JP2015131935A - In-line coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an in-line coating agent that is a coating agent used in-line coating process, and that has excellent property of not curling a resin film during the forming of a coat on the resin film surface using the coating agent (curl preventive property), storage stability of the coating agent itself, and scratch resistance and water resistance of the coat formed from coating agent.SOLUTION: Provided is an in-line coating agent that is a coating agent used during in-line coating, and characterized in containing a resin emulsion containing emulsion particles composed of (meth)acrylic polymer obtained by polymerizing a monomer component comprising (meth)acrylic monomer, and a curable monomer and/or curable oligomer.

Description

  The present invention relates to an in-line coating agent. More specifically, the present invention is, for example, when manufacturing a film used for optical materials such as lens units, displays, mechanical parts, electrical parts, electronic parts, building materials, automotive parts, etc. by an in-line coating method. The present invention relates to an in-line coating agent that can be suitably used.

  In addition, in this invention, an inline coating agent means the coating agent used when manufacturing a film by an inline coating method.

  Among the methods for manufacturing a resin film having a resin coating on the surface, the in-line coating method, in which the resin coating is formed on the surface of the resin film when manufacturing the resin film, increases the production efficiency by simplifying the manufacturing process. Has the advantage of being In the in-line coating method, for example, an unstretched resin film is uniaxially stretched, a coating agent is applied to the uniaxially stretched resin film, and dried to form a film, and then the resin on which the film is formed This is done by further stretching the film in a direction perpendicular to the uniaxial stretching and fixing the stretching by heating.

  Among the coating agents used in the in-line coating method, resin film production equipment is generally not explosion-proof, and can be coated when producing resin films. In-line coating agents are preferred.

  As the water-based in-line coating agent, water-dispersible or water-soluble acrylic resins, water-dispersible or water-soluble polyester resins, and the like have been proposed (see, for example, paragraph [0011] of Patent Document 1). When the resin is used, it is said that a film excellent in adhesiveness, anti-booking property and slipperiness can be obtained (see, for example, paragraph [0094] of Patent Document 1).

  In recent years, however, the inline coating agent has the property that it is difficult to bend the resin film when it is formed on the surface of the resin film (anti-curl property), and the storage stability of the inline coating agent itself. Therefore, it is desired to improve the scratch resistance and water resistance of a film formed from an in-line coating agent.

JP 2009-154490 A

  This invention is made | formed in view of the said prior art, Comprising: It is an inline coating agent used for an inline coating method, Comprising: When forming a film on the surface of a resin film using the said inline coating agent, a resin film is formed. It is an object of the present invention to provide an in-line coating agent that is difficult to bend (anti-curl property), the storage stability of the in-line coating agent itself, the scratch resistance of the film formed from the in-line coating agent, and the water resistance.

  The present invention is a coating agent used in an in-line coating method, and a resin emulsion containing emulsion particles composed of a (meth) acrylic polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer, and curability The present invention relates to an in-line coating agent characterized by containing a monomer and / or a curable oligomer.

  The in-line coating agent of the present invention has the property that it is difficult to bend the resin film when it is formed on the surface of the resin film using the in-line coating agent (anti-curl property), and the storage stability of the in-line coating agent itself is excellent. It has an excellent effect of forming a film excellent in scratch resistance and water resistance.

  As described above, the inline coating agent of the present invention is a coating agent used for inline coating, and is obtained from a (meth) acrylic polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer. It comprises a resin emulsion containing emulsion particles and a curable monomer and / or curable oligomer.

  In the present invention, “(meth) acryl” means acrylic or methacrylic. Further, the “curable monomer and / or curable oligomer” means a single use of a curable monomer, a single use of a curable oligomer, or a combined use of a curable monomer and a curable oligomer.

  The resin emulsion contains emulsion particles made of a (meth) acrylic polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer. The (meth) acrylic polymer constituting the emulsion particles used in the resin emulsion can be obtained, for example, by polymerizing a monomer component containing a (meth) acrylic monomer by a polymerization method such as an emulsion polymerization method. The present invention is not limited to such a method.

  Examples of (meth) acrylic monomers include (meth) acrylic acid, alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, oxo group-containing (meth) acrylate, fluorine atom-containing (meth) acrylate, and epoxy group-containing ( (Meth) acrylate, alkoxyalkyl (meth) acrylate, aralkyl (meth) acrylate, carbonyl group-containing (meth) acrylate, aziridinyl group-containing (meth) acrylate, nitrogen atom-containing (meth) acrylate, maleimide (meth) acrylate, carboxyl group terminal Although caprolactone modified (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These (meth) acrylic monomers may be used alone or in combination of two or more.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) Acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methylcyclohexylmethyl (meth) acrylate, tert-butylcyclohexyl (meth) ) An ester group such as acrylate and cyclododecyl (meth) acrylate having 1 to 18 carbon atoms and optionally having an alicyclic structure includes alkyl (meth) acrylate. It is not limited to only. These monomers may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in ester groups such as butyl (meth) acrylate and caprolactone-modified hydroxy (meth) acrylate, but the present invention is not limited to such examples. Absent. These monomers may be used alone or in combination of two or more.

  Examples of the oxo group-containing (meth) acrylate include (di) ethylene glycol (methoxy) (ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate) ( Examples thereof include, but are not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the fluorine atom-containing (meth) acrylate include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, and perfluoroisononylethyl. Examples include (meth) acrylate and fluorine atom-containing alkyl (meth) acrylate having a fluorine atom in an ester group such as perfluorooctylethyl (meth) acrylate, but the present invention is not limited to such examples. . These monomers may be used alone or in combination of two or more.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. It is not limited to only. These monomers may be used alone or in combination of two or more.

  Examples of the alkoxyalkyl (meth) acrylate include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane. Examples include tripropoxy (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, and methyl α-allyloxymethyl acrylate, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the aralkyl (meth) acrylate include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the carbonyl group-containing (meth) acrylate include acetonyl (meth) acrylate, diacetone (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, and oxocyclohexylmethyl (meth) acrylate. The invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the aziridinyl group-containing (meth) acrylate include 2-aziridinylethyl (meth) acrylate, but the present invention is not limited to such examples.

  Examples of the nitrogen atom-containing (meth) acrylate include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and ethylene oxide addition (meth) acrylate of morpholine. It is not limited. These monomers may be used alone or in combination of two or more.

  Examples of monomers other than (meth) acrylic monomers include aromatic monomers other than (meth) acrylic monomers, carboxyl group-containing aliphatic monomers other than (meth) acrylate monomers, and other than (meth) acrylate monomers. Nitrogen atom-containing aliphatic monomers, silane group-containing aliphatic monomers, carbonyl group-containing aliphatic monomers other than (meth) acrylate monomers, aziridinyl group-containing aliphatic monomers other than (meth) acrylate monomers, olefins Although the system monomer etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of aromatic monomers other than (meth) acrylic monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p. -Ethylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o -Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene , M-tert-butoxystyrene , P-tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, vinyltoluene and the like, but the present invention is not limited to such examples. Absent. These monomers may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing aliphatic monomer other than the (meth) acrylate monomer include itaconic acid and the like, but the present invention is not limited to such examples.

  Examples of nitrogen-containing aliphatic monomers other than (meth) acrylate monomers include (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide. N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, Acrylamide compounds such as N, N-dimethylaminopropylacrylamide, diacetoneacrylamide, N-vinylpyrrolidone, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinyloxazoly , N-vinylsuccinimide, N-vinylmethylcarbamate, N, N-methylvinylacetamide, (meth) acryloyloxyethyltrimethylammonium chloride, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, ( Examples include (meth) acrylonitrile and maleimide, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the silane group-containing aliphatic monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, and vinyl. Examples include trichlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of carbonyl group-containing aliphatic monomers other than (meth) acrylate monomers include, for example, acrolein, boromyrstyrene, vinyl ethyl ketone, (meth) acryloyloxyalkylpropenal, 2-hydroxypropyl (meth) acrylate acetyl acetate, Examples include butanediol-1,4-acrylate acetyl acetate, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the aziridinyl group-containing aliphatic monomer other than the (meth) acrylate monomer include (meth) acryloylaziridine, but the present invention is not limited to such examples.

  Examples of the olefin-based monomer include ethylene, propylene, 4-methyl-1-pentene, and the like, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Further, in the present invention, from the viewpoint of imparting ultraviolet stability and ultraviolet absorptivity to the coating film to be formed, an appropriate amount of an ultraviolet-stable monomer, an ultraviolet-absorbing monomer, etc., within the range that does not impair the object of the present invention. You may make it contain in a component.

  Examples of the UV-stable monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4 -(Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino -2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-si No-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano Examples include -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like. Is not limited to such examples. These monomers may be used alone or in combination of two or more.

  In the present invention, “(meth) acryloyloxy” means acryloyloxy or methacryloyloxy.

  Examples of the UV-absorbing monomer include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-absorbing monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the benzotriazole-based ultraviolet absorbing monomer include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy -5 ′-(meth) acryloylaminomethyl-5′-tert-octylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2′-Hydroxy-5 ′-(meth) acryloyloxyhe Silphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′ -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acrylyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-H Roxy-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′- tert-butylphenyl] -4-tert-butyl-2H-benzotriazole, and the like, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the benzophenone-based UV-absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy- 4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2 -(Meth) acryloyloxy] butoxybenzophenone and the like can be mentioned, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  In the present invention, “(meth) acryloyl” means acryloyl or methacryloyl.

  The content of the (meth) acrylic monomer in the monomer component is preferably 5% from the viewpoint of improving the storage stability of the inline coating agent and forming a film excellent in anti-curl property, scratch resistance and water resistance. % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and the upper limit is 100% by mass.

  Examples of the monomer component polymerization method include a polymerization method such as an emulsion polymerization method, but the present invention is not limited to such examples. When the emulsion polymerization method is employed as the monomer component polymerization method, an environmentally friendly in-line coating agent can be obtained directly.

  An aqueous medium can be used when the monomer component is subjected to emulsion polymerization. The aqueous medium means water or a mixed solvent of water and a hydrophilic organic solvent having a water content of 50% by mass or more. Examples of the hydrophilic organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, and dipropyleneglycol. Polyhydric alcohols such as acetone, methyl ethyl ketone, ketones such as methyl propyl ketone, aliphatic organic acid alkyl esters such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, although such polyhydric alkyl ethers of alcohols, such as dipropylene glycol monomethyl ether, the present invention is not limited those exemplified only. These hydrophilic organic solvents may be used alone or in combination of two or more. Of the aqueous media, water is preferred.

  Examples of the method for emulsion polymerization of the monomer component include, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, a surfactant dissolved in a medium such as water, and the monomer component and Examples thereof include a method of dropping a polymerization initiator, a method of dropping a monomer component preliminarily emulsified with a surfactant and water into water or an aqueous medium, etc., but the present invention is limited only to such a method. It is not something. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the non volatile matter amount contained in the resin emulsion obtained. The medium may be charged in the reaction vessel in advance or used as a pre-emulsion. The medium may be used when a resin emulsion is produced by emulsion polymerization of monomer components as required.

  When the monomer component is emulsion polymerized, the monomer component, the surfactant and the medium may be mixed and then the emulsion polymerization may be performed. The monomer component, the surfactant and the medium are emulsified by stirring to prepare a pre-emulsion. After that, emulsion polymerization may be carried out, or emulsion polymerization may be carried out by mixing at least one of the monomer component, surfactant and medium and the remaining pre-emulsion. The monomer component, surfactant and medium may be added all at once, may be added in portions, or may be added dropwise continuously.

  Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant. These surfactants are used individually. Two or more types may be used in combination.

  Examples of the anionic surfactant include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene. Alkyl aryl sulfonate salts such as sulfonates; polyoxyethylene alkyl phenyl ether sulfate salts; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalins Condensate; Ammonius Fatty acid salts such as laurylate and sodium stearylate; bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxy Sulfuric acid ester having allyl group such as ethylene phosphonate salt, sulfonate salt of allyloxymethylalkyloxypolyoxyethylene or its salt; Sulfuric acid ester salt of allyloxymethylalkoxyethyl polyoxyethylene, polyoxyalkylene alkenyl ether ammonium sulfate However, the present invention is not limited to such examples.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and Examples include condensates with aliphatic amines, allyloxymethylalkoxyethylhydroxypolyoxyethylene, polyoxyalkylene alkenyl ethers, and the like, but the present invention is not limited to such examples.

  Examples of the cationic surfactant include alkylammonium salts such as dodecyl ammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric surfactants include betaine ester surfactants, but the present invention is not limited to such examples.

  Examples of the polymer surfactant include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; and these polymers Although the copolymer etc. which use 1 or more types of a monomer as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Further, as a surfactant, a surfactant having a polymerizable group, that is, a so-called reactive surfactant is preferable from the viewpoint of improving the water resistance of the film, and from the viewpoint of environmental protection, a non-nonylphenyl type surfactant is used. Agents are preferred.

  Examples of the reactive surfactant include propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt, polyoxyethylene alkylpropenyl phenyl ether sulfonate. Salt, sulfonate salt of allyloxymethylalkyloxypolyoxyethylene, sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene, allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate salt, bis (polyoxyethylene polycyclic phenyl ether ) Methacrylated sulfonate salt, allyloxymethylalkoxyethylhydroxypolyoxyethylene, polyoxyethylene alkylpropenyl Vinyl ether, although such allyloxymethyl nonyl phenoxyethyl hydroxy polyoxyethylene and the like, and the present invention is not limited those exemplified only.

  The amount of the surfactant per 100 parts by mass of the monomer component is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more from the viewpoint of improving polymerization stability. In view of improving the water resistance of the coating, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.

  Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; hydrogen peroxide , Benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, peroxides such as ammonium peroxide, and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. From the viewpoint of improving the water resistance of the coating, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

  The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. Further, from the viewpoint of accelerating the completion time of the polymerization reaction, a part of the polymerization initiator may be added before or after the monomer component is added to the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.

  Moreover, in order to adjust the weight average molecular weight of the (meth) acrylic-type polymer which comprises emulsion particle | grains, a chain transfer agent can be used. Examples of the chain transfer agent include 2-ethylhexyl thioglycolate, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl. Although a styrene dimer etc. are mentioned, this invention is not limited only to this illustration. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent per 100 parts by mass of the monomer component is preferably 0.01 to 10 parts by mass from the viewpoint of adjusting the weight average molecular weight of the emulsion particles.

  If necessary, additives such as a pH buffer, a chelating agent, and a film-forming aid may be added to the reaction system. Since the amount of the additive varies depending on the type, it cannot be determined unconditionally. Usually, the amount of the additive per 100 parts by mass of the monomer component is preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 3 parts by mass.

  The atmosphere for polymerizing the monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization reaction.

  The polymerization temperature for polymerizing the monomer component is not particularly limited, but is usually preferably 0 to 100 ° C, more preferably 40 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for polymerizing the monomer component is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 8 hours.

  In addition, when carrying out emulsion polymerization of a monomer component, you may make it neutralize part or all of the acidic group which the (meth) acrylic-type polymer obtained has with a neutralizing agent. The neutralizing agent may be used after the monomer component is added in the final stage. For example, the neutralizing agent may be used between the first stage polymerization reaction and the second stage polymerization reaction. May be used at the end of

  Examples of the neutralizing agent include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide; alkali metal and alkaline earth metal carbonates such as calcium carbonate; and organic amines such as ammonia and monomethylamine. Although an alkaline substance is mentioned, this invention is not limited only to this illustration. Among these neutralizing agents, volatile alkaline substances such as ammonia are preferable from the viewpoint of improving the water resistance of the coating.

The glass transition temperature of the (meth) acrylic polymer constituting the emulsion particles is the glass transition temperature (Tg) of a homopolymer composed of monomers contained in the monomer component used as the raw material of the (meth) acrylic polymer (absolute From the temperature: K) and the mass fraction of the monomer, the formula:
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ +... + W _n / Tg _n
[Wherein Tg is the glass transition temperature (K) of the polymer to be obtained, W ₁ , W ₂ , W ₃ ... W _n are the mass fraction of each monomer, Tg ₁ , Tg ₂ , Tg ₃ ···· Tg _n are respectively the glass transition temperature (K) of homopolymer comprising a monomer corresponding to the mass fraction of each monomer]
It can obtain | require based on the Formula of Fox (Fox) represented by these. The glass transition temperature of the polymer can also be measured by DSC (Differential Scanning Calorimetry), DTA (Differential Thermal Analyzer), TMA (Thermomechanical Measuring Device), or the like.

  In the present invention, the glass transition temperature of the (meth) acrylic polymer means a glass transition temperature determined based on the Fox formula.

  In addition, about the monomer whose glass transition temperature is unknown like a special monomer, a polyfunctional monomer, etc., the glass transition temperature of a (meth) acrylic-type polymer is calculated | required only using the monomer with known glass transition temperature.

  In consideration of the glass transition temperature of the (meth) acrylic polymer constituting the emulsion particles, the composition of the monomer component used as the raw material of the (meth) acrylic polymer constituting the emulsion particles is determined. Can do.

  The glass transition temperature of the homopolymer is, for example, 105 ° C. for methyl methacrylate homopolymer, 83 ° C. for cyclohexyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, and 84 ° C. for homopolymer of methyl α-allyloxymethyl acrylate. The homopolymer of 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA) is -40 ° C, the homopolymer of acrylic acid is 95 ° C, and the homopolymer of 2-hydroxyethyl methacrylate is 55 ° C.

  The glass transition temperature of the (meth) acrylic polymer constituting the emulsion particles is preferably from the viewpoint of improving the storage stability of the in-line coating agent and forming a film excellent in curl prevention, scratch resistance and water resistance. 50 ° C. or higher, more preferably 70 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of improving the storage stability of the in-line coating agent and forming a film excellent in anti-curl property, scratch resistance and water resistance. The temperature is preferably 120 ° C. or lower.

  The (meth) acrylic polymer constituting the emulsion particles may have a crosslinked structure from the viewpoint of improving water resistance and storage stability. Examples of a method for imparting a crosslinked structure to a (meth) acrylic polymer include a method in which a monomer component contains a silane coupling agent and a polyfunctional monomer, but the present invention is limited only to such examples. It is not a thing. Examples of the silane coupling agent include a silane coupling agent having a polymerizable unsaturated bond such as a (meth) acryloyl group, a vinyl group, an allyl group, and a propenyl group. It is not limited.

  The weight average molecular weight of the (meth) acrylic polymer is a case where the (meth) acrylic polymer has a crosslinked structure and a case where it does not have a crosslinked structure, from the viewpoint of increasing the hardness of the coating film. Preferably it is 100,000 or more, More preferably, it is 300,000 or more, More preferably, it is 550,000 or more, More preferably, it is 600,000 or more. The upper limit value of the weight average molecular weight of the (meth) acrylic polymer is not particularly limited because it is difficult to measure the weight average molecular weight when it has a crosslinked structure, but when it does not have a crosslinked structure, From the viewpoint of improving film formability, it is preferably 5 million or less.

  In addition, in this invention, the weight average molecular weight of a (meth) acrylic-type polymer means the weight average molecular weight (polystyrene conversion) measured by the method as described in a following example.

  From the viewpoint of improving the dispersion stability of the emulsion particles, the average particle diameter of the emulsion particles is preferably 70 nm or more, more preferably 80 nm or more, and further preferably 100 nm or more, from the viewpoint of improving the surface smoothness of the coating film. Preferably it is 450 nm or less, More preferably, it is 400 nm or less, More preferably, it is 350 nm or less.

  In the present invention, the average particle size of the emulsion particles is determined by diluting the resin emulsion with distilled water, collecting about 10 mL of the resulting diluted solution in a glass cell, and measuring the particle size distribution measuring instrument [particle sizing by dynamic light scattering method]. It means volume average particle diameter measured using Windows-based software [Windows (registered trademark) Based Software] using a product name (NICOM P Model 380) manufactured by Systems (Particle Sizing Systems).

  The (meth) acrylic polymer constituting the emulsion particles preferably has a reactive functional group from the viewpoint of improving the scratch resistance of the formed film.

  Examples of the reactive functional group include a hydroxyl group, a carboxyl group, a glycidyl group, a vinyl group, a vinyl ether group, an allyl ether group, an amino group, a benzophenone group, an imide ring group, an oxazoline group, an isocyanate group, and a blocked isocyanate group. However, the present invention is not limited to such examples. These reactive functional groups may be used alone or in combination.

  As a method for introducing a reactive functional group into a (meth) acrylic polymer, for example, an acrylic monomer having a desired reactive functional group may be added to other (meth) acrylic monomers and acrylics constituting emulsion particles as necessary. A method of introducing a reactive functional group into a (meth) acrylic polymer by polymerizing it with a monomer other than the system, and after preparing a (meth) acrylic polymer having an appropriate functional group in advance, the (meth) acrylic polymer Examples include a method of introducing a desired reactive functional group into a (meth) acrylic polymer by reacting a compound having a desired reactive functional group with the functional group of the present invention, but the present invention is limited to such an example. Is not to be done. Among the methods for introducing these reactive functional groups into the (meth) acrylic polymer, from the viewpoint of improving productivity, an acrylic monomer having a desired reactive functional group may be used to form emulsion particles as necessary. The method of introducing into a (meth) acrylic polymer by polymerizing together with the (meth) acrylic monomer and a monomer other than acrylic is preferred.

  Examples of the acrylic monomer having a reactive functional group include hydroxyl group-containing (meth) acrylate, carboxyl group-containing (meth) acrylate, glycidyl group-containing (meth) acrylate, vinyl group-containing (meth) acrylate, vinyl ether group-containing ( (Meth) acrylate, allyl ether group-containing (meth) acrylate, amino group-containing (meth) acrylate, benzophenone group-containing (meth) acrylate, monomer having an imide ring, oxazoline group-containing monomer, isocyanate group-containing (meth) acrylate, Although block isocyanate group containing (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These acrylic monomers having a reactive functional group may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, monoester of (meth) acrylic acid and polypropylene glycol, (meth) acrylic acid and polyethylene Although monoester with glycol etc. are mentioned, this invention is not limited only to this illustration. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of carboxyl group-containing (meth) acrylates include oxalic acid monohydroxyethyl (meth) acrylate and carboxyl group-terminated caprolactone-modified (meth) acrylate, but the present invention is not limited to such examples. Absent. These monomers may be used alone or in combination of two or more.

  Examples of the glycidyl group-containing (meth) acrylate include glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. These glycidyl group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of vinyl group-containing (meth) acrylates include allyl acrylate and allyl methacrylate, but the present invention is not limited to such examples. These vinyl group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the vinyl ether group-containing (meth) acrylate include (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, ( (Meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6- Vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid 2- (vinyloxyethoxy) ethyl, (meth) acrylic acid 2 -(Vinyloxyethoxyethoxyethoxy) ethyl etc. There may be mentioned, the present invention is not limited only to those exemplified. These vinyl ether group-containing (meth) acrylates may be used alone or in combination of two or more.

  As the allyl ether group-containing (meth) acrylate, for example, α-allyloxymethyl acrylic acid, α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate, α- Isopropyl allyloxymethyl acrylate, butyl α-allyloxymethyl acrylate, tert-butyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, α-allyloxy Dicyclopentadienyl methyl acrylate, isobornyl α-allyloxymethyl acrylate, adamantyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate tetra Examples include allyloxymethyl acrylate esters such as hydrofurfuryl, but the present invention is not limited to such examples. These allyl ether group-containing (meth) acrylates may be used alone or in combination of two or more. Among these allyl ether group-containing (meth) acrylates, from the viewpoint of improving scratch resistance and adhesion to a substrate, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyl Isopropyl oxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, isobornyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate and α-allyloxymethyl acrylic acid Tetrahydrofurfuryl is preferable, methyl α-allyloxymethyl acrylate and cyclohexyl α-allyloxymethyl acrylate are more preferable, and methyl α-allyloxymethyl acrylate is more preferable.

  Examples of amino group-containing (meth) acrylates include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylamino. Although propyl (meth) acrylate, those quaternized compounds, etc. are mentioned, this invention is not limited only to this illustration. These amino group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the benzophenone group-containing (meth) acrylate include 4- (meth) acryloyloxybenzophenone, 2- (meth) acryloyloxybenzophenone, 4- (meth) acryloyloxy-4′-nitrobenzophenone, and 4- (meth) acryloyl. Oxy-2′-nitrobenzophenone, 2- (meth) acryloyloxy-2′-nitrobenzophenone, 2- (meth) acryloyloxy-4-nitrobenzophenone, 4- (meth) acryloyloxy-2-nitrobenzophenone, 4- (Meth) acryloyloxy-4′-aminobenzophenone, 4- (meth) acryloyloxy-2′-aminobenzophenone, 2- (meth) acryloyloxy-2′-aminobenzophenone, 2- (meth) acryloyloxy-4- Ami Benzophenone, 4- (meth) acryloyloxy-2-aminobenzophenone, 4- (meth) acryloyloxy-4′-chlorobenzophenone, 4- (meth) acryloyloxy-2′-chlorobenzophenone, 2- (meth) acryloyloxy -2'-chlorobenzophenone, 2- (meth) acryloyloxy-4-chlorobenzophenone, 4- (meth) acryloyloxy-2-chlorobenzophenone, 4- (meth) acryloyloxy-4'-methylbenzophenone, 4- ( (Meth) acryloyloxy-2'-methylbenzophenone, 2- (meth) acryloyloxy-2'-methylbenzophenone, 2- (meth) acryloyloxy-4-methylbenzophenone, 4- (meth) acryloyloxy-2-methylbenzophenone 4- (meth) acryloyloxy-4′-methoxybenzophenone, 4- (meth) acryloyloxy-2′-methoxybenzophenone, 2- (meth) acryloyloxy-2′-methoxybenzophenone, 2- (meth) acryloyloxy- Examples include 4-methoxybenzophenone and 4- (meth) acryloyloxy-2-methoxybenzophenone, but the present invention is not limited to such examples. These benzophenone group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the imide ring group possessed by the monomer having an imide ring include, for example, formula (I):

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to form a ring. R ³ represents a direct bond or an alkylene group having 1 to 4 carbon atoms)
And a cyclic imide group represented by the formula: When R ¹ and R ² are bonded to form a ring, examples of the group bonded to R ¹ and R ² include an alkylene group having 2 to 4 carbon atoms. Among the alkylene groups, a propylene group and a butylene group are preferable from the viewpoint of the stability of the monomer having an imide ring. R ³ is a direct bond or an alkylene group having 1 to 4 carbon atoms, preferably a direct bond, an ethylene group or a propylene group.

  Examples of the polymerizable group of the monomer having an imide ring include ethylenically unsaturated groups such as vinyl group, allyl group, (meth) acryloyl group, and (meth) acryloyloxy group. It is not limited to an example only. Among these polymerizable groups, a (meth) acryloyl group and a (meth) acryloyloxy group are preferable, and a (meth) acryloyloxy group is more preferable.

  Among the monomers having an imide ring, from the viewpoint of obtaining an active energy ray-curable aqueous resin composition that forms a film excellent in dispersion stability, film-forming property and anti-curl property, and excellent in scratch resistance and water resistance. Monomers having a cyclic imide group represented by the formula (I) and a (meth) acryloyloxy group are preferred, and the formula (II):

(In the formula, R ³ is the same as above. R ⁴ represents a hydrogen atom or a methyl group.)
Is more preferable, and maleimide (meth) acrylate in which R ³ is an ethylene group and R ⁴ is a hydrogen atom or a methyl group in formula (II) is more preferable.

  Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Examples include oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline, but the present invention is not limited to such examples. These oxazoline group-containing monomers may be used alone or in combination of two or more. Among these oxazoline group-containing monomers, 2-isopropenyl-2-oxazoline is preferable because it can be easily obtained industrially.

  Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, and (meth) acryloyl isocyanate. However, the present invention is not limited to such examples. These isocyanate group-containing (meth) acrylates may be used alone or in combination of two or more.

  The blocked isocyanate group-containing (meth) acrylate can be obtained by blocking the isocyanate group-containing (meth) acrylate with a blocking agent. Examples of the blocking agent include alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, and benzyl alcohol; cresol, ethylphenol, butylphenol, Phenolic blocking agents such as nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoate; active methylene blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone; butyl mercaptan, Mercaptan blocking agents such as dodecyl mercaptan; acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-buty Acid amide blocking agents such as lactam; succinimide, maleic imide, imidazole as imidazole, acid imide blocking agents such as 2-methylimidazole; urea blocking agents such as urea, thiourea and ethylene urea Oxime blocking agents such as formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime and cyclohexanone oxime; amine blocking agents such as diphenylamine, aniline and carbazole; imine blocking agents such as ethyleneimine and polyethyleneimine Bisulphite-based blocking agents such as sodium bisulfite; pyridine-based blocking agents such as 2-hydroxypyridine and 2-hydroxyquinoline; unsubstituted pyrazole, 3,5-dimethylpyrazole, 3-acetyl Examples include pyrazole-based blocking agents such as ruaminopyrazole and pyrazole-3,5-dicarboxylic acid diethyl ester, but the present invention is not limited to such examples. These blocking agents may be used alone or in combination of two or more. Among these blocking agents, 3,5-dimethylpyrazole and methyl ethyl ketoxime are preferred because they are easily available and have excellent curability.

  When a (meth) acrylic polymer having a reactive functional group is used, a curable monomer and / or curable oligomer having a functional group capable of reacting with the reactive functional group of the (meth) acrylic polymer, ) By using a cross-linking agent having a functional group capable of reacting with the reactive functional group of the acrylic polymer, the scratch resistance of the formed film can be improved.

  The number of functional groups that one molecule of the (meth) acrylic polymer has is preferably 1 or more, more preferably 2 or more, from the viewpoint of improving the scratch resistance of the coating film to be formed.

  The in-line coating agent of the present invention includes a curable monomer and / or a curable oligomer. Thus, since the in-line coating agent of the present invention contains a curable monomer and / or curable oligomer, it improves the storage stability of the in-line coating agent and is excellent in anti-curl property, scratch resistance and water resistance. A film can be formed.

  Curable monomers and / or curable oligomers are curable such as (meth) acryloyl groups, vinyl groups, vinyl ether groups and other unsaturated double bond groups, cyclic ether groups, maleimide groups, isocyanate groups, and blocked isocyanate groups. A compound having a group. The blocked isocyanate group is obtained by blocking an isocyanate group with a blocking agent, and examples of the blocking agent include blocking agents used in the blocked isocyanate group-containing (meth) acrylate.

  Each of the curable monomer and the curable oligomer may have two or more curable groups of the same type, or may have two or more curable groups of different types.

  The curable monomer means a compound having a curable group and a molecular weight of less than 1000, and the curable oligomer means a compound having a curable group and a molecular weight of 1000 or more.

  Since the curable monomer and / or curable oligomer has the curable group, it is possible to form a film having excellent scratch resistance. The number of curable groups possessed by the curable monomer and / or curable oligomer is preferably from the viewpoint of improving the storage stability of the in-line coating agent and forming a film excellent in anti-curl property, scratch resistance and water resistance. Is 2 or more, more preferably 3 or more.

  Further, the molecular weight / functional group number of the curable monomer and / or curable oligomer is preferably 80 or more, more preferably 85 or more from the viewpoint of forming a film having excellent scratch resistance, and a film having excellent adhesion. Is preferably 160 or less, more preferably 150 or less, and still more preferably 140 or less. When two or more kinds of curable monomers and / or curable oligomers are used in combination, the molecular weight / number of functional groups of the curable monomer and / or curable oligomer is the mass of each curable monomer and / or curable oligomer. It is a value obtained by adding the product of the fraction and the number of functional groups.

  Examples of the curable monomer and / or curable oligomer having two or more different types of curable groups include 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1 -Curing monomer having an isocyanate group and acryloyl group such as methylethyl (meth) acrylate, methacryloyl isocyanate, etc., curing having a blocked isocyanate group and (meth) acryloyl group obtained by blocking the curable monomer with a blocking agent The present invention is not limited to only such examples. As a blocking agent, a blocking agent used in the blocked isocyanate group-containing (meth) acrylate, more specifically, an alcohol blocking agent, a phenol blocking agent, an active methylene blocking agent, a mercaptan block Agent, acid amide blocking agent, acid imide blocking agent, urea blocking agent, oxime blocking agent, amine blocking agent, imine blocking agent, bisulfite blocking agent, pyridine Examples thereof include a system blocking agent and a pyrazole blocking agent.

  Specific examples of the curable monomer and / or curable oligomer include xylylene bisoxetane, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, divinylbenzene, (meth) 2- (2-vinyloxyethoxy) ethyl acrylate, diethylene glycol monovinyl ether, N, N'-methylenebisacrylamide, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether , Ethoxylation (4 [indicating the number of ethoxy groups; the same applies hereinafter)] pentaerythritol tetraacrylate (molecular weight: 528) [for example, manufactured by Sartomer, product number: SR494, etc.], ethoxylated (4) penta Rithritol tetramethacrylate, dipentaerythritol hexaacrylate (molecular weight: 578) [for example, manufactured by Sartomer, product number: DPHA, etc.], dipentaerythritol hexamethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate (molecular weight: 330) [For example, manufactured by Sartomer, product number: SR209, etc.], trimethylolpropane triacrylate (molecular weight: 296) [for example, manufactured by Sartomer, product number: SR351], trimethylolpropane trimethacrylate (molecular weight: 338) [for example, Sartomer (Product number: SR350, etc.), dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol triacrylic And urethane (meth) acrylate having a molecular weight of 290 to 2000, a molecular weight / number of functional groups of 80 to 160, and having two or more (meth) acryloyl groups. Is not limited to such examples. These curable monomers and curable oligomers may be used alone or in combination of two or more. Among these curable monomers and curable oligomers, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa, from the viewpoint of forming a film excellent in curling prevention, storage stability, scratch resistance and water resistance. (Meth) acrylate and tetraethylene glycol di (meth) acrylate are preferred.

  From the viewpoint of improving the scratch resistance, the content of the curable monomer and / or curable oligomer in the active ingredient of the in-line coating agent is preferably 40% by mass or more, more preferably 50% by mass or more, and anti-curl property. From the viewpoint of forming a film excellent in storage stability and water resistance, it is preferably 90% by mass or less, more preferably 80% by mass or less. Further, the content of the (meth) acrylic polymer in the active ingredient of the inline coating agent is preferably 10% by mass or more, more preferably from the viewpoint of forming a film excellent in curl prevention, storage stability and water resistance. From the viewpoint of improving the scratch resistance, it is preferably 60% by mass or less, and more preferably 50% by mass or less.

  The nonvolatile content in the resin emulsion is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 65% by mass or less, more preferably from the viewpoint of improving handleability. Is 60% by mass or less.

In the present invention, the non-volatile content in the resin emulsion is determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content in resin emulsion (% by mass)]
= ([Residue mass] / [resin emulsion 1 g]) × 100
Means the value obtained based on

  The in-line coating agent of the present invention may contain an appropriate amount of a crosslinking agent from the viewpoint of improving the scratch resistance. When the in-line coating agent of the present invention contains a crosslinking agent, the scratch resistance of the film formed with the in-line coating agent of the present invention is improved not only at room temperature but also at high temperatures. Can be made.

  Examples of the crosslinking agent include melamine crosslinking agent, oxazoline crosslinking agent, acrylamide crosslinking agent, polyamide crosslinking agent, epoxy crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, titanate crosslinking agent, urea crosslinking. An agent, an alkyl alcoholated urea-based cross-linking agent, and the like can be mentioned, but the present invention is not limited to such examples. These crosslinking agents may be used alone or in combination.

  Among the cross-linking agents, melamine-based cross-linking agents and oxazoline-based cross-linking agents are preferable from the viewpoint of improving the adhesion of a film formed with the in-line coating agent of the present invention to a resin film.

  Examples of the oxazoline-based crosslinking agent include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2-oxazolin-2-yl). ) Butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene 1,3-bis (2-oxazolin-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2 -Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. It is not limited only to hunt illustration. These oxazoline-based crosslinking agents may be used alone or in combination.

  The in-line coating agent of the present invention may contain an appropriate amount of a polymerization initiator from the viewpoint of improving the reaction rate, if necessary. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination.

  Examples of the thermal polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4′- Oil-soluble initiators such as dimethylvaleronitrile), benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxy-2-ethylhexanoate, Persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; water-soluble peroxides such as hydrogen peroxide; water-soluble azo compounds such as 2,2′-azobis (2-amidinopropane) dihydrochloride; heat Although a latent catalyst etc. are mentioned, this invention is not limited only to this illustration. These thermal polymerization initiators may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include benzophenone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oxyphenyl-acetic acid 2- [2-oxo-2-phenylacetoxyethoxy] -Ethyl ester, oxyphenylacetic acid 2- [2-hydroxyethoxy] -ethyl ester, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1- (4-isopropylpheny ) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-morpholinopropan-1-one, (4-Methylphenyl [4- (2-methylpropyl) phenyl])-hexafluorophosphate, diethylthioxanthone, isopropylthioxanthone, and the like can be mentioned, but the present invention is not limited to such examples. These photopolymerization initiators may be used alone or in combination of two or more.

  In addition, the in-line coating agent of the present invention may contain an appropriate amount of pigment, if necessary. Examples of the pigment include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more.

  In addition, the in-line coating agent of the present invention includes other water-soluble polymers other than the (meth) acrylic polymer used in the resin emulsion, water-dispersible polymers, and the like within the range in which the object of the present invention is not hindered. System polymers may be included.

  In addition, the in-line coating agent of the present invention includes, for example, an ultraviolet absorber, an ultraviolet inhibitor, a filler, a leveling agent, a surface conditioner, a dispersant, a thickener, and a wet within a range that does not hinder the object of the present invention. Additives such as additives, plasticizers, stabilizers, dyes, antioxidants, and inorganic particles may be contained in appropriate amounts.

  In the in-line coating agent of the present invention, an organic solvent may be contained in an appropriate amount from the viewpoint of improving the affinity between the emulsion particles and the polyfunctional (meth) acrylic acid ester.

  The amount of the active ingredient in the in-line coating agent of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 65% by mass from the viewpoint of improving handleability. Hereinafter, it is 60 mass% or less more preferably. The amount of the active ingredient in the in-line coating agent of the present invention can be easily adjusted, for example, by adjusting the amount of a solvent such as water and the amount of an additive.

  The in-line coating agent of the present invention can be easily prepared by mixing the above-described components.

  In the present invention, a curable monomer and / or a curable oligomer may be introduced into the emulsion particles. Examples of a method for introducing a curable monomer and / or a curable oligomer into emulsion particles include, for example, Journal of Dispersion Science & Technology, Vol. 5, 231 (1984). The method of mixing emulsion particles with curable monomers and / or curable oligomers by the method described in 1992), Macromolecule Chemistry, 180, 737 (1979). The curable monomer and / or curable oligomer is introduced into the emulsion particles by the two-stage swelling method, the molecular diffusion method, the dynamic swelling method, the diffusion swelling method, etc. Although a method of sex monomer and / or curable oligomer is introduced into the emulsion particles, and the like, the present invention is not limited only to those exemplified.

  Specific methods for introducing the curable monomer and / or curable oligomer into the emulsion particles include a method of adding the emulsion particles to an aqueous dispersion of the curable monomer and / or curable oligomer and mixing them. . Examples of the method of adding emulsion particles to the aqueous dispersion include a batch addition method, a continuous addition method, an intermittent addition method, or a combination of these methods. However, the present invention is limited only to such examples. is not.

  When a curable monomer and / or curable oligomer having low solubility in water is introduced into the emulsion particles, or 50% by mass or more of the curable monomer and / or curable oligomer is added to the emulsion particles based on the nonvolatile content of the emulsion particles. In the case of introducing into the inside, the curable monomer and / or curable oligomer is previously dispersed in water with a dispersant such as an emulsifier, and the obtained aqueous dispersion is dispersed with a homogenizer, for example, with a particle size of 0.01 to 1 μm. After being finely dispersed to a degree, this can be added to the resin emulsion. In this case, for example, a high-pressure homogenizer can be used as the homogenizer.

  In order to efficiently introduce the curable monomer and / or curable oligomer into the emulsion particles, an absorption accelerator can be used. The absorption accelerator may be previously contained in the resin emulsion, or may be used in combination with a curable monomer and / or a curable oligomer. The amount of the absorption accelerator is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, per 100 parts by mass of the nonvolatile content of the resin emulsion. The absorption promoter is not particularly limited as long as it exhibits an absorption promotion effect. For example, a general organic solvent such as toluene and ethyl acetate, 2,2,2-trimethyl-1,3-pentanediol A film forming aid such as monoisobutyrate can be used. When a volatile compound is used as the absorption accelerator, after preparing the in-line coating agent, the volatile compound can be removed by a degassing step or the like, if necessary.

  The in-line coating agent of the present invention obtained as described above is excellent in storage stability and forms a film excellent in anti-curl property, scratch resistance and water resistance. Therefore, a resin film having a film by an in-line coating method is formed. It can be suitably used when manufacturing.

  As a method for producing a resin film having a film by an inline coating method, for example, a resin film obtained by a melt extrusion method is uniaxially stretched in the longitudinal direction, and the inline coating agent of the present invention is applied to the uniaxially stretched resin film. Then, after drying the formed film, the resin film on which the film is formed is stretched in the width direction, and the stretched resin film is heated to fix the molecular orientation of the resin constituting the resin film. However, the present invention is not limited to such examples.

  Examples of the resin used in the resin film include polymethyl (meth) acrylate, acrylic polymers such as (meth) acrylic polymers having a ring structure in the main chain; polyesters such as polyethylene terephthalate and polybutylene terephthalate; norbornene polymers, etc. Cyclic olefin polymers: Cellulose polymers such as cellulose triacetate, cellulose acetate propionate and cellulose acetate butyrate; Polyolefin polymers such as polyethylene and polypropylene; Polycarbonate; Polystyrene; Vinyl chloride polymers; ABS resin; AS resin; However, the present invention is not limited to such examples.

  When applying the in-line coating agent of the present invention to a resin film, from the viewpoint of improving the adhesion between the film formed from the in-line coating agent and the resin film, the resin film may be subjected to corona discharge treatment in advance. Well, an adhesion improver may be used.

  Next, the resin film is stretched. The stretching of the resin film may be uniaxial stretching or biaxial stretching. Uniaxial stretching may be longitudinal stretching (stretching in the winding direction of the resin film) or transverse stretching (stretching in the width direction of the resin film). In the case of longitudinal stretching, it may be free end uniaxial stretching in which the change in the width direction of the resin film is free, or may be fixed end uniaxial stretching in which the change in the width direction of the resin film is fixed. Biaxial stretching may be sequential biaxial stretching in which transverse stretching is performed after longitudinal stretching, or simultaneous biaxial stretching in which longitudinal and transverse stretching are simultaneously performed. Moreover, you may perform the extending | stretching of the diagonal direction with respect to the extending | stretching of the thickness direction of a resin film, or the roll of a resin film. A stretching method, a stretching temperature, and a stretching ratio can be appropriately selected according to the optical characteristics, mechanical strength, and the like of the target resin film.

  The stretch ratio of the resin film is preferably 1.5 times or more, more preferably 2 times or more from the viewpoint of forming a film excellent in storage stability, anti-curl property, scratch resistance and water resistance, From the viewpoint of forming a film excellent in storage stability, anti-curl property, scratch resistance and water resistance, it is preferably 5 times or less, more preferably 4 times or less. In addition, when extending | stretching a resin film, you may heat suitably as needed.

  As a method for applying the in-line coating agent of the present invention to a resin film, for example, spray, roller, brush, iron or the like is used, or roll coating, bar coating, die coating, comma coating, gravure coating, kiss coating, spin coating, dip. Examples include coat, curtain coat, doctor blade coat, knife coat, air knife coat, reverse coat, rod coat, Meyer bar coat, micro gravure coat, offset gravure coat, and lip coat. It is not limited to.

  The stretch ratio of the resin film is preferably 1.5 times or more, more preferably 2 times or more from the viewpoint of forming a film excellent in storage stability, anti-curl property, scratch resistance and water resistance, From the viewpoint of forming a film excellent in storage stability, anti-curl property, scratch resistance and water resistance, it is preferably 5 times or less, more preferably 4 times or less. In addition, when extending | stretching a resin film, you may heat suitably as needed.

  From the viewpoint of increasing the strength of the coating, the thickness of the coating composed of the in-line coating agent after stretching the resin film having the coating formed as described above is preferably 0.001 μm or more, more preferably 0. From the viewpoint of reducing the film thickness, it is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 2 μm or less.

  Examples of the method of curing the coating include a method of curing with heat and ultraviolet rays, but the present invention is not limited to such examples. These curing methods are preferably appropriately selected according to the type of polymerization initiator used for the coating.

  As described above, the resin film on which the coating film is formed is made of an in-line coating agent on the resin film, and the coating film excellent in anti-curl, scratch resistance and water resistance is formed. It is expected to be used for films used for optical materials such as, displays, mechanical parts, electrical parts, electronic parts, building materials, automotive parts and the like.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example.

Preparation Example 1
In accordance with the description in JP-A-10-226669, 1,4-diazabicyclo [2.2.2] octane is used as a catalyst, and methyl α-hydroxymethyl acrylate and allyl alcohol are reacted to form α-allyl. Methyl oxymethyl acrylate was prepared.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water (parts by mass, the same applies hereinafter) was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution (mass%, the same shall apply hereinafter), 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of acrylic acid, of which the total amount of all monomer components 85 parts corresponding to 6% by mass of was added to the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined based on the following methods. As a result, the glass transition temperature of the polymer was 96 ° C., and the weight average molecular weight was 950,000.

〔Glass-transition temperature〕
The glass transition temperature (Tg) of the polymer was determined in accordance with the provisions of JIS K7121. More specifically, a differential scanning calorimeter [manufactured by Rigaku Corporation, product number: DSC-8230] was used, and about 10 mg of a sample was heated from room temperature to 200 ° C. at a heating rate of 20 ° C./min in a nitrogen gas atmosphere. And calculated from the obtained DSC curve by the starting point method. For reference, α-alumina was used.

(Weight average molecular weight)
The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) under the following conditions.
-System: manufactured by Tosoh Corporation, trade name: GPC system HLC-8220
・ Developing solvent: Chloroform (made by Wako Pure Chemical Industries, Ltd., special grade), flow rate: 0.6 mL / min ・ Standard sample: TSK standard polystyrene [made by Tosoh Corporation, trade name: PS-oligomer kit]
-Column configuration on the measurement side: guard column [manufactured by Tosoh Corporation, trade name: TSKguardcolumn SuperHZ-L], separation column [manufactured by Tosoh Corporation, trade name: TSKgel SuperHZM-M] in series connection-Reference-side column construction : Reference column [trade name: TSKgel SuperH-RC, manufactured by Tosoh Corporation]
-Column temperature: 40 ° C
・ Detector: Differential refractometer

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. By adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), an in-line coating agent was obtained.

Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of acrylic acid, of which 85 parts correspond to 6% by mass of the total amount of all monomer components. Was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 96 ° C., and the weight average molecular weight was 950,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. An in-line coating agent was obtained by adding 2500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA).

Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of acrylic acid, of which 85 parts correspond to 6% by mass of the total amount of all monomer components. Was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 96 ° C., and the weight average molecular weight was 950,000.

  Next, 500 parts of tetraethylene glycol dimethacrylate (product number: SR209, manufactured by Sartomer) and trimethylolpropane as a curable monomer or curable oligomer with respect to 1000 parts of the nonvolatile content contained in the polymer dispersion obtained above. An in-line coating agent was obtained by adding 500 parts of trimethacrylate (manufactured by Sartomer, product number: SR350).

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dripping consisting of 120 parts of a 25% aqueous solution, 200 parts of cyclohexyl methacrylate, 100 parts of styrene, 680 parts of methyl α-allyloxymethyl acrylate obtained in Preparation Example 1 and 20 parts of acrylic acid, 85 parts corresponding to 6% by mass of the total amount of monomer components were added to the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 70 ° C., and the weight average molecular weight was 630,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. By adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), an in-line coating agent was obtained.

Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate was prepared, of which 6% by mass of the total amount of all monomer components The corresponding 85 parts were added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 95 ° C., and the weight average molecular weight was 1,000,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. Add 500 parts of hexaacrylate (Sartomer, product number: DPHA), and further add isocyanate [Asahi Kasei Chemicals Co., Ltd., trade name: Duranate WB40-100] as a curing agent to the hydroxyl value calculated from the composition of the resin emulsion. The in-line coating agent was obtained by adding so that it might become 2.0 equivalent.

Example 6
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dripping consisting of 120 parts of a 25% aqueous solution of styrene, 680 parts of styrene, 300 parts of 2- (2-vinyloxyethoxy) ethyl acrylate and 20 parts of acrylic acid was prepared. 85 parts corresponding to mass% was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 100 ° C., and the weight average molecular weight was 870,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. By adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), an in-line coating agent was obtained.

Example 7
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 50 parts of styrene, 50 parts of maleimide acrylate and 20 parts of acrylic acid, of which 6 is the total amount of all monomer components. 85 parts corresponding to mass% was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 96 ° C., and the weight average molecular weight was 680,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. By adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), an in-line coating agent was obtained.

Example 8
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dripping comprising 120 parts of a 25% aqueous solution, 200 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 50 parts of styrene, 20 parts of acrylic acid and 50 parts of 2-[(3,5-dimethylpyrazole) carboxyamino] ethyl methacrylate. Of which 85 parts corresponding to 6% by mass of the total amount of all monomer components were added to the flask. Thereafter, the temperature was raised to 60 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to the flask to initiate the polymerization reaction. After the completion, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask uniformly over 300 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 60 ° C. for 180 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 98 ° C., and the weight average molecular weight was 780,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. By adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), an in-line coating agent was obtained.

Example 9
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate was prepared, of which 6% by mass of the total amount of all monomer components The corresponding 85 parts were added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 95 ° C., and the weight average molecular weight was 1,000,000.

  Next, 500 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and dipentaerythritol as a curable monomer or curable oligomer with respect to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above. Hydroxyl value calculated by adding 500 parts of hexaacrylate (manufactured by Sartomer, product number: DPHA), and further using blocked isocyanate [manufactured by Mitsui Chemicals, Inc., trade name: Takenate WB-3021] as a curing agent from the composition of the resin emulsion. In-line coating agent was obtained by adding so that it might become 2.0 equivalent with respect to this.

Example 10
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate was prepared, of which 6% by mass of the total amount of all monomer components The corresponding 85 parts were added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 95 ° C., and the weight average molecular weight was 1,000,000.

  Next, 2-[(3,5-dimethylpyrazoyl) carbonylamino] ethyl methacrylate [Showa Denko] as a curable monomer or curable oligomer with respect to 1000 parts of the nonvolatile content contained in the polymer dispersion obtained above. (Trade name: Karenz MOI-BP) 250 parts, dipentaerythritol hexaacrylate (Sartomer, product number: DPHA) 500 parts and trimethylolpropane triacrylate (Sartomer, product number: SR351) 250 parts By adding, an in-line coating agent was obtained.

Comparative Example 1
By adding 1000 parts of trimethylolpropane triacrylate (product number: SR351, manufactured by Sartomer) and 1000 parts of dipentaerythritol hexaacrylate (product number: DPHA) as a curable monomer or curable oligomer, an in-line coating agent Got.

Comparative Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In addition, 290 parts of deionized water in a dropping funnel, an anionic surfactant as an emulsifier [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] A pre-emulsion for dropping consisting of 120 parts of a 25% aqueous solution, 680 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of styrene and 20 parts of acrylic acid, of which 85 parts correspond to 6% by mass of the total amount of all monomer components. Was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added into the flask to initiate the polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. The obtained reaction liquid was cooled to room temperature to obtain a polymer dispersion having a nonvolatile content of 40%. The glass transition temperature and the weight average molecular weight of the polymer contained in the obtained polymer dispersion were examined in the same manner as in Example 1. As a result, the glass transition temperature of the polymer was 96 ° C., and the weight average molecular weight was 950,000. The polymer dispersion obtained above was used as an in-line coating agent.

  Next, the physical properties of the in-line coating agent obtained in each example or each comparative example were examined based on the following method. The results are shown in Table 1.

1. Transparency In a reaction kettle equipped with a stirrer, thermometer, cooler and nitrogen gas inlet tube, 40 parts of methyl methacrylate, 10 parts of methyl 2- (hydroxymethyl) acrylate, 50 parts of toluene and an antioxidant [Corporation] ADEKA, trade name: ADK STAB 2112] was charged with 0.025 part, and the temperature was raised to 105 ° C. while passing nitrogen gas, and when refluxed, tert-amyl peroxyisononanoate [ATOFINA Yoshitomi Corp. ), Trade name: Lupazole 570] While adding 0.05 parts, 0.10 parts of tert-amyl peroxyisononanoate was added dropwise over 2 hours while refluxing (temperature: about 105 to 110 ° C.). Polymerization was carried out with, and further aging was performed for 4 hours to obtain a polymer solution.

  To the polymer solution obtained above, 0.05 part of stearyl phosphate [manufactured by Sakai Chemical Industry Co., Ltd., trade name: Phoslex A-18] was added and refluxed (temperature: about 90 to 110 ° C.). The cyclization condensation reaction was allowed to proceed for 2 hours.

  Next, after passing the polymer solution obtained by the cyclization condensation reaction through a multi-tubular heat exchanger heated to 240 ° C., the cyclization condensation reaction of the polymer solution is completed, This polymer solution was treated at a barrel temperature of 240 ° C., a rotation speed of 120 rpm, a degree of vacuum of 13.3 to 400 hPa, a rear vent number of 1, a fore vent number of 4 (first vent, second vent, third vent, fourth Introduced into a vent type screw twin screw extruder (L / D = 52), which is called a vent and has a side feeder between the third vent and the fourth vent) at a processing rate of 20 parts / hour in terms of resin amount. As a result, devolatilization was performed. At that time, antioxidant (BASF, trade name: Irganox 1010) 50 parts, antioxidant (made by ADEKA, trade name: ADK STAB AO-412s) 50 parts, zinc octylate [NIPPON CHEMICAL CO., LTD. Sangyo Co., Ltd., trade name: Nikka octix zinc, active ingredient content: 3.6%] A solution obtained by dissolving 40 parts in 160 parts of toluene was placed in a high-pressure pump after the second vent. And injected into the vent type screw twin screw extruder at a charging rate of 0.3 part / hour. Further, after the first vent and after the side feeder, ion exchange water was injected into the vent type screw twin screw extruder at a charging rate of 0.33 parts / hour using a high pressure pump. Further, AS resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Stylac AS783L] was added from the side feeder into the vent type screw twin screw extruder at a supply rate of 2.12 parts / hour.

  The melt-kneaded product extruded from the vent type screw twin screw extruder was filtered with a leaf disk type polymer filter (manufactured by Nagase Sangyo Co., Ltd., filtration accuracy: 5 μm). The filtered melt-kneaded product was devolatilized to obtain pellets of a thermoplastic acrylic resin composition. When the weight average molecular weight and glass transition temperature of the thermoplastic acrylic resin contained in the pellets obtained above were measured based on the following method, the glass transition temperature was 125 ° C., and the weight average molecular weight was 132,000. there were.

〔Glass-transition temperature〕
The glass transition temperature (Tg) of the thermoplastic acrylic resin was determined in accordance with JIS K7121 regulations. More specifically, a differential scanning calorimeter [manufactured by Rigaku Corporation, product number: DSC-8230] was used, and about 10 mg of a sample was heated from room temperature to 200 ° C. at a heating rate of 20 ° C./min in a nitrogen gas atmosphere. And calculated from the obtained DSC curve by the starting point method. For reference, α-alumina was used.

(Weight average molecular weight)
The weight average molecular weight of the thermoplastic acrylic resin was determined by gel permeation chromatography (GPC) under the following conditions.
-System: manufactured by Tosoh Corporation, trade name: GPC system HLC-8220
・ Developing solvent: Chloroform (made by Wako Pure Chemical Industries, Ltd., special grade), flow rate: 0.6 mL / min ・ Standard sample: TSK standard polystyrene [made by Tosoh Corporation, trade name: PS-oligomer kit]
-Column configuration on the measurement side: guard column [manufactured by Tosoh Corporation, trade name: TSKguardcolumn SuperHZ-L], separation column [manufactured by Tosoh Corporation, trade name: TSKgel SuperHZM-M] in series connection-Reference-side column construction : Reference column [trade name: TSKgel SuperH-RC, manufactured by Tosoh Corporation]
-Column temperature: 40 ° C
・ Detector: Differential refractometer

  The pellet obtained above was melt-extruded from a T-die at 280 ° C. using a single-screw extruder equipped with a leaf disk type polymer filter (manufactured by Nagase Sangyo Co., Ltd., filtration accuracy: 5 μm). By discharging onto a cooling roll, an unstretched resin film having a thickness of about 200 μm was obtained.

  After stretching the unstretched resin film obtained in the above to 15 cm in length and 15 cm in width in the longitudinal direction at 140 ° C. by 2.0 times, each example or so that the film thickness after drying becomes 10 μm The in-line coating agent obtained in each comparative example was applied with a bar coater to form a film.

  Next, the uniaxially stretched resin film on which the coating film obtained above was formed was stretched 2.0 times in the transverse direction at 140 ° C. Obtained.

  The appearance of the biaxially stretched resin film obtained above was compared with the appearance of the uniaxially stretched resin film on which the film was formed, and evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: Even if the film is observed visually or with a magnifier of 50 times, the film is not turbid and cracks are not observed, and no change is observed in the appearance of the film compared to before stretching.
15: When visually observed, no change is observed in the film, but when the film is observed with a 50-fold magnifier, some cracks are observed in the film.
10: When the film is visually observed, no change is observed in the film, but when the film is observed with a 50 times magnifier, many cracks are observed in the film.
5: When the film is visually observed, turbidity is observed in the film, but no crack is observed in the film.
0: When the film is visually observed, turbidity is observed in the film, and cracks are further observed in the film.

2. Anti-curling Polyethylene terephthalate (hereinafter referred to as PET) film [manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine (registered trademark) A4300, thickness: 100 μm] Each implementation was carried out so that the film thickness after drying was 10 μm. The in-line coating agent obtained in the example or each comparative example was applied with a bar coater, and heated at 200 ° C. for 10 minutes to form a cured film.

In addition, about the case where the in-line coating agent obtained in Example 7 was used, the film was hardened | cured by further irradiating an ultraviolet-ray with the integrated light quantity of 1000 mJ / cm < ² > with an ultraviolet irradiation lamp.

  The laminate of the cured film and PET film obtained above was cut into a size of 50 mm in length and 50 mm in width, and the obtained test piece was left on a horizontal table having a smooth plane, and then the surface of the horizontal table 4 points to the four corners of the test piece were measured, an average value was obtained from these values, and the anti-curl property was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: Average value of 0 mm or more and less than 15 mm 15: Average value of 15 mm or more and less than 20 mm 10: Average value of 25 mm or more and less than 30 mm 5: Average value of 30 mm or more and less than 35 mm 0: No coating film is formed or the average value is 35 mm or more Or the height cannot be measured due to curling.

3. Storage stability The in-line coating agent was allowed to stand in an atmosphere of 50 ° C., the time-dependent change in the appearance of the in-line coating agent was visually observed, and the storage stability was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
No change such as sedimentation is observed even after 20: 1 months.
15: No change such as the occurrence of sediment is observed after 3 weeks or more, but the change such as the occurrence of sediment is observed after one month.
10: No change such as the occurrence of sediment is observed even after 2 weeks or more, but the change such as the occurrence of sediment is observed after 3 weeks.
5: No change such as sedimentation is observed after 10 days or more, but a change such as sedimentation is observed after 2 weeks.
0: It is recognized that sediment is clearly generated when 10 days have passed.

4). Scratch resistance A laminate of the cured film obtained by the “2. Anti-curl property” and the PET film was used. A test piece was prepared by cutting the laminate into an appropriate size. Test piece by applying a load of 150 g / cm ^{2 to} steel wool [manufactured by Nippon Steel Wool Co., Ltd., count: # 0000] using a dyeing fastness tester [manufactured by Suga Test Instruments Co., Ltd., product number: FR-II]. The coating surface was rubbed 20 times, and the number of scratches generated on the coating surface of the test piece was counted and evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: No scratch 15: Number of scratches 1 to 5 10: Number of scratches 6 to 10 5: Number of scratches 11 to 15 0: Number of scratches 16 or more

5. Water-resistant PET film [trade name: Cosmo Shine (registered trademark) A4300, thickness: 100 μm, manufactured by Toyobo Co., Ltd.], in-line so that the thickness of the coating after drying with a bar coater (No. 11) is 10 μm A coating was formed by applying a coating agent. The formed film was heated at a temperature of 200 ° C. for 10 minutes to form a cured film.

In addition, about the case where the in-line coating agent obtained in Example 7 was used, a laminated body was obtained by hardening a film by further irradiating an ultraviolet-ray with an ultraviolet irradiation lamp with the integrated light quantity of 1000 mJ / cm < ² >. It was.

The laminate obtained above was cut into a size of 50 mm in length and 50 mm in width to prepare a sample, the sample was immersed in deionized water at 25 ° C., and after 1 week, the PET film was taken out from the water, Measure the mass of the sample and formula:
[Water absorption (mass%)]
= {[Mass of sample after immersion-Mass of sample before immersion]
÷ [mass of sample before immersion]} × 100
The water absorption was determined based on the above, and the water resistance was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: Water absorption is less than 0.5% by mass 15: Water absorption is less than 0.5% by mass and less than 10% 10: Water absorption is 1% by mass to less than 3% by mass 5: Water absorption is 3% by mass to less than 5% by mass 0: No coating film is formed or water absorption is 5% by mass or more

6). Comprehensive evaluation Comprehensive evaluation was performed by summing up the scores of the respective physical properties. In addition, the highest score of comprehensive evaluation is 100 points, and the lowest score is 0 points.

  From the results shown in Table 1, the in-line coating agent obtained in each example was compared with the in-line coating agent obtained in each comparative example, as compared with the anti-curl property, storage stability, scratch resistance and water resistance. It can be seen that an excellent film is formed.

Claims (1)

  A coating agent used in in-line coating, which is a resin emulsion containing emulsion particles made of a (meth) acrylic polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer, a curable monomer, and / or Alternatively, an in-line coating agent comprising a curable oligomer.