JP2012057007A - Resin composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin composition which has high weatherability and exhibits good stain resistance and storage stability even in the form of a one-component type coating material, and further exhibits adhesion with a substrate.SOLUTION: The resin composition for an aqueous coating material contains (I) a synthetic resin emulsion, (II) a silicon compound represented by general formula (1): (RO)SiR, and/or its partially hydrolyzed condensate and/or its modified substance, (III) a specific silane coupling agent, (IV) a photo-sensitizer and/or (V) a photoacid generator and/or (VI) a photo-base generator. In the general formula (1), Rare the same or different and each represent 1-10C alkyl group, 6-10C aryl group or a 7-10C aralkyl group; Rare the same or different and each represent 1-10C alkyl group, 6-10C aryl group or a 7-10C aralkyl group; and a is an integer of 0-2.

Description

  The present invention relates to a resin composition for water-based paints that can form a hydrophilic surface, which is suitably used as a paint for various coatings on architectural interiors and exteriors, roofs, ceramic building materials, automobiles, household appliances, plastics, and the like.

  In recent years, in the paint field, it has been required to impart high performance to a coating film, among which is imparting weather resistance and stain resistance. As a method for imparting stain resistance to a paint, a method is known in which a hydrolyzable silicon compound, particularly an organosilicate is blended in the paint (Patent Document 1). The coating film formed by this method suppresses the adhesion of oily contaminants because the coating surface becomes hydrophilic, and the adhered contaminants can be washed away with water droplets such as rain. To express.

  In general, in order to make the organosilicate-containing paint exhibit stain resistance, the organosilicate is stable during storage and needs to undergo a process in which the organosilicate undergoes hydrolysis during or after the coating is formed. However, organosilicates have poor storage stability and are easily hydrolyzed in the presence of a catalyst such as tin in water-based paints, so it has been necessary to take a two-component type that complicates the operation.

  Very recently, a method for stabilizing organosilicates has been reported (Patent Document 2), and the coating surface can be applied even after coating after storage by using a photoacid generator as a curing agent for water-based paints containing organosilicates. One-component stain-resistant paints that become hydrophilic have been reported. (Patent Document 3). However, the weather resistance is greatly inferior to that of the two-pack type organosilicate-containing paint, and further high weather resistance has been demanded.

WO1994 / 06870 Publication Japanese Patent No. 3437672 JP 2010-13634 A

  The problems to be solved by the present invention are the stability as a paint capable of forming a one-pack type paint, and the resin for water-based paints capable of forming a hydrophilic surface exhibiting high weather resistance and good stain resistance. It is to provide a composition. Furthermore, it is providing the resin composition for 1 liquid type water-system paints which has favorable adhesiveness with respect to a foundation | substrate.

  The present inventor has found that an aqueous resin composition containing a synthetic resin emulsion, a silicon compound, a specific silane coupling agent, a photosensitizer and / or a photoacid generator and / or a photobase generator is a common paint storage. It can be a one-component composition that has stability in the dark, which is a condition, and the obtained coating or coating film has excellent hydrophilicity due to outdoor exposure or other light exposure that is the normal use condition of the object to be coated It has been found that an adhesive surface can be formed, and that good adhesion to the substrate is exhibited.

The resin composition for water-based paints according to the present invention comprises (I) a synthetic resin emulsion, (II) a silicon compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof and / or a modified product thereof: (III It contains a specific silane coupling agent, (IV) a photosensitizer, and / or (V) a photoacid generator and / or (VI) a photobase generator.
(R ¹ O) _4-a SiR ² _a (1)
(Wherein R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ² is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)
Examples of (II) silicon compounds and / or partial hydrolysis condensates thereof and / or modified products thereof include, for example, organosilicates (compounds represented by the following general formula (2) and / or partial hydrolysis condensates thereof) and / or Alternatively, a modified product thereof can be preferably used.
(R ³ O) ₄ Si (2)
(In formula, R < ³ > is the same or different, and is a C1-C10 alkyl group, a C6-C10 aryl group, or a C7-C10 aralkyl group.)
(III) As the silane coupling agent, aminosilane, epoxysilane, and mercaptosilane can be preferably used, and particularly, epoxysilane and / or bis (alkoxysilylalkyl) amine can be preferably used.
(I) As the synthetic resin emulsion, an acrylic resin emulsion having an alkoxysilyl group-containing monomer unit can be suitably used.
(I) As the surfactant used in the synthetic resin emulsion, an anionic surfactant that is an alkali metal salt can be suitably used.
(II) A silicon compound and / or a partially hydrolyzed condensate thereof and / or a modified product thereof as an emulsion obtained by dispersion in an aqueous medium using a nonionic surfactant and / or an anionic surfactant It can be used suitably.
(II) An anionic surfactant that is an alkali metal salt can be suitably used as the surfactant used in the emulsion of the silicon compound and / or its partially hydrolyzed condensate and / or its modified product.
(IV) As a photosensitizer, an anthracene derivative, an acetophenone derivative, a benzophenone derivative, a thioxanthone derivative, and an anthraquinone derivative can be used. In particular, a compound having a benzophenone skeleton or an anthracene skeleton can be preferably used.
(V) As the photoacid generator, an organic halogen compound can be used, and a halogen-containing triazine compound, a vinylidene chloride copolymer, a vinyl chloride copolymer, and a chlorinated polyolefin can be suitably used.
(V) As the photoacid generator, sulfonium salts can be preferably used.
(VI) As the photobase generator, cobaltamine complexes, O-acyloximes, carbamic acid derivatives, formamide derivatives, quaternary ammonium salts, tosylamines, carbamates, and amine imide compounds can be used. Acyl oxime compounds can be suitably used.
(VI) As the photobase generator, an O-acyl oxime having an aryl group represented by the general formula (3) can be suitably used.

(R ⁴ , R ⁵ , and R ⁶ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or the like. Have
(V) a photosensitizer, (VI) a photoacid generator, (VII) a photobase generator is (II) a silicon compound and / or a partial hydrolysis condensate thereof as an accelerator for hydrolysis in the dark. Therefore, water-based paints containing synthetic resin emulsions and (II) silicon compounds and / or their partially hydrolyzed condensates and photosensitizers can be stored in the dark, the usual storage conditions for paints. .
The resin composition for water-based paints according to the present invention can further suitably use (XI) inorganic pigment.
The aqueous paint resin composition according to the present invention can be suitably used as a one-component paint resin composition.
When the paint according to the present invention is used, UV irradiation with a UV lamp may be performed after painting. However, the outdoor exposure, which is a normal use condition of an object to be coated, has excellent stain resistance and high weather resistance with hydrophilicity. A coated product and a coating film can be obtained.

  Since the resin composition for water-based paints of the present invention has high storage stability, a one-pack type paint form is possible. Further, the composition of the present invention may be irradiated with UV light from a UV lamp, but forms an excellent stain-resistant and highly weather-resistant coating film having hydrophilicity due to outdoor exposure which is a normal use condition of an object to be coated. obtain. Furthermore, a coating film having good adhesion to the base can be formed.

  Hereinafter, the present invention will be described in detail based on an embodiment thereof.

(I) Synthetic resin emulsion Examples of the synthetic resin emulsion that can be used in the present invention include acrylic resin emulsion, urethane resin emulsion, fluorine resin emulsion, epoxy resin emulsion, polyester resin emulsion, alkyd resin emulsion, and melamine resin emulsion. However, it is not limited to these. These may be used alone or in combination of two or more. Among these, acrylic resin emulsions are advantageous because of their high cost and high degree of freedom in resin design.

  As the acrylic resin emulsion, those obtained by radical copolymerization of (A) an acrylic monomer and (B) a monomer copolymerizable with (A) can be used.

  (A) The acrylic monomer is a methacrylate and / or acrylate having an alkyl or aralkyl group, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, Examples include lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and isobonyl (meth) acrylate. In this specification, (meth) acrylate represents methacrylate and / or acrylate.

  Among these, if a (meth) acrylate monomer having an alkyl group having 3 or more and 12 or less carbon atoms is used, stable emulsion polymerization is possible and preferable from the viewpoint of durability such as weather resistance of the coating film. In particular, (meth) acrylate monomers having branched and / or cyclic alkyl groups, such as iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate and isobornyl (meth) acrylate are preferred.

  The amount of component (A) in the total amount of monomers is not particularly limited, but 50 to 99 parts by weight with respect to 100 parts by weight of the total amount of monomers is preferable in terms of durability such as weather resistance of the coating film. More preferably, it is 80-99 weight part.

  (B) Unlike (A), the monomer copolymerizable with (A) is not particularly limited as long as it is copolymerizable with these. Specific examples thereof include aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyl toluene; vinyl acetate, vinyl propionate, vinyl versatate, diallyl phthalate, and the like. Vinyl esters and allyl compounds; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics M-5700 (manufactured by Toa Gosei Kagaku Co., Ltd.), packageFA-1, packageFA-4, packageFM-1, and packageFM-4 (and above) Daicel Chemical Co., Ltd.), HE-10, HE-20, HP-10, HP-20 (manufactured by Nippon Shokubai Chemical Co., Ltd.), Bremer PEP series, Bremer NKH-5050, Bremer GLM Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. -6, compounds such as AK-5, vinyl methyl ether, propylene, butadiene and the like.

  Furthermore, hydrophilic vinyl monomers can also be used. Examples of the vinyl monomer having a hydrophilic group that can be used include sodium styrenesulfonate, sodium 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, and vinyl monomers having a polyoxyalkylene chain. Although there is no limitation in the vinyl-type monomer which has a polyoxyalkylene chain, the acrylic acid ester or methacrylic acid ester which has a polyoxyalkylene chain is preferable, As a specific example, Blenmer PE-90, PE- by NOF Corporation is mentioned. 200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP- 800B, 50AOEP-800B, AEP, ET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, MTG, light acrylate EC-A, MTG- A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30 manufactured by Nippon Emulsifier Co., Ltd., MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, new Nakamura Chemical Co., Ltd. NK-ESTER M-20G, M-40G, M-9 G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, and the like.

  In addition, a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate, allyl (meth) acrylate, divinylbenzene or the like is used. It is also possible. In this case, the generated particles have a structure having cross-linking, and the water resistance of the formed coating film is improved.

  Moreover, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, etc. It is also possible to impart high water and oil repellency by using a fluorine-containing vinyl monomer.

  It is also possible to impart crosslinkability by using a carbonyl group-containing vinyl monomer such as diacetone acrylamide or methyl vinyl ketone and blending a compound containing hydrazine and / or hydrazide group. The water resistance of the coated film is improved.

  The amount of component (B) in the total amount of monomers is not particularly limited, but it is economical that component (B) is contained in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. From the viewpoint of imparting functions such as crosslinkability and stability of the emulsion. The vinyl monomer having hydrophilicity is more preferably 0.5 to 3 parts by weight.

  Furthermore, if an alkoxysilyl group-containing monomer is used as the component (C), durability of the coating film is improved, such as water resistance and weather resistance, and contamination resistance due to the silicon compound and / or its partial hydrolysis condensate of (II) It is preferable because the effect is improved.

(C) The alkoxysilyl group-containing monomer is
R ⁷ R ⁸ _(3-b) Si (OR ⁹ ) _b (4)
(Wherein R ⁷ is a monovalent organic group having a polymerizable double bond, R ⁸ is an alkyl group having 1 to 4 carbon atoms, R ⁹ is an alkyl group having 1 to 4 carbon atoms, and b is 1 to 3). The organosilicon compound shown is a compound having an alkoxy group and a reactive double bond. Specific examples thereof include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; γ- (meth) acryloxypropyl Trimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, γ- (meth) acryloxypropyltri Butoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxy Propyl methyl diisopropoxy silane, acrylic silane such as .gamma. (meth) acryloxy propyl methyl dibutoxy silane and the like, can be used in combination of these one or more.

  Although the usage-amount of (C) component is not specifically limited, 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of a monomer, More preferably, it is excessive by using 0.5-10 weight part. It is possible to suppress embrittlement due to crosslinking and improve durability.

The carbon number of R ^{9 in} the component (C) is inversely proportional to the reactivity of hydrolysis / condensation of the alkoxysilyl group, and the reactivity tends to decrease as the carbon number increases. Considering the stability in the emulsion, 2 to 4 are preferable. Among the above specific examples, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, γ- (Meth) acryloxypropylmethyldiethoxysilane is preferred. Further, in (I) as a core / shell type emulsion, the component (C) having a low R ⁹ carbon number (for example, γ- (meth) acryloxypropylmethyldimethoxysilane having a methoxysilyl group) in the core portion, shell portion If a component (C) having a high carbon number of R ⁹ (for example, γ- (meth) acryloxypropyltriethoxysilane having an ethoxysilyl group) is used, a moderate cross-linked structure is introduced into the core portion, which impairs flexibility. In addition, the water resistance and the coating strength can be improved together with the stabilized reactivity of the shell portion.

  When component (C) is used, if component (A) is 60 parts by weight or more of a methacrylic acid ester having an alkyl group and / or cycloalkyl group having 4 or more carbon atoms in 100 parts by weight of the total monomer, This greatly improves the stability of the alkoxysilyl group.

  When 0.5 to 20 parts by weight of a hydroxyl group-containing vinyl monomer and / or a vinyl monomer having a polyoxyalkylene chain is used as the component (B) in 100 parts by weight of the total monomer, (C ), The stability of the alkoxysilyl group of the component (II) silicon compound and / or its partially hydrolyzed condensate, and the mechanical and chemical stability of the emulsion can be improved. Of these, vinyl monomers having a polyoxyalkylene chain are particularly effective.

  Next, the manufacturing method of an acrylic resin emulsion is demonstrated.

  A monomer mixture comprising the components (A) and (B) is obtained by polymerization by a known emulsion polymerization method, for example, a batch polymerization method, a monomer dropping polymerization method, an emulsion monomer dropping polymerization method or the like.

  In addition, the production of the core / shell type emulsion is carried out by polymerizing the monomer mixture forming the core part by a known emulsion polymerization method, and in the presence of the obtained aqueous dispersion of the core component, the monomer forming the shell part. The mixture is polymerized by a known emulsion polymerization method, and a shell component is introduced. In addition, you may divide | segment several times and superpose | polymerize in each component of a core part and a shell part.

  In emulsion polymerization, a commonly used anionic or nonionic surfactant can be used.

  The aqueous medium used for the emulsion polymerization only needs to contain water as an essential component, and may contain other organic solvents. Other organic solvents include alcohol solvents such as ethanol and isopropanol; glycol solvents such as propylene glycol; ether solvents such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol dimethyl ether, propylene glycol monobutyl ether acetate, An ester solvent such as CS-12 manufactured by Chisso Corporation may be mentioned, but it is preferable not to contain an organic solvent from the viewpoint of stability during polymerization of the emulsion and the environment.

  Examples of the anionic surfactant include polyoxyethylene aryl ether sulfate such as polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, and polyoxyethylene alkyl ether sulfate such as polyoxyethylene tridecyl ether sulfate. Sulfates having a polyoxyethylene chain; sulfonic acids such as lauryl sulfonic acid, dodecylbenzene sulfonic acid, alkylnaphthalene sulfonic acid; sulfate esters such as lauryl sulfate; alkyl sulfosuccinic acids such as di (2-ethylhexyl) sulfosuccinic acid, and the like These salts are mentioned.

  Various types of neutralized cation species of an anionic surfactant can be selected. If a surfactant using an alkali metal such as sodium or potassium ion is used, the stability of (II) silicon compound and (C) component is improved. be able to.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid. Those having a polyoxyethylene chain such as ester; those having a hydroxyl group such as sorbitan fatty acid ester and glycerin fatty acid ester; KF-351, KF-352, KF-353, KF-354, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 355, KF-615, KF-618, KF-945, KF-907, X-22-6008, X-22-811, X-22-812, SH3748, SH3749, SH3771, SH8400 manufactured by Toray Dow Corning SF8410, such as one terminal and / or both ends and / or side chains of the silicone-based surfactant is a modified polyorganosiloxane polyalkylene oxides such SF8700 and the like.

  In the present invention, the use of a so-called reactive emulsifier having an unsaturated group in one molecule as a surfactant suppresses foaming in a composition and an aqueous paint using the composition, and the water resistance and weather resistance of the resulting coating film. From the viewpoint of sex. In particular, when a reactive emulsifier having a polyoxyalkylene group in the molecule is used, the mechanical stability can be improved.

  Specific examples of such a reactive emulsifier include, for example, Adeka Soap SR-05, SR-10, SR-20, SR-1025, SR-2025, SR-3025, SR-3025, SR-10S, NE-A manufactured by ADEKA Corporation. 10, NE-20, NE-30, NE-40, SE-10, SE-20, SE-10S, ER-10, ER-20, ER-30, ER-40), Antox manufactured by Nippon Emulsifier Co., Ltd. -MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, BC0515, BC1025, Elyonol JS-2, JS-20 manufactured by Sanyo Chemical Industries, Ltd. RS-30, manufactured by Kao Corp. LATEMUL S-180, S-180A, such as PD-104, PD-420, PD-430 and the like.

  The surfactant can be used alone or in combination of two or more, and the neutralized cation species in the anionic surfactant is not limited to the effect of the present invention, for example ammonia, organic amines other than alkali metals. Neutralized products can also be used.

  The total amount of the surfactant used is 10 parts by weight or less, preferably 0.5 to 8 parts by weight as the amount of active ingredient with respect to 100 parts by weight of the total amount of monomers.

  The amount of the anionic surfactant that is an alkali metal salt in the total amount of the surfactant as the active ingredient amount should be 0.5 to 100 parts by weight with respect to 100 parts by weight of the total amount of the surfactant. However, (II) is preferable from the viewpoint of the stability of the emulsion of the silicon compound and the mechanical stability of the emulsion.

  The polymerization initiator is not particularly limited. An azo compound such as azobis-2-methylbutyronitrile; an inorganic peroxide such as potassium persulfate; an organic peroxide such as cumene hydroperoxide; a peroxide and a reduction Known polymerization initiators such as a redox system combined with an agent can be exemplified. Among them, it is desirable to use a redox system as a polymerization initiator in order to perform polymerization more stably. Further, in order to maintain the stability of the mixed solution during the polymerization and perform the polymerization stably, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is 5 using a base and / or a buffer. It is preferable to adjust to ~ 9.

  Examples of the initiator used for the redox system include potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, t-butyl peroxylaurate, and the like. Examples of the reducing agent to be combined with these include acidic sodium sulfite, Rongalite (manufactured by Bruggamann Chemical US, Sodium formaldehydrate sulfonate), Bruggolite FF-6 (manufactured by Brugganmann Chemical US, 2-hydroxy-US) Sodium sulfide, 2-hydroxy-2-sulfonate-a etic-acid di-sodium salt mixture), thiourea dioxide, etc. L- ascorbic acid. In particular, a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and the like and Rongalite, Bruggolite FF-6 or thiourea dioxide is preferable.

  Note that the reducing agent is particularly preferably Bruggolite FF-6 or thiourea dioxide which does not generate formaldehyde in consideration of the environment.

  The amount of the polymerization initiator used is 0.01 to 10 parts, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of monomers. When the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed. When the amount exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.

  In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the total amount of monomers.

  Chain transfer agents can be added to control the molecular weight of the polymer. Known chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include mercaptan compounds such as γ-mercaptopropylmethyldiethoxysilane, organic halides such as chloroform and carbon tetrachloride, sulfide benzene, isopropylbenzene, and ferric chloride. The amount of the chain transfer agent used is 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight based on 100 parts by weight of the total amount of monomers.

  In order to maintain the stability of the emulsion, it is preferable to maintain the pH at 6 to 10 with a base and / or a buffer after completion of the polymerization. The adjustment and maintenance are not particularly limited as long as the base and / or buffering agent are generally used. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia and organic amines. Examples of buffering agents include carbonates such as sodium hydrogen carbonate and disodium hydrogen phosphate, phosphates, and carboxylates.

  If these pH adjusting agents and buffering agents containing an alkali metal are used, the stability of the (II) silicon compound and the (C) component can be improved, and the use of sodium bicarbonate is more preferable.

  The resin solid content concentration in the acrylic resin emulsion is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the viscosity of the system is remarkably increased, so that it becomes difficult to remove heat generated by the polymerization reaction, or it takes a long time to take out from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in the aspect of the polymerization operation, but the amount of resin generated by one polymerization operation is small, which is disadvantageous in terms of economy. This is disadvantageous in terms of coating workability and coating film performance degradation, such as a reduced coating film thickness.

  The average particle diameter of the acrylic resin emulsion of the present invention is preferably about 0.02 to 1.0 μm. The average particle diameter can be adjusted by the amount of surfactant charged at the initial stage of polymerization.

(II) Silicon Compound and / or Partially Hydrolyzed Condensate thereof The silicon compound as the component (II) in the present invention is represented by the general formula (1).
(R ¹ O) _4-a SiR ² _a (1)
(Wherein R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ² is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)

  Examples of silicon compounds and / or partial hydrolysis condensates thereof include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, and tetra-i-butyl silicate. Tetraalkyl silicates such as tetra-t-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl Triethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyl Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxy Trialkoxysilanes such as silane, vinyltrimethoxysilane, vinyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Sialkoxysilanes such as 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane Emissions and / or one or more partially hydrolyzed condensate chosen from silanes and the like. These may be used alone or in combination of two or more.

Among the above silicon compounds and / or partial hydrolysis condensates thereof, a compound represented by the following general formula (2) and / or an organosilicate which is a partial hydrolysis condensate thereof and / or a modified product thereof is a coating film: It is preferable because it is excellent in the effect of imparting hydrophilicity to the surface and developing stain resistance.
(R ³ O) ₄ Si (2)
(Wherein R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms).

  Examples of the organosilicate include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-t-butyl silicate, etc. Examples thereof include tetraalkyl silicates and one or more partially hydrolyzed condensates selected from these.

R ³ of the organosilicate has a large number of carbon atoms and is branched and the reactivity of hydrolysis / condensation is lowered, and considering the storage stability and stain resistance of the composition, it has 2 to 4 carbon atoms. Are preferred. Further, as R ³ , the reactivity is widened by selecting two or more kinds of short-chain alkyl (for example, ethyl) and long-chain or branched alkyl (for example, i-propyl), so that both storage stability and stain resistance are achieved. It can also be improved.

  Moreover, if it is set as a partial hydrolysis-condensation product, stain resistance can be improved. The degree of condensation is 2-20, preferably 3-15.

  In addition, a hydrophilic polyether containing a hydroxyl group such as polyoxyalkylene or polyoxyalkylene monoalkyl ether is introduced by transesterification or the like, and a hydrophilic group-containing silane compound such as γ-aminopropyltriethoxysilane is used together. Dispersibility in an aqueous medium can also be improved by modification that introduces a hydrophilic group by condensation or the like.

  The addition method of (II) is not particularly limited, but it is directly added to the aqueous coating composition using (I) or (I), for example, as an emulsion described in JP-A-8-259892. Addition after water-solubilization by co-condensing (II) described in Kaihei 9-221611 and a hydrophilic group-containing silane compound such as γ-aminopropyltriethoxysilane, WO 1999/05228 (II) as a modified product having a polyoxyalkylene group described in JP-A-8-337754, a water-soluble or self-emulsifying type (block) isocyanate group-containing compound and / or carbodiimide compound And (II) as a mixture, and (I) synthetic resin including (II) described in JP-A-2002-138123 Such as the use of Marujon and the like.

  Among the addition methods of (II) above, addition as an emulsion, in particular, (II) silicon compounds and / or partially hydrolyzed condensates thereof using anionic surfactants and / or nonionic surfactants Addition as an emulsion obtained by dispersing in an aqueous medium is preferable in terms of improving storage stability in the aqueous coating composition, appearance of the resulting coating film, and the like.

  The aqueous medium used for this emulsion should just contain water as an essential component, and may contain the other organic solvent. Other organic solvents include alcohol solvents such as ethanol and isopropanol; glycol solvents such as propylene glycol; ether solvents such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol dimethyl ether, propylene glycol monobutyl ether acetate, Although ester solvents such as CS-12 manufactured by Chisso Corporation are listed, it is preferable not to contain an organic solvent from the viewpoint of stability of the emulsion and the environment.

  Examples of the anion of the anionic surfactant include polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene aryl ether sulfate such as polyoxyethylene polycyclic phenyl ether sulfate, and polyoxyethylene such as polyoxyethylene tridecyl ether sulfate. Sulfate ester having polyoxyethylene chain such as alkyl ether sulfate; Sulfate ester such as lauryl sulfate; Sulfonic acid such as lauryl sulfonic acid, dodecylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid; Di (2-ethylhexyl) Alkylsulfosuccinic acid such as sulfosuccinic acid; alkyl phosphate ester, polyoxyethylene alkyl ether phosphoric acid And phosphoric acid esters such as ester, and the like.

  Various neutralizing cationic species of the anionic surfactant can be selected. If an alkali metal, preferably sodium or potassium ion, is used, the (II) silicon compound and / or its partial hydrolysis in emulsions and aqueous coating compositions are used. The stability of the decomposition condensate can be improved.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid. Those having a polyoxyethylene chain such as ester; those having a hydroxyl group such as sorbitan fatty acid ester and glycerin fatty acid ester; KF-351, KF-352, KF-353, KF-354, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 355, KF-615, KF-618, KF-945, KF-907, X-22-6008, X-22-811, X-22-812, SH3748, SH3749, SH3771, SH8400 manufactured by Toray Dow Corning Silicone surfactants that are polyorganosiloxanes modified with polyalkylene oxide at one and / or both ends and / or side chains, such as SF8410 and SF8700; acetylene glycol surfactants, polyvinyl alcohol, hydroxyethyl cellulose, acrylamide Examples thereof include water-soluble polymer systems such as polymers.

  These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the silicon compound. If it is less than 0.05 part by weight, a stable emulsion cannot be obtained, and the storage stability is also lowered. If it exceeds 50 parts by weight, problems such as the appearance of the resulting coating film and a decrease in water resistance occur. The amount of the anionic surfactant that is an alkali metal salt in the total amount of the surfactant as the active ingredient amount should be 0.5 to 100 parts by weight with respect to 100 parts by weight of the total amount of the surfactant. (II) is preferable from the viewpoint of the stability of the emulsion of the silicon compound. More preferably, it is 30-100 weight part.

  This emulsion preferably has a pH of 6-10. Outside this range, hydrolysis / condensation of the silicon compound and / or its partially hydrolyzed condensate tends to occur and storage stability tends to decrease. In particular, when the pH is less than 6, hydrolysis is accelerated, and thus condensation proceeds rapidly. Moreover, when the pH is exceeded, not only is it unstable, but there are also operational problems.

  The method or order for adjusting and maintaining the pH is not particularly limited, but it is preferably performed from the time of preparation of the emulsion. The acid used to adjust the pH, the base, and the buffer used to maintain the pH are not particularly limited as long as they are generally used. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Examples of buffers such as ammonia and organic amines include carbonates such as sodium hydrogen carbonate and disodium hydrogen phosphate, phosphates, and carboxylates. Among these pH adjusters and buffering agents, those containing an alkali metal are preferred, and the use of sodium bicarbonate is more preferred.

  The solid content concentration of the silicon compound and / or its partially hydrolyzed condensate in the emulsion is preferably 5 to 60% by weight, more preferably 10 to 40% by weight. If the solid content concentration exceeds 60% by weight, the viscosity of (II) may increase, and the emulsion stability may be impaired. If it is less than 5% by weight, It is disadvantageous in terms of coating workability and coating film performance degradation, such as a thin film thickness.

  The preparation of the emulsion is performed by emulsifying the above components and the aqueous medium by a general emulsification method. As the emulsification method, a silicon compound and / or a partially hydrolyzed condensate thereof and a surfactant are mixed, water is slowly added thereto, and the phase inversion from a water-in-oil emulsion to an oil-in-water emulsion is so-called. Phase inversion emulsification method: a method in which each component is mixed, or after preliminary emulsification, mechanically finely dispersed with a disper, a high-pressure homogenizer, or the like.

  (II) is added in an amount of 1 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the solid content of (I) the synthetic resin emulsion. If the amount is less than 1 part by weight, the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 50 parts by weight, problems such as deterioration of the coating film appearance and cracks tend to occur.

(III) Silane coupling agent Although it does not specifically limit as a silane coupling agent which is (III) component, Aminosilane, an epoxy silane, a mercaptosilane, an isocyanate silane, ketiminosilane etc. are mentioned.

  Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ- (2-aminoethyl) aminopropyl. Trimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ- Examples include aminosilanes such as aminopropyltrimethoxysilane and γ-ureidopropyltrimethoxysilane, and bisalkoxysilyl type amines such as bis (trimethoxysilylpropyl) amine and bis (triethoxysilylpropyl) amine.

  Moreover, water-soluble aminosilane can also be used suitably, and DynasylanHS1151, DynasylanHS2627, DynasylanHS2776, DynasylanHS2909 (all are made by Evonik Degussa Japan Co., Ltd.), A-1106 (made by Momentive Performance Materials), etc. are mentioned as a commercial item. It is done.

  Specific examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

  Moreover, water-soluble epoxy silane can also be used suitably and DynasylanHS2926 (Evonik Degussa Japan Co., Ltd. product) etc. are mentioned as a commercial item.

  Specific examples of mercaptosilane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and the like.

  Specific examples of the isocyanate silane include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanatopropylmethyldiethoxysilane.

  Specific examples of the ketiminosilane include N- (1,3 dimethylbutylidene) -γ-aminopropyltrimethoxysilane and N- (1,3 dimethylbutylidene) -γ-aminopropyltriethoxysilane.

  In addition, aminosilane and epoxy silane such as a reaction product of γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane and a reaction product of γ-aminopropyltrimethoxysilane and γ-isocyanatopropyltrimethoxysilane. A silane coupling agent synthesized by reacting aminosilane and isocyanate silane can also be suitably used.

  Of these, bisalkoxysilyl-type amines, epoxy silanes, mercaptosilanes, and water-soluble silane coupling agents are preferable from the viewpoint of long-term adhesion stability.

  Furthermore, bisalkoxysilyl type amines and epoxy silanes are particularly preferred from the viewpoint of not causing a decrease in stain resistance due to storage and the point of odor.

  A silane coupling agent may be used independently and 2 or more types may be used together.

  Further, it may be added and mixed as it is at the time of blending or the like, or may be once added as an emulsion in order to improve the stability in water.

  The amount of (III) added is 0.05 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid content of (I) the synthetic resin emulsion. This is the amount to be part. If the amount is less than 0.05 part by weight, the effect of improving the adhesion of the obtained coating film tends to be insufficient. If the amount exceeds 30 parts by weight, problems such as deterioration of the appearance of the coating film, coloring, and a decrease in stability tend to occur. It is in.

(IV) Photosensitizer The photosensitizer as the component (V) in the present invention is not particularly limited, and examples thereof include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives, and the like. Specifically, 9,10-dialkoxyanthracene, 2-alkylthioxanthone, 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p'-aminobenzophenone, 2-hydroxy-4-alkoxybenzophenone And benzoin ether. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, butyl 2-benzoylbenzoate, Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Roaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene, etc. are mentioned. A photosensitizer may be used independently and 2 or more types may be used together.

  Among the above sensitizers, benzophenone, benzophenone derivatives such as 9,10-dipropoxyanthracene, anthracene derivatives are benzoin derivatives, benzyl and the like are in terms of improving surface hydrophilicity of coating films by light irradiation and resistance to yellowing. preferable.

  The method of adding (IV) is not particularly limited. For example, it is dissolved in (II) and added, dissolved in a film-forming aid or solvent, and added as a powder when (V) is solid. And (V) in the form of an emulsion are added.

  The amount of addition of (IV) needs to be adjusted according to the amount of generated base and the rate of generation, but (I) 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the synthetic resin emulsion, The amount is 0.5 to 20 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount is less than 0.05 parts by weight, the hydrolysis of the silicon compound does not proceed sufficiently, and the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration occur. Tend to occur.

  The resin composition for water-based paints of the present invention can be obtained by adding (I) to (IV) in any order and mixing. The mixing method can use a general mixing method, and is not particularly limited.

  The composition obtained from the above (I) to (IV) can be made into a one-component composition having stability in a dark place, and further forms an excellent hydrophilic surface by light exposure of the coating film. Is possible.

(V) Photoacid generator The photoacid generator as the component (VI) in the present invention is a compound that generates an acid upon exposure to light. For example, a strong acid such as toluenesulfonic acid or a sulfonium salt such as boron tetrafluoride, Onium salts such as ammonium salts, phosphonium salts, iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates And sulfonic acid derivatives such as benzoin sulfonates; organic halogen compounds and the like, and compounds that generate an acid upon irradiation with radiation as disclosed in JP-A-5-34412.

  Among the photoacid generators described above, sulfonic acid derivatives and organic halogen compounds having no ionicity are particularly (I) when the synthetic resin emulsion is provided with dispersion stability by an ionic surfactant. This is preferable in that the influence on the stability of the composition is small. Examples of the sulfonic acid derivatives include sulfonic acid esters such as benzoin tosylate, nitrobenzyl tosylate, and succinimide tosyl sulfonate disclosed in US Pat. No. 4,618,564; US Pat. No. 4,540,598 and JP-A-6-67433. Oxime sulfonates such as α- (4-tosyloxyimino) -4-methoxybenzylcyanide shown in Japanese Patent Publication No. 6-348015; tris (methanesulfonyloxy) benzene shown in Japanese Patent Publication No. 6-348015; And 9,10-dialkoxyanthracenesulfonic acid nitrobenzyl ester shown in No. 18143; N- (p-dodecylbenzenesulfonyloxy) -1,8-naphthalimide and the like. Examples of the organic halogen compounds include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halogen-containing triazine compounds disclosed in JP-A-55-32070, JP-A-48-36281, and JP-A-63-238339; 2-pyridyl-tri described in JP-A-2-304059 Halogen-containing sulfone compounds such as bromomethylsulfone; tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tri Halogenated alkyl phosphates such as (2,3-dibromopropyl) phosphate; halogen-containing heterocyclic compounds such as 2-chloro-6- (trichloromethyl) pyridine; 1,1-bis [p-chlorophenyl] -2 , 2,2-trichloroethane, vinylidene chloride copolymers, vinyl chloride copolymers, halogen-containing hydrocarbon compounds such as chlorinated polyolefins, and the like.

  The addition method of (V) is not particularly limited. For example, it is dissolved in (II) and added, dissolved in a film forming aid or solvent, and added as a powder when (V) is solid. And (V) in the form of an emulsion are added.

  The amount of (V) added needs to be adjusted according to the amount of acid generated and the rate of generation, but (I) 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the synthetic resin emulsion, The amount is 3 to 20 parts by weight. If the amount is less than 0.05 parts by weight, the acid generated is insufficient, and the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration tend to occur. It is in.

  The resin composition for water-based paints of the present invention can be obtained by adding (I) to (V) in any order and mixing. The mixing method can use a general mixing method, and is not particularly limited.

  The composition obtained from the above (I) to (V) can be a one-component composition having stability in a dark place, and further, the excitation of (IV) by the light exposure of the coating film, followed by The acid generated by the energy transfer to (V) occurring as a catalyst serves as a catalyst for the hydrolysis / condensation reaction of (II) and can form an excellent hydrophilic surface.

(VI) Photobase generator The photobase generator that is the component (VI) in the present invention is not particularly limited, and examples thereof include cobaltamine complexes, O-acyloximes, carbamic acid derivatives, formamide derivatives, and quaternary ammonium salts. , Tosylamine, carbamate, and amine imide compounds. Specific examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, and the like. . A photobase generator may be used independently and 2 or more types may be used together.

  As the photobase generator, an O-acyloxime compound is preferably used. Examples thereof include compounds represented by the following general formula (3).

(R ⁴ , R ⁵ , and R ⁶ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or the like. Have
The method of adding (VI) is not particularly limited. For example, it is dissolved in (II) and added, dissolved in a film-forming aid or solvent, and added as a powder when (VI) is solid. And (VI) in the form of an emulsion are added.

  The amount of (VI) added needs to be adjusted according to the amount and generation rate of the base to be generated, but (I) 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the synthetic resin emulsion, The amount is 0.5 to 20 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount is less than 0.05 parts by weight, the generated base is insufficient, and the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration tend to occur. It is in.

  The resin composition for water-based paints of the present invention can be obtained by adding (I) to (IV) and (VI) in any order and mixing. The mixing method can use a general mixing method, and is not particularly limited.

  The compositions obtained from the above (I) to (IV) and (VI) can be made into a one-component composition having stability in a dark place. The base generated by the excitation of the energy followed by the energy transfer to (VI) serves as a catalyst for the hydrolysis / condensation reaction of (II), and can form an excellent hydrophilic surface.

(VII) Inorganic Pigment The inorganic pigment which is the component (VII) in the present invention is not particularly limited, but pigments usually used in paints, for example, colored pigments such as titanium dioxide, carbon black and bengara, kaolin, talc, silica Body pigments such as aluminum phosphate, calcium carbonate, mica and clay, zinc phosphate, iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, molybdenum Examples thereof include rust preventive pigments such as aluminum oxide, calcium molybdate, aluminum phosphomolybdate, and aluminum zinc phosphomolybdate.

  The method for adding the inorganic pigment is not particularly limited, but it is directly added to the aqueous coating composition using (I) or (I), and the inorganic pigment is added to the ball mill or sand until the particle size becomes a predetermined uniform particle size. Examples of the pigment dispersion paste include dispersion in an aqueous medium using an ordinary dispersing apparatus such as a grind mill.

  Among the addition methods of the above (VII), addition as a pigment dispersion paste is preferable from the viewpoint of improving the storage stability in the aqueous coating composition, the appearance of the resulting coating film, and the like.

  The resin composition for water-based paints of the present invention can be obtained by adding (I) to (VII) in any order and mixing. The mixing method can use a general mixing method, and is not particularly limited.

  The amount of (VII) added needs to be adjusted according to the purpose, but I) is an amount that is 5 to 200 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the solid content of the synthetic resin emulsion. If it exceeds 200 parts by weight, problems such as deterioration of the coating film appearance tend to occur.

  The composition obtained from the above (I) to (VII) can be a composition having stability in a dark place. Furthermore, it is possible to form an excellent hydrophilic surface by light exposure of the coating film.

  About the compounding form of the resin composition for water-based paints of this invention, the 1 liquid type compounding form which mix | blended all the compounds is possible. The storage stability of the resin composition for water-based paints of the present invention is good, all formulations are blended, and it is stable for a long time in a sealed state protected from light, and the physical properties of the resulting coating film do not deteriorate.

  The resulting composition may contain organic pigments such as anthraquinone pigments, anthrapyrimidine pigments, azo pigments, azomethine pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, indanthrone pigments, isoindoline pigments, Film forming aids such as indolinone pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments, pyranthrone pigments, pyrazoloquinazolone pigments and thioindigo pigments; alcohols such as benzyl alcohol; ethylene glycol monobutyl ether, propylene glycol Glycols such as monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, ethylene glycol Glycol esters such as monobutyl ether acetate and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, colloidal silica, plasticizer, solvent, dispersant, wetting agent, thickener, preservative, Additives commonly used in paints such as antifreeze agents and antifoaming agents can also be added.

  The composition of the present invention is used for, for example, interior / exterior of buildings, automotive such as metallic base or clear on metallic base, direct coating of metal such as aluminum and stainless steel, slate, concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos It is used as a paint for ceramics such as board, precast concrete, lightweight cellular concrete, calcium oxalate plate, tile, brick, etc., for glass, natural marble, granite and other stones, or as a top treatment.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

(Materials used)
(Synthesis example of acrylic resin emulsion)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 160 parts by weight of deionized water as an initial charge, Newcol-707SN (manufactured by Nippon Emulsifier Co., Ltd .: 30% active ingredient, polyoxyethylene) Polycyclic phenyl ether sulfate sodium salt) 0.35 parts by weight, 0.25 parts by weight of 5% aqueous sodium hydrogen carbonate solution were charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas. After the temperature rise, 0.5 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 0.28 parts by weight of 20% Bruggolite FF-6 aqueous solution, 0.10% ferrous sulfate and heptahydrate and 0.40% 0.35 part of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium was added, and the first stage was 16.04 parts by weight of 2-ethylhexyl acrylate, 33 parts by weight of butyl methacrylate, 0.94 parts by weight of γ-methacryloxypropylmethyldimethoxysilane. ADEKA rear soap SR-10S (manufactured by ADEKA: 100% active ingredient, polyoxyethylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether sulfate sodium salt) 0.75 in 50 parts by weight of the mixture Part by weight, Adekaria soap ER-20 (manufactured by ADEKA Corporation: 75% active ingredient, polyoxye A monomer emulsion obtained by adding 0.47 part by weight of tylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether) and 20 parts by weight of deionized water was added at a constant rate over 200 minutes. Meanwhile, 0.55 parts by weight of 7% t-butyl hydroperoxide aqueous solution and 0.43 parts by weight of 2.5% Bruggolite FF-6 aqueous solution were added in three portions. Polymerization was performed after 1 hour after the addition of the monomer emulsion was completed. Further, 0.25 parts by weight of a 7% t-butyl hydroperoxide aqueous solution, 0.55 parts by weight of a 2.5% Bruggolite FF-6 aqueous solution, and 0.10% ferrous sulfate heptahydrate and 0.40% Add 0.35 parts of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium, and in the second stage, 9.25 parts by weight of methyl methacrylate, 37 parts by weight of butyl methacrylate, 0.5 parts by weight of γ-methacryloxypropyltriethoxysilane, polyoxy Adecalia Soap SR-10S in a mixture of 3 parts by weight of Blemmer PE-200 (manufactured by NOF Corporation), a vinyl monomer having an ethylene chain, and 0.25 parts by weight of n-dodecyl mercaptan. Monomer emulsion emulsified by adding 75 parts by weight, 0.47 parts by weight of Adeka Soap ER-20, and 20 parts by weight of deionized water Was added at a constant speed over 200 minutes. Meanwhile, 0.6 part by weight of 7% t-butyl hydroperoxide aqueous solution and 0.85 part by weight of 2.5% Bruggolite FF-6 aqueous solution were added in four portions. After completion of the addition of the monomer emulsion, polymerization was carried out 1.5 hours later. After adding 5.5 parts of 5% aqueous sodium hydrogen carbonate solution to the obtained emulsion, the solid content was adjusted to 50% with deionized water to obtain an acrylic resin emulsion (I-1). The obtained emulsion had a volume average particle size of 200 nm by a dynamic light scattering particle size measuring device MICROTRAC UPA MODEL 9340-UPA manufactured by Nikkiso Co., Ltd.

(Example of production of emulsion of silicon compound)
Silicate 40 (manufactured by Tama Chemical Co., Ltd.) 30 parts by weight, Neocor SW-C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 70%, dialkylsulfosuccinic acid sodium salt) 10 parts by weight, Haitenol XJ-630S ( Daiichi Kogyo Seiyaku Co., Ltd .: Mixture of 28% active ingredient, polyoxyalkylene alkyl ether sulfate ammonium salt and polyoxyalkylene alkyl ether) 6% 5% sodium bicarbonate water, 4 parts deionized water at 40 ° C Added with stirring. After 1 hour, 50 parts by weight of deionized water was added dropwise at 40 ° C. to obtain an emulsion of a silicon compound (II-1) having an effective solid content concentration of 30%.

(Production example of aqueous resin composition)
An acrylic resin emulsion (I-1) 51.5 parts by weight, a silicon compound (II-1) emulsion 8.5 parts by weight of (I) solid content 100 parts by weight (II) silicon compound and / or 10 parts by weight of its partially hydrolyzed condensate} was added, and mixed at room temperature with a stirrer for 10 minutes. In this mixture, 29 parts by weight of the pigment paste shown in Table 1, 0.7 part of Adekaol UH-526 manufactured by ADEKA Co., Ltd. as a thickener, and deionized water obtained by making Natrozol Plus 330 made by Aqualon basic with aqueous ammonia 3.4 parts of a 3 wt% solution obtained by dissolution, 0.2 part of AGITAN295 made by MUNZING CHEMIE as an antifoaming agent, 3.2 parts of 5% sodium bicarbonate water, and 4. part of dipropylene glycol monobutyl ether as a film forming aid. 8 parts and further the additives shown in Table 3 were added at room temperature with stirring to obtain a white enamel paint.

  On a JIS A5430 slate plate having a thickness of 4 mm, a width of 40 mm, and a length of 150 mm, a sealer, an undercoat material and an intermediate coat material shown in Table 2 were applied and dried with an air spray at room temperature at a coating interval of 1 day.

  The white enamel paint shown in Table 3 was applied by air spray at room temperature with a coating interval of 24 hours so that the dry film thickness would be about 30-40 μm, and cured for 7 days at room temperature in a room not exposed to direct sunlight. A coated plate was prepared. A cross-cut adhesion test (primary adhesion) was performed on the prepared coated plates, and these coated plates were fixed at a south surface of 45 ° in Takasago City, Hyogo Prefecture, and exposed outdoors for 2 weeks. Then, it was immersed in 23 degreeC water for 7 days, and the cross-cut adhesion test (secondary adhesion) was done. In addition, the coated plate made by applying the white enamel paint twice with a coating interval of 1 day using the substrate 6 is cured at room temperature in a room not exposed to direct sunlight for 7 days, and then at an angle of 30 °. Subjected to outdoor exposure, water contact angle and contamination resistance were tracked.

  Further, for the white enamel paints shown in Table 3 which were stored at 50 ° C. for 2 weeks under shading, the water contact angle was followed in the same manner. The results are shown in Table 3.

The measurement was performed according to the following method.
Cross-cut adhesion test A cross-cut adhesion test at intervals of 2 mm was performed in accordance with JIS K5600.
-Water contact angle The contact angle measuring device CA-S150 by Kyowa Interface Science Co., Ltd. was used, and the contact angle of pure water was measured. The lower the value, the higher the surface hydrophilicity and the better the stain resistance. When the value is 70 ° or less, the effect of the stain resistance in the actual outdoor exposure test tends to be remarkable.
・ Contamination resistance Using a color meter CR-300 manufactured by Minolta Co., Ltd., measured L *, a *, b * values before the start of exposure and during each exposure period, and L * and start of exposure during each exposure period The brightness difference (ΔL) was calculated from the previous L *. The smaller the absolute value of ΔL, the smaller the hue change due to the adherence of contaminants, and the better the stain resistance.

  In Examples 1 to 10 in which a specific silane coupling agent was blended, secondary adhesion (after water resistance) was improved in most base materials compared to Comparative Examples 1 to 3. Further, in Comparative Example 5, there was a substrate on which no improvement in adhesion was observed.

  Moreover, the water contact angle in outdoor exposure also decreased to 70 ° or less after one month, and excellent surface hydrophilization due to exposure under actual use conditions was observed. In particular, when epoxy silane or bis (alkoxysilylalkyl) amine was blended, the water contact angle decreased to the same extent as in Comparative Examples 1 to 3 without the silane coupling agent. Although Example 5 which mix | blended water-soluble aminosilane was also slow, the water contact angle fell to 70 degrees or less.

  On the other hand, in Comparative Example 4 with relatively good adhesion, the water contact angle was 70 ° or more, and no surface hydrophilization was observed. Also in Comparative Example 5, no decrease in contact angle was observed.

  Also for the white enamel paint stored at 50 ° C., the water contact angle decreased to 70 ° or less, and surface hydrophilicity was developed. In addition, there exists a tendency for stain resistance to improve by expressing hydrophilicity.

  Regarding actual stain resistance, Examples 1 to 10 had a small absolute value of ΔL and exhibited good stain resistance.

  As described above, it was confirmed that the resin composition of the present invention has improved adhesion to the base while maintaining surface hydrophilicity and stain resistance. Further, even in the one-pack type paint form, it was confirmed that it was useful as an aqueous resin composition that maintained good surface hydrophilicity and gave a coating film excellent in adhesion to the base and stain resistance.

Claims (19)

(I) Synthetic resin emulsion (II) A silicon compound represented by the following general formula (1) and / or a partial hydrolysis condensate thereof and / or a modified product thereof (R ¹ O) _4-a SiR ² _a (1)
(Wherein R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ² is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)
(III) A resin composition for aqueous coatings containing a silane coupling agent (IV) a photosensitizer and / or (V) a photoacid generator and / or (VI) a photobase generator. (II) The silicon compound and / or its partially hydrolyzed condensate and / or its modified product is an organosilicate (compound represented by the following general formula (2) and / or its partially hydrolyzed condensate) and / or its modified product The resin composition for water-based paints according to claim 1 which is a thing.
(R ³ O) ₄ Si (2)
(Wherein R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms)   (III) The resin composition for paints according to any one of claims 1 to 2, wherein the silane coupling agent is one or more selected from aminosilane, epoxysilane, and mercaptosilane.   (III) The resin composition for paints according to any one of claims 1 to 3, wherein the silane coupling agent is epoxysilane and / or bis (alkoxysilylalkyl) amine.   (I) The synthetic resin emulsion is an acrylic resin emulsion having an alkoxysilyl group-containing monomer unit, The resin composition for water-based paints according to any one of claims 1 to 4.   (I) The surfactant used for a synthetic resin emulsion is an anionic surfactant which is an alkali metal salt, The resin composition for water-based paints of any one of Claims 1-5.   (II) As an emulsion obtained by dispersing a silicon compound and / or a partially hydrolyzed condensate thereof and / or a modified product thereof in an aqueous medium using a nonionic surfactant and / or an anionic surfactant The resin composition for water-based paints of any one of Claims 1-6 added.   The water-based paint according to claim 7, wherein the surfactant used in the emulsion of (II) silicon compound and / or a partially hydrolyzed condensate thereof and / or a modified product thereof is an anionic surfactant which is an alkali metal salt. Resin composition.   (IV) The photosensitizer is at least one selected from the group consisting of anthracene derivatives, acetophenone derivatives, benzophenone derivatives, thioxanthone derivatives, and anthraquinone derivatives. Resin composition for paint.   The resin composition for water-based paint according to claim 9, wherein the photosensitizer (IV) is a compound having a benzophenone skeleton or an anthracene skeleton.   (V) The photo-acid generator is an organic halogen compound, The resin composition for water-based paints of any one of Claims 1-10.   The resin composition for water-based paints according to claim 11, wherein the photoacid generator is a halogen-containing triazine compound, a vinylidene chloride copolymer, a vinyl chloride copolymer, or a chlorinated polyolefin.   (V) The photo-acid generator is sulfonium salts, The resin composition for water-based paints of any one of Claims 1-10.   (VI) The photobase generator is one or more selected from the group consisting of cobaltamine complexes, O-acyloximes, carbamic acid derivatives, formamide derivatives, quaternary ammonium salts, tosylamines, carbamates, and amine imide compounds. The resin composition for water-based paints according to any one of claims 1 to 13.   (VI) The photobase generator is an O-acyloxime compound, The resin composition for water-based paints of Claim 14. (VI) The photobase generator is an O-acyloxime having an aryl group represented by the general formula (3).

(R ⁴ , R ⁵ , and R ⁶ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or the like. Have   Furthermore, the resin composition for water-based coatings of any one of Claims 1-16 containing an inorganic pigment (VII).   The resin composition for one-component water-based paints according to any one of claims 1 to 17. A coated product and a coating film obtained from the one-component aqueous coating composition according to claim 1.