JP2009013337A - Water dispersion type composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water dispersion type composition imparting an ultraviolet ray absorbing layer exhibiting an excellent weatherability even in a thin film, with stabilized oil particles in emulsion polymerization of the producing process, and to provide a method for producing the same. <P>SOLUTION: The invention relates to the water dispersion type composition used for forming the ultraviolet ray absorbing layer consisting of an ultraviolet ray absorbing polymer obtained by carrying out an emulsion polymerization of a 30-85 pts.mass of an ultraviolet ray absorbing monomer (I) which is in a solid state at 25°C, 70-15 pts.mass of a monomer (II) copolymerizable with the prescribed monomer (I), and 20-50 pts.mass of a polymerizable nonionic surfactant based on the 100 pts.mass of the sum of the prescribed monomer (I) and monomer (II), in a water containing medium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a water-dispersed composition used as a material for forming an ultraviolet-absorbing layer for imparting weather resistance to a molded product such as a film, a plate, and a fiber, and a functional film coated on the surface of the molded product, And a manufacturing method thereof.

  Various resin molded bodies have been used for various purposes in the past, but resin molded bodies are generally sensitive to ultraviolet rays, so that they can absorb ultraviolet rays for the purpose of improving weather resistance (ultraviolet absorption layer). ) Is provided on the surface of the molded body.

  The ultraviolet absorbing layer is known, for example, to be formed by coating a molded body with an ultraviolet absorbing polymer solution obtained by solution polymerization of a raw material monomer mixture containing an ultraviolet absorbing monomer (patent) Literature 1 etc.).

  Moreover, as a well-known coating liquid for obtaining an ultraviolet absorption layer, for example, as disclosed in Patent Documents 2 to 5, a water-dispersed (emulsion type) ultraviolet-absorbing polymer composition in consideration of the influence on the environment. There is. A water-dispersed composition can be obtained by emulsion polymerization of an ultraviolet-absorbing monomer together with other monomers. The present inventor has a high proportion of ultraviolet-absorbing monomer (for example, 30 mass) in order to increase the ultraviolet-absorbing property of the ultraviolet-absorbing layer. %), There was a problem that emulsion polymerization stability was lowered and a large number of aggregates were formed. The cause of this problem is that UV-absorbing monomers, which are mostly solid (powder) at room temperature, are not compatible with other polymerization partner monomers unless heated, and proceed in the aqueous phase where oil droplets are present. In the emulsion polymerization, stable oil droplets cannot be formed. In the case of solution polymerization, such a problem did not occur because the UV-absorbing monomer could be dissolved in the polymerization solvent.

While having the above problems, the present applicant has obtained a water-based UV-absorbing resin composition by utilizing a method of producing an UV-absorbing polymer without using an emulsifier in an aqueous medium, An application (Patent Document 6) relating to the composition has already been filed. Even in the method disclosed in Patent Document 6, the polymerization stability is insufficient when a large amount of ultraviolet absorbing monomer is used.
JP 2000-177070 A Japanese Patent No. 3580832 JP 2000-313705 A JP 2002-212237 A JP 2004-160734 A JP 2004-217695 A

  As described above, in the emulsion polymerization using a large amount of the UV-absorbing monomer, the oil droplets are not stable, which has led to low stability of polymerization, which is an industrial problem. On the other hand, in order to realize an ultraviolet absorbing layer having sufficient weather resistance with a thin film, it is desired to use a large amount of an ultraviolet absorbing monomer in the production of an ultraviolet absorbing polymer.

  In view of the above circumstances, the present invention provides a water-dispersed composition that can form an ultraviolet absorbing layer that exhibits excellent weather resistance even in a thin film, and in which oil droplets are stable in emulsion polymerization in the production process, and a method for producing the same. For the purpose of provision.

  The water-dispersed composition according to the present invention is a composition that has water and is used for forming an ultraviolet absorbing layer, and is 30 to 85 parts by mass of a UV-absorbing monomer (I) that is solid at 25 ° C. Polymerization of 70 to 15 parts by mass of monomer (II) copolymerizable with the monomer (I) and having no crosslinkability, and a mass ratio of 20 to 50 with respect to the total amount of the monomer (I) and the monomer (II) of 100 And a UV-absorbing polymer obtained by emulsion polymerization of a nonionic surfactant in a water-containing medium.

  The water-containing medium may contain an ultraviolet stabilizer. In this case, yellowing of the ultraviolet absorbing layer is suppressed. A part of the non-polymerizable UV stabilizer and / or the monomer (II) may be the UV stabilizer. When a non-polymerizable ultraviolet stabilizer is selected as the ultraviolet stabilizer, the mixing stability of the cationic compound and the aqueous dispersion composition according to the present invention is improved.

  The average particle size of the UV-absorbing polymer is preferably 30 to 80 nm from the viewpoint of preventing defects in the UV-absorbing layer and ensuring practical water resistance.

  The monomer (I) preferably contains a benzotriazole-based UV-absorbing monomer. This is because the ultraviolet absorbing layer exhibits excellent weather resistance over a long period of time.

  It is preferable that the non-polymerizable surfactant is not contained in the water-containing medium. This is because depending on the content of such a compound, the stability of oil droplets in emulsion polymerization may be affected.

  By forming the ultraviolet absorbing layer using the aqueous dispersion composition according to the present invention, an ultraviolet absorbing layer laminate can be produced.

  The production method according to the present invention comprises 30 to 85 parts by mass of a solid UV-absorbing monomer (I) at 25 ° C., and a monomer (II) 70 to be copolymerizable with the monomer (I) and having no crosslinkability. 15 parts by mass, a polymerizable nonionic surfactant having a mass ratio of 20 to 50 to the total amount 100 of the monomer (I) and the monomer (II), and a water-containing medium are mixed, and the monomer (I) is mixed by heating. A polymerization initiator is added after dissolving in the monomer (II). According to this method, stable oil droplets can be formed in the process of producing an ultraviolet absorbing polymer, which is one composition of the aqueous dispersion composition according to the present invention, by emulsion polymerization.

  The ultraviolet absorbing layer formed from the water-dispersed composition according to the present invention is manufactured using a large amount of the monomer (I), and thus exhibits excellent weather resistance even in a thin film. In addition, since the water-dispersed composition according to the present invention contains a predetermined amount of a polymerizable nonionic surfactant in emulsion polymerization for production thereof, oil droplets in the emulsion are stabilized and the amount of aggregates generated is increased. It is suppressed. This suppression reduces the work of removing aggregates from the polymerization facility and reduces the loss of the UV-absorbing polymer.

  The water-containing medium and the UV-absorbing polymer dispersed in the medium are essential components of the water-dispersed composition according to the present invention. This composition is excellent in coatability, and the ultraviolet absorbing layer formed by applying the composition is not only excellent in weather resistance but also excellent in stain resistance.

  The ultraviolet-absorbing polymer that is a constituent of the aqueous dispersion composition includes an ultraviolet-absorbing monomer (I), a monomer (II) copolymerizable with the monomer (I) and having no crosslinkability, and a polymerizable nonionic type It is obtained by emulsion polymerization with a surfactant in a water-containing medium. In this emulsion polymerization, a compounding agent may be added to the water-containing medium.

(Monomer (I))
Monomer (I) is a UV-absorbing monomer that is solid at 25 ° C. When a liquid UV-absorbing monomer liquid at 25 ° C. is used as a raw material, oil droplets are stabilized in emulsion polymerization, so that the monomer can be used in a large amount as a UV-absorbing polymer raw material. On the other hand, when the monomer (I) that is solid at 25 ° C. is used as a raw material, oil droplets are generally not stable, but a large amount of the monomer (I) is used in combination with a polymerizable nonionic surfactant. Can be used. In addition, as long as the oil droplet in emulsion polymerization is stabilized, you may use an ultraviolet absorptive monomer liquid at 25 degreeC.

  Suitable monomers (I) include, for example, benzotriazole monomers represented by the following general formula (1). The benzotriazole monomer is more excellent in ultraviolet absorption than the benzophenone monomer represented by the following general formula (2) and the triazine monomer represented by the general formula (3).

In the general formula (1), R ¹ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group. To express. R ² may form a hydrocarbon group having 1 to 12 carbon atoms, —R′—O— (R ′ represents a linear or branched alkylene group having 2 or 3 carbon atoms) or a hydrogen bond. A group having an element is represented. R ³ represents a hydrogen atom or a methyl group.

The halogen atom of R ¹ and R ⁴ in the general formula (1) is any one of fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group (isopentyl group), tert-pentyl group (2,2-dimethylpropyl group), n-heptyl group, n-octyl group, tert-octyl group (1,1,3,3, -tetramethylbutyl) Group), a linear or branched alkyl group such as 2-ethylhexyl group; and an alicyclic alkyl group such as cyclohexyl group. The alkoxy group having 1 to 6 carbon atoms is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, or the like.

Examples of the hydrocarbon group having 1 to 12 carbon atoms of R ² in the general formula (1) include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, and a tert-butylene. Group, n-pentylene group, sec-pentylene group, tert-pentylene group, n-heptylene group, n-octylene group, tert-octylene group, 2-ethylhexylene group, nonylene group, decylene group, undecylene group, dodecylene group Linear or branched alkylene groups such as alicyclic alkylene groups such as cyclohexylene groups; aromatic hydrocarbon groups such as phenylene groups, xylylene groups, benzylene groups, and phenethylene groups. The “group having an element capable of forming a hydrogen bond” of R ² means that a hydrogen bond is formed between the UV-absorbing polymer molecules and the coating film (UV-absorbing layer) has physical properties such as flex resistance and water resistance. It is a group having the effect of increasing Specific examples of R ² include —NH—, —CH ₂ NH—, —OCH ₂ CH (OH) CH ₂ O—, —CH ₂ CH ₂ COOCH ₂ CH (OH) CH ₂ O—.

  Examples of the monomer (I) represented by the above formula (1) include 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy- 3′-tert-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(methacryloyloxypropyl) phenyl] -2H -Benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxypropoxy) phenyl] -2H-methoxy-benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) ) -5- (2'-methacryloyloxyethyl) -2H-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5- ( '-Methacryloyloxyethyl) -2H-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methoxyphenyl) -5- (3'-methacryloyloxypropoxy) -2H-benzotriazole, 2- [2′-Hydroxy-3′-methacryloylaminomethyl-5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-methacryloyl Amino-5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-acryloylaminomethyl-5- (1,1,3,3) -Tetramethylbutyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid- (2-methacryloyloxy) ethyl ester-2 -Benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) -5-carboxylic acid- (2-methacryloyloxy) ethyl ester-2H-benzotriazole, 2- [2'-hydroxy-3 ' -Tert-butyl-5'-2- (2-methacryloyloxyethoxycarbonyl) ethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-2- (3- Methacryloyloxy-2-hydroxypropoxycarbonyl) ethylphenyl] -2H-benzotriazole. Among these monomers (I) represented by the above formula (1), those having particularly good polymerization stability include, for example, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H -Benzotriazole.

  Examples of other suitable monomer (I) include benzophenone monomers represented by the following general formula (2). In this monomer, the benzophenone skeleton absorbs ultraviolet rays.

In the general formula (2), R ⁵ , R ⁶ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or Represents a nitro group. R ⁷ represents —O—, —OCH ₂ CH ₂ O—, —OCH ₂ CH (OH) CH ₂ O—. R ⁸ represents a hydrogen atom or a methyl group.

  Suitable benzophenone monomers represented by the general formula (2) include, for example, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-3-tert-butyl-4- [ 2- (meth) acryloyloxy] ethoxybenzophenone. The benzophenone-based monomer is obtained by reacting a corresponding benzophenone (commercially available as an ultraviolet absorber) with glycidyl (meth) acrylate.

  Examples of the other monomer (I) include a triazine monomer represented by the following general formula (3).

In the general formula (3), R ¹⁰ represents — (CH ₂ ) n —O— or —CH ₂ CH (OH) —CH ₂ O—, and n represents an integer of 1 to 20. R ¹¹ represents a hydrogen atom or a methyl group. R ^{12 to} R ¹⁹ each independently represents a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group, or an alkyl group.

  Examples of the monomer (I) represented by the general formula (3) include 2- [2-hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1,3. , 5-triazine, 2- [2-hydroxy-4- (11-methacryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -4,6-bisdiphenyl-1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4 -(11-Methacryloyloxy-undecyloxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxy) Ethoxy) phenyl] -1,3, - triazine.

  The monomer (I) can be used alone or in combination of two or more thereof. At this time, the larger the amount of monomer (I) used, the better the UV absorption characteristics of the UV absorbing layer.On the other hand, if the amount of monomer (I) is excessive, the stability of emulsion polymerization is reduced and UV absorption is reduced. Industrial production of the conductive polymer becomes difficult. Therefore, the amount of monomer (I) used is preferably 30 to 85 parts by mass, and 40 to 85 parts by mass, when the amount of monomers (I) and monomer (II) used is 100 parts by mass. Preferably, it is more preferable in it being 50-75 mass parts.

(Monomer (II))
As described above, the monomer (II) is a monomer that is copolymerizable with the monomer (I) and has no crosslinkability. Here, “not having crosslinkability” means that the produced UV-absorbing polymer does not have a crosslinked structure. Therefore, a monomer having a crosslinkability and a bifunctional or higher functional monomer and a monomer that leads to a crosslinked structure of the ultraviolet absorbing polymer by a reaction with a functional group of the ultraviolet absorbing polymer does not correspond to the monomer (II).

  If a monomer having no crosslinkability is selected as the monomer (II), the film-forming property of the ultraviolet absorbing layer is improved, and the decrease in flexibility and stretchability of the ultraviolet absorbing layer is suppressed. In addition, by selecting the type and amount of monomer (II), it is possible to change the properties of the obtained ultraviolet absorbing polymer.

  As the monomer (II), a monomer capable of realizing a UV-absorbing polymer excellent in weather resistance and having good copolymerizability with a benzotriazole-based monomer is preferable. Such a monomer (II) is (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate , N-la Uril (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate (for example, Eastman "Eastman AAEM"), phenoxyethyl (meth) acrylate.

  In addition, vinyl ester, halogen-containing monomer, nitrogen-containing monomer, vinyl ether, epoxy group-containing monomer, hydroxyl group-containing monomer, and acidic functional group-containing monomer also correspond to monomer (II).

  Examples of the vinyl ester include vinyl acetate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, octyl. Vinyl acid vinyl, monochloro vinyl acetate, vinyl benzoate and the like.

  Examples of the halogen-containing monomer include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluorodecyl (meth) acrylate, β -(Perfluorooctyl) ethyl (meth) acrylate, ethylene oxide addition (meth) acrylate of tribromophenol, tribromophenyl (meth) acrylate, and the like.

  Examples of the nitrogen-containing monomer include (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl (meth) acrylate sulfate, and morpholine ethylene oxide. Addition (meth) acrylate, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylmethylcarbamate, N, N-methylvinylacetamide 2-isopropenyl-2-oxazoline, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, acryloylmorpholine, N-iso Propylacrylamide, N, N-diethylacrylamide, N, N, N-trimethylammonium ethyl acrylate and the like.

  Examples of the vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl n-propyl ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl n-amyl ether, vinyl isoamyl ether, vinyl-2-ethylhexyl. Ether, vinyl-n-octadecyl ether, cyanomethyl vinyl ether, 2,2-dimethylaminoethyl vinyl ether, 2-chloroethyl vinyl ether, β-difluoromethyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether and the like.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, α-methyl glycidyl acrylate, α-methyl glycidyl methacrylate (for example, “MGMA” manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl acrylate (for example, Daicel). “Silomer A400” manufactured by Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, “Silomer M100” manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, “Placcel F” series manufactured by Daicel Chemical Industries, Ltd.) and the like.

  Examples of the acidic functional group-containing monomer include sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, and the like.

  There are many compounds that fall under the monomer (II), and some of these compounds improve the UV stability of UV absorbing polymers. As monomer (II) which raises the stability, for example, a compound represented by the following general formula (4) corresponds to monomer (II). The compound represented by the formula is a suitable monomer (II) that can further improve the weather resistance of the ultraviolet absorbing layer.

In the general formula (4), R ²⁰ represents a hydrogen atom or a cyano group. R ²¹ represents an oxygen atom or an imino group. R ²² and R ²³ each independently represents a hydrogen atom or a methyl group. R ²⁴ represents a hydrogen atom or an alkyl group.

  Examples of the monomer (II) represented by the general formula (4) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine (for example, “ADEKA STAB LA87” manufactured by ADEKA), 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine (for example, “Adeka Stub LA manufactured by ADEKA) -82 "), 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine.

  Monomer (II) can be used alone or in combination of two or more thereof. When two or more kinds of monomers (II) are used, it is preferable to select a hydroxyl group-containing monomer and a compound represented by the general formula (4). This is because the hydroxyl group-containing monomer improves the adhesion of the ultraviolet absorbing layer to the adherend, and the compound represented by the general formula (4) improves the weather resistance of the ultraviolet absorbing layer.

  The amount of monomer (II) used is 15 to 70 parts by mass in order to achieve both good polymerization stability and film forming properties when the amount of monomer (I) and monomer (II) used is 100 parts by mass. The amount is preferably 15 to 60 parts by mass, more preferably 25 to 50 parts by mass.

  When the compound represented by the general formula (4) is a kind of the monomer (II), the compound represented by the general formula (4) in the total amount of 15 to 70 parts by mass of the monomer (II) is 0. The amount is preferably 5 to 30 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. When the compound represented by the general formula (4) is less than 0.5 parts by mass, the effect of improving the weather resistance is not exhibited, and when it exceeds 30 parts by mass, the film forming property is remarkably lowered and the polymerization is performed. Stability may be reduced.

(Polymerizable nonionic surfactant)
The polymerizable nonionic surfactant is a compound having a radical polymerizable group such as a propenyl group capable of radical polymerization with the monomer (I) and the monomer (II). The said surfactant is taken in as a structure of the ultraviolet absorptive polymer produced | generated by superposition | polymerization.

  Examples of the polymerizable nonionic surfactant include a polyethylene glycol alkyl ether compound represented by the following general formula (5). When the compound is selected, the polymerization stability is particularly good.

In the above formula (5), R ²⁵ represents an alkyl group, and n is an integer. Examples of the polyethylene glycol alkyl ether compounds represented by the above formula (5) include compounds in which R ²⁵ is —C ₁₁ H ₂₃ and n is 10 to 50.

  Moreover, as another polymerizable nonionic surfactant, the polyoxyethylene alkylphenyl ether type compound represented by following General formula (6) is mentioned, for example.

In the above formula (6), R ²⁶ represents an alkyl group, and n is an integer. Examples of the polyoxyethylene alkylphenyl ether compounds represented by the above formula (6) include compounds in which R ²⁶ is —C ₉ H ₁₉ and n is 10 to 50.

  A polymerizable nonionic surfactant is available on the market. Examples of such a polymerizable nonionic surfactant include “ADEKA rear soap ER” series (ER-10, ER-20, ER-30, ER-40, etc.) manufactured by ADEKA and “ADEKA rear soap NE” manufactured by ADEKA. "Series (NE-10, NE-20, NE-30, etc.)," AQUALON RN "series (RN-10, RN-20, RN-30, RN-50, RN-2025, etc.) manufactured by Daiichi Kogyo Seiyaku Etc.

  One or two or more kinds of polymerizable nonionic surfactants can be used. If the amount of the surfactant is small, not only the oil droplets are not stabilized in the emulsion polymerization but also a lot of aggregates are generated. On the other hand, if the amount of the surfactant is excessive, the absolute amount of the UV-absorbing monomer (I) constituting the UV-absorbing layer is reduced, so that the non-adhesiveness and water resistance of the UV-absorbing layer are reduced. There is. Therefore, the amount of the polymerizable nonionic surfactant relative to the total amount 100 of the monomer (I) and the monomer (II) is preferably 20 to 50 parts by mass, and preferably 25 to 40 parts by mass, More preferably, it is 25-35 mass parts.

(Combination agent)
The compounding agent is compounded in the water-containing medium in the emulsion polymerization of the UV-absorbing polymer, and is composed of one or two or more compounds other than the monomer (I), the monomer (II), and the polymerizable nonionic surfactant. is there. As long as the stability of the oil droplets is not impaired, it is allowed to add a compounding agent to the water-containing medium.

  As the compounding agent, a non-polymerizable ultraviolet stabilizer is preferable from the viewpoint of suppressing yellowing of the ultraviolet absorbing layer. As the stabilizer, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2, A hindered amine-based UV stabilizer such as 6,6-pentamethyl-4-piperidyl) sebacate is preferred. The amount of the UV stabilizer used as a compounding agent is preferably 0.5 to 30 as the mass ratio of the monomer (I) and the monomer (II) to the total amount 100 (however, the monomer (II) has UV stability). When the compound is contained, the total amount of the UV-stabilizing monomer (II) and the UV-stabilizing agent as a compounding agent is, as a mass ratio with respect to the total amount of monomer (I) and monomer (II) 100, 0.5 to 30 is good).

  Anionic, nonionic, cationic, or amphoteric and non-polymerizable surfactants may be used as a compounding agent, but depending on the amount used, oil droplets in emulsion polymerization may become unstable. There is a case. Therefore, it is preferable to avoid the use of non-polymerizable surfactants.

  Non-polymerizable anionic surfactants include, for example, alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; Alkali sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiate; Alkali metals of sodium dodecylbenzene sulfonate and alkali phenol hydroxyethylene Alkyl aryl sulfonates such as sulfate; higher alkyl naphthalene sulfone Salts; naphthalenesulfonic acid-formalin condensate; dialkyl sulfosuccinate, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates; and the like.

  Non-polymerizable nonionic surfactants include, for example, alkylphenols; polyoxyethylene alkyl ethers; polyoxyethyleneoxypropylene copolymers; sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyols such as glycerol monolaurate, and the like. And esters of fatty acids; condensation products of ethylene oxide and fatty acid amines, amides or acids.

  Examples of the non-polymerizable cationic surfactant include amine salts, imidazole salts, quaternary ammonium salts and the like.

  Non-polymerizable amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants. Specific non-polymerizable amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N , N-betaine type (for example, “Amorgen K” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

(Production method of water dispersion composition)
The aqueous dispersion composition of the present invention is produced by the following emulsion polymerization. The ultraviolet absorbing polymer, which is one component of the water dispersion composition, is composed of monomer (I), monomer (II), and polymerizability in oil droplets formed by a polymerizable nonionic surfactant in an aqueous medium. A nonionic surfactant is generated by radical polymerization.

  A batch charging method, a monomer dropping method, a pre-emulsion method and the like can be used as the emulsion polymerization method, and the batch charging method is preferable as the emulsion polymerization method. Since heating is required to dissolve the monomer (I) in the monomer (II) at 25 ° C., when the monomer dropping method is employed, a heating facility must be provided in the dropping funnel. However, such equipment is not necessary for the batch charging method.

  When the batch charging method is adopted, the monomer (I), the monomer (II), the polymerizable nonionic surfactant, and water are charged into the reaction vessel (the compounding agent may also be charged if necessary). At this time, the order of charging into the reaction vessel is not particularly limited. The amounts of monomer (I), monomer (II), and polymerizable nonionic surfactant charged in the reaction vessel are as described above. The total amount of the monomer (I) and the monomer (II) is preferably 25 to 45% by mass when the total of the monomer (I), the monomer (II) and water is 100% by mass. If it is this range, the temperature control at the time of superposition | polymerization will become easy, and the ultraviolet-ray absorption layer of appropriate thickness can be formed. The total amount of the monomer (I) and the monomer (II) is more preferably 25 to 35% by mass.

  The water charged into the reactor vessel may contain about 4.0% by mass or less of an organic solvent. For example, when a high boiling point solvent such as diethylene glycol or butyl cellosolve is used as the organic solvent, the monomer (I) is easily dissolved in the monomer (II) and acts as an auxiliary agent for forming the ultraviolet absorbing layer. Other organic solvents that can be used include propylene glycol solvents such as ethyl carbitol, butyl carbitol, and dawanol (registered trademark: manufactured by Dow Chemical Company). However, in order to achieve VOC-free described later, it is preferable to use only water as a polymerization medium.

  The monomer (I) can be dissolved in the monomer (II) by charging the monomer (I) and the like into the reaction vessel and then heating the reaction vessel to 80 ° C. or higher. In order to confirm the dissolution of the monomer (I), a small amount of the liquid in the reaction vessel is sampled and visually confirmed.

  Subsequently, the temperature in the reaction vessel is maintained at about 70 to 80 ° C., and a polymerization initiator is added to perform emulsion polymerization. Examples of the polymerization initiator include persulfates (ammonium persulfate, sodium persulfate, potassium persulfate, etc.), inorganic peroxides such as hydrogen peroxide; t-butyl hydroperoxide, benzoyl peroxide, peracetic acid, and the like. Organic peroxides: 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, etc. An azo compound. Moreover, it is good also as a redox type | system | group initiator by using sodium bisulfite, L-ascorbic acid, etc. as a reducing agent with these polymerization initiators. The preferred amount of the polymerization initiator used is 0.01 to 1% by mass when the total amount of monomer (I) and monomer (II) is 100% by mass. If the amount of the polymerization initiator is too small, it may take time to complete the polymerization, but if it is too large, the polymerization stability and storage stability will be lowered, and the physical properties such as the water resistance of the UV absorbing layer may be deteriorated. This is not preferable.

  After the polymerization initiator is added, heat generation starts when emulsion polymerization starts, but the initial heat generation at that time is preferably suppressed to 95 ° C. or lower. The initial polymerization time is about 30 minutes although it depends on the mass of the monomer (I) and the like. Thereafter, the polymerization is continued at 75 to 95 ° C. The polymerization reaction is preferably performed at a pH of 2 to 10.

  The reaction time may be appropriately set so that the emulsion polymerization reaction can be completed efficiently according to the mass and type of monomer (I), polymerization initiator, etc. charged in the reaction vessel. The time is usually about 1 to 10 hours. When the ultraviolet absorbing polymer contains an acid group, it may be neutralized before, during or after the emulsion polymerization.

  After the emulsion polymerization, the water-dispersed composition according to the present invention is obtained by adjusting the solid content as necessary. The composition is preferably VOC-free. Here, VOC is a volatile organic compound having a boiling point of 50-100 ° C. to 240-260 ° C. among organic compounds that may become indoor air pollution sources classified by WHO. In order to be VOC-free, such a volatile organic compound is desirably 0.5% by mass or less in the composition.

(UV absorbing polymer)
It is preferable for the average particle size of the ultraviolet absorbing polymer to be 30 to 80 nm because it is easy to form an ultraviolet absorbing layer having good coating properties and excellent water resistance. A more preferable average particle diameter is 30 to 60 nm. Here, the average particle diameter of the polymer particles of the emulsion can be measured using, for example, “NICOMP MODEL 380” manufactured by Particle Sizing System. The analysis method may be VOLUME Weighted GAUSSIAN DISTRIBUTION Analysis (Solid Particle). In order to adjust the average particle size, the produced aqueous dispersion composition may be treated by a known classification method such as filtration. In this case, it is preferable to remove coarse particles having an average particle size exceeding 5 μm. This is because coarse particles may cause defects in the ultraviolet absorbing layer.

  In addition, if an ultraviolet-absorbing polymer is blended as a high-molecular-weight ultraviolet absorber in a resin that is deteriorated by ultraviolet rays described later, the weather resistance of the resin can be improved.

  The mass average molecular weight (Mw) of the ultraviolet absorbing polymer is 50,000 or more. Mw can be measured by, for example, GPC. The UV-absorbing polymer in the present invention may have a Mw exceeding 1 million.

  Moreover, Tg of an ultraviolet absorptive polymer is preferable in it being 0-80 degreeC, and it is more preferable in it being 10-60 degreeC. Tg can be determined by DSC (Differential Scanning Calorimetry) or TMA (Thermomechanical Measurement Device). In addition, it is convenient to use a calculated value (hereinafter sometimes referred to as “calculation Tg”) obtained by the following formula as a guide.

In the above formula, Tg represents the glass transition temperature _{(K), W 1, W} 2, ... Wn represents the mass fraction of each _{monomer, Tg 1, Tg 2, ...} Tg n is the corresponding monomers homo- The glass transition temperature (K) of the polymer is shown. The Tg of the homopolymer may be a value described in a publication such as “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.).

(Water dispersion composition)
The aqueous dispersion composition produced by the emulsion polymerization corresponds to the aqueous dispersion composition of the present invention. An aqueous dispersion composition containing water and an ultraviolet absorbing polymer produced by the above emulsion polymerization method also falls under the present invention.

  Other components may be added to the aqueous dispersion composition of the present invention. As an additive component, a curing agent such as a polyisocyanate compound, an aminoplast resin, a metal-based cross-linking agent such as aluminum chelate and zirconia (in this case, a hydroxyl group and / or a carboxyl group is introduced into the ultraviolet absorbing polymer) Benzotriazole-based, benzophenone-based, triazine-based, indole-based organic ultraviolet absorbers; zinc oxide and other inorganic ultraviolet absorbers; sterically hindered piperidine compounds (for example, “Tinuvin 123” manufactured by Ciba Specialty Chemicals, "Tinuvin 144", "Tinuvin 765"), hindered amine UV stabilizers (for example, "ADEKA STAB LA-31" manufactured by ADEKA), etc .; vinyl chloride resins, polyester resins, acrylic resins , Silicone resin, urethane resin Resins such as epoxy resins; leveling agents, antioxidants, fillers such as talc, rust inhibitors, fluorescent whitening agents, antioxidants, antistatic agents, pigments, dyes, thickeners, colloidal silica, alumina sol Additives common in the paint field such as inorganic fine particles such as polymethyl methacrylate acrylic fine particles and film forming aids. These other additive components are desirably used so that the amount of the UV-absorbing polymer in the UV-absorbing layer is 50% by mass or more (more preferably 80% by mass or more).

  If the water-dispersed composition according to the present invention is applied to any surface of a molded body itself such as a film, a plate, and a fiber, and a functional film coated on the surface of the molded body, an ultraviolet absorbing layer is provided. A laminated body can be obtained. At this time, a resin that is easily deteriorated by ultraviolet rays can be used as a molded body (base material). “Degraded by ultraviolet rays” means that the main chain is cleaved by ultraviolet rays and the molecular weight is reduced, or conversely, gels are formed by crosslinking, resulting in changes in mechanical strength, transparency, yellowing, etc. This refers to causing a decrease in physical properties.

  Examples of the resin that deteriorates due to ultraviolet rays include, for example, polycarbonate resins, polyarylate resins, acrylic resins, polyolefin resins, polyester resins, ABS resins, polystyrene resins, vinyl chloride resins, triacetyl cellulose, Polyethersulfone, polyphenylene ether, aromatic polyamide, polyvinyl alcohol, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamideimide, polyetherimide, polyetheretherketone, fluorine resin (for example, polytetrafluoroethylene), An ultraviolet absorbing layer can be formed by applying the aqueous dispersion composition of the present invention to these resin surfaces. Also, using the aqueous dispersion composition of the present invention, an ultraviolet absorbing layer is formed on the surface of an optical resin such as “ARTON” manufactured by JSR, “ZEONEX” manufactured by Nippon Zeon Co., Ltd., and “OPTREZ” manufactured by Hitachi Chemical Co., Ltd. You may do it. Among these, a polycarbonate resin, a polyester resin, and an acrylic resin that are inexpensive, light, durable, and excellent in transparency are preferable.

  In addition, examples of the resin include a polymer having a lactone structure represented by the following formula (7).

In said formula (7), R <^27> , R <^28> and R < ²⁹ > represent a hydrogen atom or a C1-C20 organic residue each independently. The organic residue may contain an oxygen atom. Examples of the organic residue include an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkylene group, and an aromatic ring.

  The shape of the molded body is not particularly limited, and may be a plate shape such as a flat plate shape, a curved plate shape, and a corrugated plate shape or a film shape having high versatility. Moreover, it is also possible to use for the said molded object the resin base material by which the surface was decorated by printing, such as wood grain printing. Furthermore, for the purpose of protecting contents such as a container made of an inorganic transparent substrate such as glass from ultraviolet rays, an ultraviolet absorbing layer can be provided on the outer surface of the inorganic transparent substrate.

  Examples of a method for applying the water-dispersed composition to the molded body include known coating methods such as dipping, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, and bar coating.

  The ultraviolet absorbing performance of the ultraviolet absorbing layer depends on the thickness of the layer and the amount of the ultraviolet absorbing group introduced into the ultraviolet absorbing polymer according to Lambert-Beer's law. That is, the ultraviolet absorption performance depends on the amount of monomer (I) used. Therefore, the thickness of the ultraviolet absorbing layer may be determined in consideration of the amount of monomer (I) used and the weather resistance and ultraviolet absorbing performance required for the ultraviolet absorbing layer. Usually, it exists in the range of 0.5-500 micrometers. When the thickness exceeds 500 μm, the ultraviolet absorption performance is saturated, which is wasteful in cost. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the molded body, and the ultraviolet absorption performance may be insufficient. A more preferable thickness range is 1 to 300 μm, and more preferably 2 to 50 μm.

  The drying temperature when forming the ultraviolet absorbing layer by applying the composition of the present invention to a molded body in a thin film is usually preferably from room temperature (or outside temperature) to 200 ° C.

  An ultraviolet absorbing layer laminate having a molded body and an ultraviolet absorbing layer (this laminate also includes those having other layers between the molded body and the ultraviolet absorbing layer). Since it is excellent in various properties such as strength and weather resistance, it can be used in various applications as it is, but a hard coat layer may be provided on the outermost surface. The hard coat layer is preferably formed using a resin that can form a coating film having high hardness and excellent scratch resistance. As a resin capable of forming such a coating film, for example, a silicone-based curable resin and an organic curable resin as disclosed in JP-A-2000-177070 are preferable.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples, and can be implemented with appropriate modifications within a range that can be adapted to the purpose described above and below. These are all included in the technical scope of the present invention. In the following examples and comparative examples, “parts” and “%” represent mass parts and mass%, respectively.

Example 1
As monomer (I), 65 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (hereinafter “UVA-1”) was used, and as monomer (II), 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 2.0 parts (“ADEKA STAB LA-82” manufactured by ADEKA; UV stabilizer), 31 parts 2-ethylhexyl acrylate, and hydroxyethyl methacrylate 2 Using 0.0 part, an aqueous dispersion composition was prepared as follows. Monomer (I) was charged into a separable flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube, thermometer and dropping funnel, and monomer (II) was further charged, and nitrogen gas was introduced and stirred. Thereafter, 120 parts of a 25% aqueous solution of polymerizable nonionic surfactant 1 (“ADEKA rear soap ER-20” manufactured by ADEKA) and 239.1 parts of deionized water were added to the flask while heating. , And stirred at 80 to 85 ° C. for 1 hour. After confirming that UVA-1 which was powder was completely dissolved, the temperature was adjusted to 70 ° C. Next, 5.0 parts of a 10% aqueous solution of 2,2-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator was added to the flask to initiate emulsion polymerization. In the polymerization, after about 30 minutes had passed while the initial heat generation was suppressed to 95 ° C. or lower, the temperature was adjusted to 80 to 85 ° C., and then aged for about 2 hours, and then cooled. A water-dispersed composition was prepared by the above operation. In this water-dispersed composition, the average particle diameter of the dispersed particles was 41 nm, the solid content was 30%, the pH was 6.5, and the viscosity was 6.4 mPa · s. Moreover, the aggregate amount was 0.00%.

  The average particle diameter, solid content, pH, and viscosity of the dispersed particles are values determined as follows. For the calculation of the average particle size, “NICOMP MODEL 380” manufactured by Particle Sizing System was used, and VOLUME Weighted GAUSSIAN DISTRIBUTION Analysis (Solid Particle) was adopted as an analysis method. The solid content was calculated by taking about 1 g of the water-dispersed composition in an aluminum dish and precisely weighing the mass before and after drying in a hot air dryer at 110 ° C. for 1 hour. The pH value was measured with a digital pH meter (manufactured by Horiba Seisakusho) for an aqueous dispersion composition adjusted to 25 ° C. For the viscosity, a B-type viscometer (digital viscometer “M-BII” manufactured by Tokimec Co., Ltd.) was used. 1. Measurement was performed under the condition of a rotational speed of 60 rpm.

  Moreover, the said aggregate amount was computed as follows. The aqueous dispersion composition was filtered through a pre-weighed 300 mesh wire mesh, and the collected agglomerate was dried together with the wire mesh in a hot air dryer at 100 ° C. for 3 hours. Thereafter, the wire mesh was weighed, and the amount of aggregate was calculated by the following formula.

(Examples 2-22, Comparative Examples 1-7)
In the same manner as in Example 1, the aqueous dispersion compositions of Examples 2 to 22 and Comparative Examples 1 to 7 were prepared, and the average particle diameter, solid content, pH, viscosity, and aggregate amount in each aqueous dispersion composition were determined. . Here, the raw material ratio used for preparation of each water dispersion composition was set to the ratio shown in Tables 1-3 below. In Example 15, a non-polymerizable UV stabilizer was charged into the reaction vessel together with the monomer (II). In Comparative Examples 2 and 3, a non-polymerizable nonionic surfactant or a non-polymerizable anionic surfactant was added in place of the polymerizable nonionic surfactant. In Comparative Examples 4, 6 and 7, the non-polymerizable nonionic surfactant was added together with the polymerizable nonionic surfactant. In Comparative Example 5, glycidyl methacrylate (GMA) was added together with monomer (II).

  About the water dispersion composition of the above Example and comparative example, the polymerization stability in the manufacture process was confirmed. Furthermore, each water-dispersed composition was evaluated for coatability and cation miscibility. The ultraviolet absorbing layer formed using each aqueous dispersion composition was evaluated for coarse particles, stain resistance, non-adhesiveness, water resistance, yellowing resistance, standard weather resistance, and post-extension weather resistance. . Details of these evaluations are as follows. In the following, “ultraviolet absorption layer” and “coating film” are synonymous.

(Polymerization stability)
Polymerization stability in emulsion polymerization was evaluated from the above calculated amount of aggregate in the aqueous dispersion composition. The evaluation criteria were as follows.
Aggregate amount 0.00-0.09%: ◎
Aggregate amount 0.10 to 0.19%: ○
Aggregate amount 0.20 to 0.49%: Δ
Aggregate amount 0.50% or more: ×

(Coating property)
The water-dispersed composition was dried on a bar coater # 30 and coated on a glass plate (7 cm × 15 cm; the same applies hereinafter) so that the thickness of the coating film was 11.7 μm. This glass plate was placed on a horizontal glass plate in a hot air dryer at 110 ° C. and dried for 3 minutes. Thereafter, the film was taken out from the dryer and allowed to stand at room temperature (25 ° C.) for a while, and then the presence or contraction of defects such as repellency, wrinkles, and crocodiles (such as bubbles) of the coating film and shrinkage were visually observed. The evaluation criteria for the observation are as follows.
There were no defects and no shrinkage of the coating was observed:
Slight defects were observed, and the shrinkage of the coating was within 10% of the coating width (7 cm):
Defects were confirmed and the shrinkage of the coating film was within 30% of the coating width (7 cm): Δ
Defects were confirmed on the entire surface of the coating film, and the shrinkage of the film was within 50% of the coating width (7 cm): ×

(Cation miscibility)
A 50% aqueous solution of 5% polyvinyl alcohol (“Kuraray Poval” manufactured by Kuraray Co., Ltd.) and 10 parts of an aqueous dispersion composition were mixed and stirred, and 1% polyethyleneimine (“Epomin SP-006” manufactured by Nippon Shokubai Co., Ltd.) was stirred. A cation mixture was prepared by gradually adding 10 g of an aqueous solution. The state of the cation mixture immediately after this preparation and the state of the mixture after standing at 50 ° C. for 1 month were visually confirmed. The evaluation criteria for the confirmation were as follows.
There was no abnormality immediately after preparation and after standing: ◎
Although there was no abnormality immediately after preparation, the viscosity increased slightly after standing: ○
Generation of a small amount of blisters was observed immediately after preparation, no abnormality after standing, or slightly increased viscosity: △
A large amount of bumps occur immediately after preparation, or the viscosity greatly increases after standing: ×

(Coarse particles)
Qualitative filter paper No. 5 with a reserved particle size of 5 μm and a collection efficiency of 80%. 2 was used for natural filtration of the water-dispersed composition. The aqueous dispersion composition after filtration was dried with a bar coater # 12 and coated on a glass plate so that the thickness of the coating film became 4.7 μm. This glass plate was placed on a horizontal glass in a hot air dryer at 110 ° C. It was placed on a plate and dried for 3 minutes. Thereafter, the coated glass plate was taken out from the dryer and allowed to stand at room temperature (25 ° C.), and then the presence of coarse particles having a particle size of 5 μm or more was visually confirmed. In this confirmation, in the case of a contracted coating film, the entire coating film was confirmed (hereinafter the same). The evaluation criteria for coarse particles were as follows.
No coarse particles were observed: ◎
Less than 3 coarse particles were observed:
4-10 coarse particles were observed: Δ
Coarse particles were observed on the entire surface: ×

(Contamination resistance)
The water-dispersed composition was dried on a bar coater # 30 and then coated on a glass plate so that the thickness of the coating film was 11.7 μm, and this glass plate was placed on a horizontal glass plate in a hot air dryer at 110 ° C. And dried for 3 minutes. Thereafter, the coated glass plate is taken out from the dryer and allowed to stand at room temperature (25 ° C.), then the four sides of the coating are sealed with a two-component epoxy resin, and water enters the gap between the coating and the glass plate. I prevented it. This sample was allowed to stand in a constant temperature and humidity chamber at 23 ° C. and 65% RH for 1 day, and then a suspension in which 0.05% of carbon black particles were dispersed was applied to the coating surface of the sample with a brush. It was applied once and dried at 50 ° C. for 1 hour. Next, the coating surface was rubbed 30 times with a brush while being washed with running water. After drying at room temperature, the surface contamination was visually observed. The evaluation criteria for contamination resistance were as follows.
The coating film was not contaminated at all and was transparent:
The film was partially blackish, but the transparency was maintained:
Although the coating was generally blackish, transparency was maintained to some extent, and small letters on newspapers could be identified through the coating:
The coating was generally blackish and not transparent, making it difficult to distinguish small letters on newspapers through the coating: ×

(Non-adhesive)
The water-dispersed composition was dried on a bar coater # 30 and then coated on a glass plate so that the thickness of the coating film was 11.7 μm, and this glass plate was placed on a horizontal glass plate in a 110 ° C. hot air dryer. And dried for 3 minutes. This sample was allowed to stand in a constant temperature and humidity chamber at 23 ° C. and 65% RH for one day. On this sample, a sheet of gauze (Japanese pharmacopoeia gauze: type 1: obtained from Comet Sanitary Materials Co., Ltd.), a glass plate (cover glass; 2 cm × 2 cm), and a weight (400 g) are stacked in this order. And heated in a hot air dryer at 50 ° C. for 10 minutes. Then, it removed from the dryer and left still at room temperature (25 degreeC) for 1 hour, after removing the weight and the cover glass, the gauze was peeled by hand. The state at that time was evaluated according to the following criteria.
When the gauze was peeled off, it peeled off quickly and no gauze marks were observed on the coating film:
There was a little resistance when gauze was peeled off, but it peeled off cleanly, and no gauze marks were found on the coating film: ○
There was considerable resistance when gauze was peeled off, and gauze marks were clearly recognized:
When the gauze was peeled off, lint remained on the coating film: ×

(water resistant)
The water-dispersed composition was dried on a bar coater # 30 and then coated on a glass plate so that the thickness of the coating film was 11.7 μm, and this glass plate was placed on a horizontal glass plate in a hot air dryer at 110 ° C. And dried for 3 minutes. This sample was allowed to stand in a constant temperature and humidity chamber at 23 ° C. and 65% RH for 1 day, and then one drop of deionized water was applied to the coating film with a glass pipette, and the coating film state was evaluated according to the following criteria.
There was no abnormality: ◎
Slight fluorescence, but transparency of the coating was maintained: ○
A tendency toward whitening of the coating film was observed, and it was difficult to distinguish small letters on newspapers through the coating film:
A tendency toward whitening of the coating film was observed, and water droplet marks were observed on the coating film after evaporation of the water droplets: ×

(Yellowing resistance)
100 parts of binder (“Acryset EX-35” manufactured by Nippon Shokubai Co., Ltd.), 5 parts of high boiling point solvent (“CS-12” manufactured by Chisso), 0.3 part of dispersant (“Demol EP” manufactured by Kao) Foaming agent (San Nopco "Nopco 8034L") 0.2 parts, viscosity modifier (ADEKA "Adecanol UH-420") 0.3 parts, pigment (Ishihara Sangyo titanium oxide "R-930") 40 Part and 19 parts of water were blended to prepare a white paint. This white paint is applied to the glass plate surface with an applicator, dried for one day at room temperature, further dried in an oven at 80 ° C. for 5 days, and then left for one day at room temperature to give a white coating on the glass plate surface. Formed. A water-dispersed composition was applied to the surface of the white coating film so that the thickness of the coating film after drying with a bar coater # 30 was 11.7 μm, and the glass plate was placed on a horizontal glass in a hot air dryer at 110 ° C. Placed on the plate for 60 minutes. The coating film after this placement was evaluated. Separately, apply the aqueous dispersion composition to the surface of the white coating film in the same manner as described above, and place the glass plate in a 110 ° C. dryer for 3 minutes to prepare a reference coating film for comparison with the coating film to be evaluated. did. The evaluation target coating film and the reference coating film were visually compared to confirm yellowing of the evaluation target coating film. The yellowing resistance was evaluated according to the following criteria.
There was no difference from the standard coating:
Yellowish slightly lighter than the standard coating film: ○
Yellowish paler than the reference coating: △
Clearly yellowing or browning than the reference coating: ×

(Standard weather resistance)
A polyvinyl chloride film (20 cm × 30 cm; thickness 100 μm) for film fixation is placed on a glass plate (30 cm × 30 cm), and the four corners of the film are attached to the glass plate with a cellophane tape, The water-dispersed composition was dried with a bar coater # 12 and then coated so that the thickness of the coating film became 4.7 μm, and this glass plate was placed on a horizontal glass plate in a hot air dryer at 80 ° C. Dry for 3 minutes. The sample was allowed to stand at room temperature for 1 hour, and then the film coated with the coating film was peeled off from the glass plate. Attach a double-sided tape to the end of the back of this film, about 1 cm, place it on a glass plate, reciprocate a 1 kg load roller, and press-bond it. Set at Denki Co., Ltd.) and continuously irradiated with 120 mW / cm ² of ultraviolet rays for 50 hours in an atmosphere of 60 ° C. and 50% RH. The appearance of the coating after irradiation was visually observed and evaluated according to the following criteria.
There was no abnormality in the coating film: ◎
The coating was slightly colored: ○
About half of the coating was colored:
The entire coating was colored: ×

(Weather resistance after elongation)
A coating film was formed in the same manner as the standard weather resistance evaluation, and was peeled off from the polyvinyl chloride film. The peeled coating film was pulled and fixed by a tensile tester (“Autograph AGS100D” manufactured by Shimadzu Corporation) at 50 ° C. and at a pulling speed of 5 mm / min, and left for 1 hour. Thereafter, the stretched coating film was removed from the test machine, and ultraviolet irradiation for 50 hours was performed in the same manner as in the evaluation of standard weather resistance. The appearance of the coating film was evaluated according to the same criteria as described above.

The above evaluation results are shown in Tables 1-3. The terms in the table have the following meanings.
UVA-1: 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole UVA-2: 2- [2-hydroxy-3-methacryloylaminomethyl-5- (1,1,3 , 3-tetramethylbutyl) phenyl] -2H-benzotriazole HALS: 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (“ADEKA STAB LA82” manufactured by ADEKA)
CHMA: cyclohexyl methacrylate 2EHA: 2-ethylhexyl acrylate HEMA: 2-hydroxyethyl methacrylate BMA: butyl methacrylate MMA: methyl methacrylate BA: butyl acrylate GMA: glycidyl methacrylate (corresponding to a crosslinkable monomer because it reacts with a hydroxyl group)
Polymerizable nonionic surfactant 1: “ADEKA rear soap ER-20” manufactured by ADEKA (polyethylene glycol alkyl ether system in which R ²⁵ represented by the above general formula (5) is —C ₁₁ H ₂₃ and n is 20 Applicable to compounds.)
Polymerizable nonionic surfactant 2: “AQUALON RN-20” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (polyoxyethylene alkyl in which R ²⁶ represented by the general formula (6) is —C ₉ H ₁₉ , and n is 20) (Applicable to phenyl ether compounds.)
Non-polymerizable nonionic surfactant: Polyoxyethylene alkyl ether surfactant “Emulgen 1118S” manufactured by Kao Corporation
Non-polymerizable anionic surfactant: “Hitenol LA-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Polymerization initiator: 2,2-azobis (2-amidinopropane) dihydrochloride

The following can be confirmed from the results of Tables 1 to 3.
(1) In all Examples using a polymerizable nonionic surfactant as an emulsifier, the polymerization stability was excellent (the polymerization stability of Example 20 was also within a practically acceptable range). On the other hand, in Comparative Examples 1 to 4, Comparative Example 6, and Comparative Example 7, the polymerization stability was inferior due to generation of aggregates during emulsion polymerization or gelation during emulsion polymerization. That is, in the examples, oil droplets in emulsion polymerization were stable.
(2) In Comparative Example 5 using a crosslinkable monomer, although the polymerization stability was excellent, the weather resistance after extension of the ultraviolet absorbing layer was worse than in all Examples.
(3) In the examples, not only the polymerization stability and weather resistance, but also the coating property and stain resistance were excellent.

  The water-dispersed composition of the present invention can prevent environmental contamination due to an organic solvent, and can impart excellent weather resistance to a molded article made of various materials over a long period of time.

  Therefore, the water-dispersed composition of the present invention has a UV protection layer for use in deterioration protection for protecting the contents and the molded body (base material) from UV rays, for example, materials for packaging medicines and foods, glass bottles, and the like. It can be used as a coating agent for forming. In addition, as a coating agent for preventing fading of pigments such as dyes, as a pressure-sensitive adhesive or adhesive when laminating plastic substrates such as fluororesin films, or as a primer for silicone or acrylic hard coat layers Can also be used. Furthermore, it can also be used as a weather-resistant recording liquid, a fiber treatment agent, and an insulating coating agent for insulating elements and display elements.

  The ultraviolet-absorbing layer laminate of the present invention (including a laminate expressed as “film”) is a recording material (for reversible thermosensitive, melt transfer, sublimation transfer, inkjet, thermosensitive, IC card, IC tag). Etc.), packaging materials for chemicals and foods, back sheets for solar cells, marking films, photosensitive resin plates, adhesive sheets, dye-sensitized solar cells, polymer solid electrolytes, ultraviolet absorbing insulating films, various optical films (polarized light) Board protection film, antireflection film, light diffusion film, etc.), building material film (glass scattering prevention film, decorative sheet, window film), indoor / outdoor overlay film (display material, electric signboard), agricultural film It can be used as a shrink film.

Claims (8)

A water-dispersed composition that has water and is used to form an ultraviolet absorbing layer,
30 to 85 parts by mass of a solid UV-absorbing monomer (I) solid at 25 ° C., 70 to 15 parts by mass of a monomer (II) copolymerizable with the monomer (I) and not crosslinkable, It contains an ultraviolet-absorbing polymer obtained by emulsion polymerization of a polymerizable nonionic surfactant having a mass ratio of 20 to 50 with respect to 100 of the total amount of I) and monomer (II) in a water-containing medium. Water-dispersed composition.   The water-dispersed composition according to claim 1, wherein an ultraviolet stabilizer is contained in the water-containing medium.   The water-dispersed composition according to claim 1 or 2, wherein the ultraviolet stabilizer is a non-polymerizable ultraviolet stabilizer and / or a part of the monomer (II).   The water-dispersed composition according to any one of claims 1 to 3, wherein the ultraviolet absorbing polymer has an average particle size of 30 to 80 nm.   The water-dispersed composition according to any one of claims 1 to 4, wherein the monomer (I) contains a benzotriazole-based ultraviolet absorbing monomer.   The water-dispersed composition according to any one of claims 1 to 5, wherein a non-polymerizable surfactant is not contained in the water-containing medium.   The ultraviolet absorption layer laminated body in which the ultraviolet absorption layer was formed with the water dispersion-type composition of any one of Claims 1-6. A method for producing a water-dispersed composition comprising:
30 to 85 parts by mass of a solid UV-absorbing monomer (I) solid at 25 ° C., 70 to 15 parts by mass of a monomer (II) copolymerizable with the monomer (I) and not crosslinkable, 20) to 50 parts by weight of a polymerizable nonionic surfactant with respect to 100 parts by weight of the total amount of I) and monomer (II), and a water-containing medium,
A method for producing a water-dispersed composition, comprising adding a polymerization initiator after dissolving the monomer (I) in the monomer (II) by heating.