, in the case of Comparative Example 2-1 where no acrylic resin is combined and Comparative Example 2-3 where the composite amount is small, the dust resistance is inferior, and even when the acrylic resin is combined, In the case of Comparative Example 2-2 in which the specific isocyanate compound of the present invention is not blended, the dust resistance is inferior. Furthermore, in the case of Comparative Example 2-4 in which the amount of the acrylic resin is large, the dust resistance is excellent, but the flex resistance is inferior, and the good dust resistance and flex resistance obtained in the present invention cannot be obtained. Was confirmed.

  The acrylic urethane resin composition of the present invention is excellent in water resistance and useful as a paint or a coating agent, and the coating film of the present invention coated with the acrylic urethane resin composition of the present invention is dustproof and flex-resistant. It is extremely useful in the industry because it is excellent in use and is particularly suitable for applications such as agricultural films.

Claims (7)

A water-based acrylic urethane resin composition containing 2 to 70% by mass of a resin containing 20 to 80% by mass of a polyurethane resin and 80 to 20% by mass of an acrylic resin in terms of solid content, wherein the polyurethane resin is a polyether At least one polyol component (a) selected from the group consisting of polyols, polyester polyols, polyester polycarbonate polyols, crystalline polycarbonate polyols and amorphous polycarbonate polyols, represented by the following general formula (1) Isocyanate component (b) essentially comprising the isocyanate compound represented, and an aqueous polyurethane resin obtained using water as an essential component, wherein the acrylic resin is selected from (meth) acrylic acid and (meth) acrylate At least one unsaturated monomer In addition to the water-based acrylic resin obtained by polymerizing c), the content of the isocyanate compound represented by the general formula (1) is 2 to 35% by mass in the solid content of the water-based polyurethane resin. A water-based acrylic urethane resin composition characterized in that:

However, R ¹ in the above formula represents an alkyl group having 10 to 30 carbon atoms, R ² represents —N═C═O, or the following group, and A represents two —N═C from the diisocyanate compound. = Represents a residue without O;

However, R ¹ in the above formula represents an alkyl group having 10 to 30 carbon atoms.   The aqueous acrylic urethane resin composition according to claim 1, wherein A in the general formula (1) is a residue obtained by removing two -N = C = O from 1,6-hexamethylene diisocyanate.   3. The isocyanate component (b) according to claim 1 or 2, further comprising dicyclohexylmethane-4,4'-diisocyanate and / or isophorone diisocyanate together with the isocyanate compound represented by the general formula (1). Water-based acrylic urethane resin composition.   The aqueous acrylic urethane resin according to any one of claims 1 to 3, further comprising an ionic group-introducing compound as component (d) and an ionic group neutralizer as component (e) as essential components. Composition.   A coating film obtained by applying and drying the water-based acrylic urethane resin composition according to any one of claims 1 to 4 on one side or both sides of a synthetic resin film.   The coating film according to claim 5, wherein the synthetic resin film is a vinyl chloride resin film, a polyolefin resin film, or a polyester resin film.   The coating film according to claim 5 or 6, wherein the product film is used as an agricultural film.