CN105086819B

CN105086819B - Aqueous coating agent composition, film and coated articles

Info

Publication number: CN105086819B
Application number: CN201510259262.4A
Authority: CN
Inventors: 月森康之; 青柳尚久; 小迫勲
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2014-05-21
Filing date: 2015-05-20
Publication date: 2018-05-25
Anticipated expiration: 2035-05-20
Also published as: CN105086819A; JP6140764B2; TWI570194B; TW201610022A; JP2016000808A

Abstract

The present invention provides a kind of aqueous coating agent composition, film and coated articles, which can form the film that can maintain appearance and stain resistance with high level for a long time.A kind of aqueous coating agent composition, it contains the dispersion of copolymer (C) (CD) and inorganic oxide (D), the copolymer (C) includes structural unit (A) and structural unit (B), the structural unit (A) derives from the silane (a) with specific structure, and the structural unit (B) derives from the silane (b) with specific structure；The content of structural unit (A) in copolymer (C) is scaled 32~70 mass % with hydrolytic condensate, and the content of the structural unit (B) in copolymer (C) is scaled 23~45 mass % with hydrolytic condensate.

Description

Aqueous coating agent composition, film and coated articles

Technical field

The present invention relates to aqueous coating agent composition, film and coated articles.

Background technology

The external coating of the outdoor constructions object such as construction exterior, bridge, tank has coating etc., but its film coated surface is by air Dust, coal smoke, sand etc.；By the dirt composition dissolved out in sealing material；And the polluter discharged by the outlet of building Deng being polluted.The pollution of such film is usually light/dark balance, the beauty of notable crime of injuries by explosive substances to buildings and goods therein and outdoor construction object.

As the aqueous upper coating layer agent composition as described above for applying fouling membrane is inhibited, applicant proposed a kind of bilayers Film, possesses priming coat and the upper coating being arranged on the priming coat, and above-mentioned priming coat is to make containing polymer emulsion particles (A) dried coating film of primary coat coating agent composition (I) and the film formed, the polymer emulsion particles (A) are using including Obtained from the method for making the process that vinyl monomer and water-disintegrable silicon compound polymerize respectively in the presence of water and emulsifier； Above-mentioned upper coating is makes the film that the dried coating film of painting coating agent composition (II) is formed, painting coating agent composition on this (II) metal oxide particle (B), polymer emulsion particles (C) and cabosil (D) with photocatalytic activity are included, it should Polymer emulsion particles (C) are to make vinyl monomer and water-disintegrable silicon compound point using being included in the presence of water and emulsifier (referring to patent document 1) obtained from the method for the process not polymerizeing.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2010-005595 publications

The content of the invention

Problem to be solved by the invention

Patent document 1 record technology in, the material for having used glass transition temperature high as priming coat, therefore even if For the upper coating formed by upper painting coating agent composition, sufficient stain resistance and weatherability also can obtain.In this way, patent is literary 1 technology is offered as excellent technology, but the present inventor attempts to carry out further improvement to develop superior technology.Example Such as, by such upper painting described in patent document 1 with being applied to general in construction exterior etc. use on coating agent composition When glass transition temperature is on the base material of -5~20 DEG C or so of material, the upper coating that is formed by upper painting with coating agent composition Sometimes it cannot fully follow variation for being subject to ambient temperature etc. and flexible base material occurs.Under such circumstances, have in upper coating When can generate cracking etc., also sometimes because the cracking cause gloss reduce due to damage appearance.And then in the part of cracking also sometimes Adhere to dust, coal smoke, sand etc. and be contaminated., can be from the limitation of base material if the above-mentioned aspect of film can be improved, it and being capable of the phase A kind of long-term excellent film of various physical property headed by appearance and stain resistance to be achieved.

The present invention has been made in view of the above-described circumstances, it is therefore an objective to which providing one kind can form and can be maintained for a long time with high level The aqueous coating agent composition of the film of appearance and stain resistance.

The means solved the problems, such as

Present inventor has performed further investigation, it turns out that, by using following aqueous coating agent compositions, solve The above problem, so as to complete the present invention, the aqueous coating agent composition contain the dispersion (CD) of copolymer (C) and inorganic Oxide (D), the copolymer (C) include structural unit (A) and structural unit (B), and the structural unit (A), which derives from, has spy Determine the silane (a) of structure, structure of the structural unit (B) in the silane (b) with specific structure, copolymer (C) The content of structural unit (B) in the content and copolymer (C) of unit (A) is in specific scope.

That is, the present invention is as described below.

[1]

A kind of aqueous coating agent composition, contains：

The dispersion (CD) of copolymer (C), the copolymer (C) include structural unit (A) and structural unit (B), the knot Structure unit (A) is derived from as the silane (a) shown in the following general formula (1), and the structural unit (B) is derived from by the following general formula (2) Shown silane (b)；With

Inorganic oxide (D)；

The content of said structure unit (A) in above-mentioned copolymer (C) is scaled 32~70 mass % with hydrolytic condensate,

The content of said structure unit (B) in above-mentioned copolymer (C) is scaled 23~45 mass % with hydrolytic condensate.

(R¹)₂-Si-(R²)₂···(1)

(R¹Each independently represent hydrogen atom, the aliphatic alkyl that carbon number is 1~16, carbon number are 6~10 The acrylic acid alkyl ester group or carbon number that cycloalkyl that aryl, carbon number are 5~6, phenyl, carbon number are 1~10 For 1~10 alkyl methacrylate base, R²Each independently represent carbon number be 1~8 alkoxy, acetoxyl group, Or hydroxyl.)

R³-Si-(R⁴)₃···(2)

(R³Represent that aliphatic alkyl, carbon number that hydrogen atom, carbon number are 1~16 are 6~10 aryl, carbon atom Count the acrylic acid alkyl ester group that the cycloalkyl for 5~6, phenyl, carbon number are 1~10 or the first that carbon number is 1~10 Base acrylic acid alkyl ester group, R⁴Each independently represent alkoxy, acetoxyl group or the hydroxyl that carbon number is 1~8.)

[2]

Aqueous coating agent composition as described in [1], wherein, the dispersion (CD) of above-mentioned copolymer (C) is by least Using above-mentioned silane (a) and above-mentioned silane (b) and obtained from carrying out emulsion polymerization.

[3]

Aqueous coating agent composition as described in [1] or [2], wherein, above-mentioned inorganic oxide (D) is silica.

[4]

Such as [1]~[3] any one of them aqueous coating agent composition, wherein, the composition, which further contains, to be had The inorganic oxide (E) of photocatalytic activity.

[5]

Such as [1]~[4] any one of them aqueous coating agent composition, wherein, the composition further contains fluorine carbon Surfactant (F).

[6]

Such as [1]~[5] any one of them aqueous coating agent composition, wherein, the composition is further containing colour fading Property pigment (G).

[7]

Such as [1]~[6] any one of them aqueous coating agent composition, wherein, the composition further contains fiber Prime system thickener (H).

[8]

Such as [1]~[7] any one of them aqueous coating agent composition, wherein, the composition, which further contains, to be selected from The substance of one or more of the group be made of algaecide and mould inhibitor (J).

[9]

A kind of aqueous coating contains [1]~[8] any one of them aqueous coating agent composition.

[10]

A kind of film is obtained as the aqueous coating described in [9].

[11]

A kind of coated articles, containing the film described in base material and [10], which is formed at the surface of above-mentioned base material At least partially.

[12]

Coated articles as described in [11], wherein, above-mentioned base material is organic substrate.

Invention effect

In accordance with the invention it is possible to provide a kind of aqueous coating agent composition, said composition can be formed can be for a long time with Gao Shui The flat film for maintaining appearance and stain resistance.

Specific embodiment

Present embodiment (hereinafter referred to as " present embodiment ") is illustrated below.Following present embodiment is For illustrating the illustration of the present invention, it is not intended that limit the invention to herein below.The present invention can be in the range of its main points It suitably deforms and implements.As long as it should be noted that not special declaration, " (methyl) acrylate " refer to " acrylate " and with Its corresponding " methacrylate ", " (methyl) acrylic acid " refer to " acrylic acid " and corresponding " methacrylic acid ".

[waterborne compositions]

The waterborne compositions of present embodiment contain the dispersion (CD) of copolymer (C) and inorganic oxide (D), the copolymerization Object (C), which includes, to be derived from as the structural unit (A) of the silane (a) shown in general formula (1) and from as the silane shown in general formula (2) (b) structural unit (B).Also, in aqueous coating agent composition, the content of the structural unit (A) in copolymer (C) is to hydrolyze Condensation product is scaled 32~70 mass %, and the content of the structural unit (B) in copolymer (C) is scaled 23 with hydrolytic condensate~ 45 mass %.

Dispersion (CD) is the dispersion of copolymer (C).As the dispersion of copolymer (C), be not particularly limited, from for It is preferably aqueous dispersion from the aspect of water-based.As such aqueous dispersion, it can be cited for example that, use (a) ingredient, (b) Ingredient and the water-disintegrable silicon compound and/or vinyl monomer in addition to (a) ingredient and (b) ingredient being added as needed on Deng aqueous dispersion (CD) of copolymer (C) etc. obtained from progress emulsion polymerization.

Copolymer (C) contains is calculated as the structural unit (A) of 32~70 mass %, with hydrolysis with hydrolytic condensate conversion ingredient Condensation product conversion ingredient is calculated as the structural unit (B) of the ratio of 23~45 mass %.Structural unit (A) in copolymer (C) When the content of content and structure of unit (B) is outside above range, the weatherability and stain resistance of film become inadequate.It needs Bright, hydrolytic condensate described herein refers to the reactive group of (a) ingredient contained in such as system and (b) ingredient (such as alkoxy etc.) is by hydrolyzing with condensation reaction to be converted to the condensation products of silanol bonds.Structural unit (A) and structure list The copolymerization that the content (quality %) of the hydrolytic condensate conversion of first (B) can be obtained according to the heating residue as (CD) ingredient Content (total solid content content), (a) ingredient, the inventory of (b) ingredient of object (C) are obtained using calculating.Specifically, It can be obtained using method recorded in aftermentioned embodiment.In addition, structural unit (A) and structure list in copolymer (C) The content (quality %) of first (B) can also be used Si solid NMRs and directly measure.

The lower limiting value of the content of structural unit (A) in copolymer (C) for more than 32 mass %, be preferably 47 mass % with On.The upper limit value of the content of structural unit (A) in copolymer (C) is below 70 mass %, is preferably below 65 mass %.

The lower limiting value of the content of structural unit (B) in copolymer (C) for more than 23 mass %, be preferably 25 mass % with On.The upper limit value of the content of structural unit (B) in copolymer (C) is below 45 mass %, is preferably below 39 mass %, more Preferably below 35 mass %.

As the concrete example of the silane (a) shown in general formula (1), dimethyldimethoxysil,ne, dimethyl two can be enumerated Ethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diη-propyl dimethoxysilane, two positive third Base diethoxy silane, diisopropyl dimethoxy silane, diisopropyldiethoxysilane, di-n-butyl dimethoxy silicon Alkane, second, isobutyl dimethoxy silane, di-n-butyl diethoxy silane, two n-pentyl dimethoxysilanes, two n-pentyls two Ethoxysilane, di-n-hexyl dimethoxysilane, di-n-hexyl diethoxy silane, two n-heptyl dimethoxysilanes, two N-heptyl diethoxy silane, di-n-octyl dimethoxysilane, di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxies Base silane, two positive cyclohexyl diethoxy silanes, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, diformazan Oxygroup aminomethyl phenyl silane, diphenyl diethoxy silane, 3- (methyl) acryloxypropyl dimethoxysilane etc..

Among these, from the weatherability of obtained film and stain resistance aspect, preferably dimethylformamide dimethyl oxygen Base silane, dimethyl diethoxysilane, diisopropyl dimethoxy silane, dimethoxydiphenylsilane, dimethoxy first Base phenyl silane, more preferable dimethyldimethoxysil,ne, dimethoxymethylphenylsilane, further preferred dimethylformamide dimethyl Oxysilane.These can be used alone, and can also share two or more.

As the concrete example of the silane (b) shown in general formula (2), methyltrimethoxysilane, three ethoxy of methyl can be enumerated Base silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl trimethoxy silane, n-propyl triethoxysilicane Alkane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, n-butyltrimethoxysilane, normal-butyl triethoxysilicane Alkane, n-pentyl trimethoxy silane, n-hexyl trimethoxy silane, n-heptyl trimethoxy silane, n-octyl trimethoxy silicon Alkane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilanis, cyclohexyl trimethoxy silicon Alkane, cyclohexyltriethyloxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3- (methyl) acryloxy third Base trimethoxy silane, 3- (methyl) acryloxypropyls triethoxysilane, 3- (methyl) acryloxypropyl three are just Npropoxysilane, three isopropoxy silane of 3- (methyl) acryloxypropyl, vinyltrimethoxysilane, three second of vinyl Oxysilane etc..Among these, from the hydrolysis rate and the weatherability and stain resistance of obtained film during polymerization etc. Aspect is set out, preferably methyltrimethoxysilane, phenyltrimethoxysila,e, 3- (methyl) acryloxypropyl trimethoxy Silane.These can be used alone, and can also share two or more.

As for manufacturing the water-disintegrable silicon compound in addition to (a) ingredient and (b) ingredient of copolymer (C), there is no spy It does not limit, preferably enumerates the following general formula (3) compound represented and their condensation product etc..

SiW_xR_y···(3)

In formula, W represents to be selected from the acetyl oxygen that the alkoxy for being 1~20 by carbon number, hydroxyl, carbon number are 1~20 What base, halogen atom, hydrogen atom, the oximido that carbon number is 1~20, alkene oxygen (エノキシ) base, aminooxy group and amide groups formed At least one of group.Alkyl that it is 1~30 by the carbon number of straight-chain or branched that R, which represents to be selected from, carbon number be 5~ The aryl composition that alkoxy that 20 cycloalkyl, carbon number are 1~20, the carbon number with halogen atom substitution are 6~20 At least one of group group.X is less than more than 14 integer, and y is less than more than 03 integer, meets the pass of x+y=4 System.When W is 2 or more, when R is 2 or more, each W and R mutually may be the same or different.

The silicon alkoxide of a mode as the water-disintegrable silicon compound shown in general formula (3), as long as being (a) ingredient and (b) Substance beyond ingredient is just not particularly limited, it can be cited for example that tetramethoxy-silicane, tetraethoxysilane, four positive propoxies The tetraalkoxysilanes classes such as silane, tetraisopropoxysilan, four n-butoxy silanes.In tetraalkoxysilane, from polymerization when It sets out in terms of hydrolysis rate, preferably tetramethoxy-silicane, tetraethoxysilane.These can be used alone, can also It shares two or more.

As the concrete example for the vinyl monomer that can be used in the manufacture of copolymer (C), it can be cited for example that (methyl) Acrylate, aromatic ethenyl compound, vinyl cyanide compound, carboxylic vinyl compound, the ethylene of hydroxyl Based compound, the vinyl compound containing glycidyl, the vinyl compound with secondary amide base and/or teritary amide base, The vinyl monomer containing functional group such as anionic vinyl based compound.

As the concrete example of (methyl) acrylate, be not particularly limited, it can be cited for example that with carbon number for 1~ (methyl) alkyl acrylate of 50 alkyl, (poly-) ethylene oxide two with the oxyethylene group that carbon number is 1~100 (methyl) acrylate etc..

As the concrete example of (methyl) acrylate, it is not particularly limited, it can be cited for example that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) propylene acid methyl Cyclohexyl, (methyl) cyclohexyl acrylate, (methyl) lauryl acrylate, (methyl) dodecylacrylate etc..

It as the concrete example of (poly-) ethylene oxide two (methyl) acrylate, is not particularly limited, it can be cited for example that two (first Base) acrylic acid glycol ester, two (methyl) acrylic acid diethylene glycol (DEG) esters, methoxyl group (methyl) acrylic acid diethylene glycol (DEG) ester, two (methyl) Acrylic acid tetraethylene glycol ester etc..

It as the concrete example of aromatic ethenyl compound, is not particularly limited, it can be cited for example that styrene, Alpha-Methyl Styrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene etc..

It as the concrete example of vinyl cyanide compound, is not particularly limited, it can be cited for example that acrylonitrile, metering system Nitrile, α-chloro-acrylonitrile etc..

It as the concrete example of carboxylic vinyl compound, is not particularly limited, it can be cited for example that acrylic acid, methyl The binary acid such as acrylic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride or itaconic acid, maleic acid, fumaric acid Half ester.By using the vinyl monomer containing carboxyl, carboxyl can be imported in structural unit (A).It in this way, can be further It improves as emulsion intercalation method, thus it is speculated that can be to there is high resistance (but this embodiment party from external scattered destruction The effect of formula is not limited to these).At this point, part or all of the carboxyl imported can also use ammonia, triethylamine, dimethyl second The alkali such as the amines such as hydramine, NaOH, KOH are neutralized.Carboxylic vinyl monomer in the total amount of above-mentioned vinyl monomer Dosage from water resistance aspect preferably 0~10 mass %, but it is not limited to this.

The concrete example of vinyl compound as hydroxyl, is not particularly limited, it can be cited for example that (methyl) propylene Acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -3- hydroxypropyl acrylates, (methyl) acrylic acid -2- hydroxyl fourths The hydroxyalkyl acrylate of (methyl) acrylic acid such as ester, (methyl) acrylic acid -3- hydroxy butyl esters, (methyl) acrylic acid -4- hydroxy butyl esters；Two- 2- hydroxyethyls fumarate, single -2- hydroxyethyl monobutyls fumarate, the number of allyl alcohol or oxyethylene group for 1~ 100 (poly-) ethylene oxide list (methyl) acrylate；The number of oxypropylene group is 1~100 (poly-) oxypropylene list (methyl) Acrylate and " PRAXCELL FM, FA monomers " (commodity of the caprolactone addition monomer of Daicel Chemical societies manufacture Name), others α, the hydroxy alkyl esters of β-ethylenic unsaturated carboxylic acid.

It as the concrete example of (poly-) ethylene oxide (methyl) acrylate, is not particularly limited, it can be cited for example that (methyl) Acrylic acid glycol ester, methoxyl group (methyl) acrylic acid glycol ester, (methyl) acrylic acid diethylene glycol (DEG) ester, methoxyl group (methyl) third Olefin(e) acid diethylene glycol (DEG) ester, (methyl) acrylic acid tetraethylene glycol ester, methoxyl group (methyl) acrylic acid tetraethylene glycol ester etc..

The concrete example of (poly-) oxypropylene (methyl) acrylate, is not particularly limited, it can be cited for example that (methyl) propylene Acid propylene glycol ester, methoxyl group (methyl) propylene acid propylene glycol ester, (methyl) acrylic acid dipropylene glycol ester, methoxyl group (methyl) propylene Sour dipropylene glycol ester, four propylene glycol ester of (methyl) acrylic acid, four propylene glycol ester of methoxyl group (methyl) acrylic acid etc..

It as the concrete example of the vinyl compound containing glycidyl, is not particularly limited, it can be cited for example that (first Base) glycidyl acrylate, the sweet base ether of allyl glycidyl, allyl dimethyl base glycidol ether etc..

It as the concrete example of the vinyl monomer with secondary amide base and/or teritary amide base, is not particularly limited, Ke Yiju Go out such as N- alkyl substitutes (methyl) acrylamide, N- alkylidenes substitution (methyl) acrylamide.

As the concrete example of N- alkyl substitution (methyl) acrylamide, it is not particularly limited, it can be cited for example that N- methyl (methyl) acrylamide, N- ethyls (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl acryloyls Amine, N- methyl-N ethyls (methyl) acrylamide, N- isopropyls (methyl) acrylamide, N- n-propyls (methyl) acrylamide, N- methyl-N-n-propyls (methyl) acrylamide, N- methyl-N-isopropyls (methyl) acrylamide, N- (methyl) acryloyl pyrrole Cough up alkane, N- (methyl) Antiepilepsirin, N- acryloyl hexahydros azepine, N- (methyl) acryloyl morpholine, N- vinyl pyrroles Alkanone, N- caprolactams, N, N '-di-2-ethylhexylphosphine oxide (methyl) acrylamide, N- vinyl acetamides, two acetone (methyl) Acrylamide, N- methylols (methyl) acrylamide etc..

As the concrete example of the vinyl monomer beyond above-mentioned substance, it can be cited for example that (methyl) acrylamide, ethylene, The olefines such as propylene, isobutene；The dienes such as butadiene；Ethlyene dichloride, vinylidene chloride, ethylene fluoride, tetrafluoroethene, trifluoro The haloalkenes hydro carbons such as vinyl chloride；Vinyl acetate, vinyl propionate, vinyl propionate, vinyl benzoate, to tert-butyl benzene The generating vinyl carboxylates such as vinyl formate, new vinyl acetate acid, 2 ethyl hexanoic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate base Base ester class；The carboxylic acids isopropenyl esters such as isopropyl acetate alkenyl esters, propionic acid isopropenyl ester；Ethyl vinyl ether, isobutyl group second The vinyl ethers such as alkene ether, cyclohexyl vinyl ether；The aromatic ethenyl compounds such as styrene, vinyltoluene；Acetic acid The pi-allyls esters such as allyl ester, benzoic acid allyl ester；The allyl ether series such as pi-allyl ether, pi-allyl phenylate；4- (first Base) acryloxy -2,2,6,6- tetramethyl piperidines, 4- (methyl) acryloxy -1,2,2,6,6- pentamethvls, perfluor Methyl (methyl) acrylate, perfluoro propyl (methyl) acrylate, perfluoro propyl methyl (methyl) acrylate, vinylpyridine Pyrrolidone, trimethylolpropane tris (methyl) acrylate, (methyl) allyl acrylate etc..These substances can individually make With one kind, can also share two or more.

In the case of manufacturing copolymer (C) by polymerisation in present embodiment, in order to control used ethylene The molecular weight of the polymerizate of base monomer can use chain-transferring agent.

It as the concrete example of chain-transferring agent, is not particularly limited, it can be cited for example that n octylmercaptan, dodecyl sulphur The alkyl mercaptos alcohols such as alcohol, tert-dodecylmercaotan；Aromatic mercaptans class as benzyl mercaptan, dodecyl benzyl mercaptan；Thiol apple The thiocarboxylic acids such as tartaric acid or their salt or their alkyl esters；Polythiols；Dithiodiisopropyl xanthate, two sulphur Change the disulfides such as two (methylene tri hydroxymethyl-propane) xanthates；Thioglycol, the dimer of α-methylstyrene Wait allyl compounds etc..These substances can be used alone, and can also share two or more.

Total dosage of chain-transferring agent is preferably 0.001~1.0 mass % compared with the total amount of above-mentioned vinyl monomer.

It as the emulsifier that can be used in the manufacture of copolymer (C), is not particularly limited, it can be cited for example that alkylbenzene Sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinate, polyxyethylated sulfuric acid, polyxyethylated aromatic sulfuric acid, polyoxyethylene two The acidity such as styrylphenyl ether sulfonic acid emulsifier, alkali metal (Li, Na, K etc.) salt of acid emulsifier, the ammonium of acid emulsifier The anionic surfactant such as salt, fatty acid soaps；Such as alkyl trimethyl ammonium bromide, cetylpyridinium bromide, the imidazoline moon The quaternary ammonium salts such as cinnamic acid salt, pyridiniujm, the cationic surface active agent of imidazoline salt form, polyxyethylated aryl Ether, Polyoxyethylene Sorbitan acid esters, polyoxyethylene oxypropylene block copolymer, polyoxyethylene diphenylethyllene phenyl ether Wait nonionic surface active agent；Reactive emulsifier with free-radical polymerised double bond etc..

In these emulsifiers, the reactive emulsifier (reactive emulsifier) of free-radical polymerised double bond is preferably had.It is logical It crosses using such reactive emulsifier, the dispersion stability of polymer beads is very good, and obtained film Water resistance also further improves.

For the anionic emulsifier as reactive emulsifier, it can be cited for example that with sulfonic group, sulfonate group Or ethylenically unsaturated monomers of sulfate group and their salt etc., preferably have sulfonic group or as its ammonium salt or alkali gold Belong to the compound of the group (sulfonic acid ammonium or alkali metal sulfamate alkali) of salt.Specifically it can be cited for example that polyoxyethylene Base sulfosuccinate is (it can be cited for example that the manufacture of chemical conversion society of Sanyo, " ELEMINOL (trade mark) JS-20 "；Such as Hua Wang societies system Make, " LATEMUL (trade mark) S-120 ", " LATEMUL S-180A ", " LATEMUL S-180 " etc.), it is for example polyxyethylated Allyl phenyl ether sulfuric acid (it can be cited for example that the first industrial pharmaceutical society manufactures, " Aquaron (trade mark) HS-10 " etc.), Such as α-[1- [(allyloxy) methyl] -2- (Nonylphenoxy) ethyl]-ω-polyoxyethylene sulfates (can enumerate example If ADEKA societies manufacture, " Adeka Reasoap (trade mark) SE-10N " etc.), such as ammonium-α-sulfonate radical conjunction-ω -1- (allyloxys Methyl) alkyl oxy polyoxyethylene (it can be cited for example that the first industrial pharmaceutical society manufactures, " Aquaron KH-1025 " etc.), example As styrene sulfonate (it can be cited for example that Tosoh organic chemistry society manufactures, " Supinoma (trade mark) NaSS " etc.), such as α- [2- [(allyloxy) -1- (alkyl oxy methyl) ethyl]-ω-polyoxyethylene sulfates is (it can be cited for example that ADEKA societies Manufacture, " Adeka Reasoap (trade mark) SR-1025 " etc.), such as polyoxyethylene polybutylene (3- methyl -3- cyclobutenyls) ether Sulfuric acid (it can be cited for example that Hua Wang societies manufacture, " LATEMUL (trade mark) PD-104 " etc.) etc..Among these, preferably ammonium- α-sulfonate radical conjunction-ω -1- (allyloxy methyl) alkyl oxy polyoxyethylene, α-[2- [(allyloxy) -1- (alkyl oxy first Base) ethyl]-ω-polyoxyethylene sulfates.

In addition, for the nonionic emulsifier as reactive emulsifier, it can be cited for example that α-[1- [(allyl oxygen Base) methyl] -2- (Nonylphenoxy) ethyl]-ω-hydroxyl polyoxyethylene (it can be cited for example that (ADEKA societies manufacture, " Adeka Reasoap NE-20 ", " Adeka Reasoap NE-30 ", " Adeka Reasoap NE-40 " etc.), such as polyoxyethylene alkane Base allyl phenyl ether (it can be cited for example that the first industrial pharmaceutical society manufactures, " Aquaron RN-10 ", " Aquaron RN- 20 ", " Aquaron RN-30 ", " Aquaron RN-50 " etc.), such as α-[2- [(allyloxy) -1- (alkyl oxy methyl) Ethyl]-ω-hydroxyl polyoxyethylene (it can be cited for example that ADEKA societies manufacture, " Adeka Reasoap (trade mark) ER-10 " etc.), Such as polyoxyethylene polybutylene (3- methyl -3- cyclobutenyls) ether (it can be cited for example that Hua Wang societies manufacture, " LATEMUL (trade mark) PD-420 " etc.) etc..

The dosage of emulsifier is (a) ingredient, (b) ingredient, except (a) compared with the raw material of the copolymer (C) as polymer 100 mass parts of total amount of water-disintegrable silicon compound and vinyl monomer beyond ingredient and (b) ingredient are preferably 10 mass parts Below, 0.001~5 mass parts are more preferably.It is above range by the dosage for making emulsifier, polymerization stability further carries Height, the water resistance of film are better.

(a) ingredient, (b) ingredient, water-disintegrable silicon compound and vinyl monomer in addition to (a) ingredient and (b) ingredient Deng polymerisation preferably implement in the presence of polymerization catalyst.As used polymerization catalyst, it can be cited for example that salt The halogenations hydrogen species such as acid, hydrofluoric acid；The carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid, lactic acid；The sulfonic acid such as sulfuric acid, p-methyl benzenesulfonic acid Class；Alkyl benzene sulphonate, alkyl sulfonic acid, alkyl sulfosuccinate, polyxyethylated sulfuric acid, polyxyethylated aromatic sulfuric acid, The acidity emulsifier class such as polyoxyethylene diphenylethyllene phenyl ether sulfonic acid；Acid or weakly acidic inorganic salts；Phthalic acid, phosphorus The acid compounds class such as acid, nitric acid；Sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, tetramethyl ammonium chloride, tetramethyl hydrogen-oxygen Change ammonium, tri-n-butylamine, diazabicyclo endecatylene, ethylenediamine, diethylenetriamines, ethanolamines, gamma-amino propyl trimethoxy The alkali compounds classes such as base silane, γ-(2- amino-ethyls)-TSL 8330；Dibutyl tin octoate, two bays Tin compounds such as sour dibutyl tin etc..

Among these, as the polymerization catalyst of water-disintegrable silicon compound, from the work not only having as polymerization catalyst By the use of also playing an important role of as from the aspect of emulsifier, preferred acidic emulsifier class.As acid emulsifier class, more preferable carbon Atomicity is 5~30 alkyl benzene sulphonate (such as dodecyl benzene sulfonic acid etc.).

It as the polymerization catalyst of vinyl monomer, is not particularly limited, preferably by hot or reducing substances etc. The lower free radical that itself occurs of effect decomposes and triggers the catalysts for radical polymerization of the addition polymerization of vinyl monomer.As so Catalysts for radical polymerization, be not particularly limited, it can be cited for example that persulfate, peroxide, two compound of azo etc.. These can be water-soluble substances, or oil soluble material.

It as the concrete example of catalysts for radical polymerization, is not particularly limited, it can be cited for example that potassium peroxydisulfate, persulfuric acid Sodium, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, peroxidized t-butyl perbenzoate, 2,2- azodiisobutyronitriles, 2,2- Azo two (2- diaminopropanes) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile) etc..

The combined amount of catalysts for radical polymerization is not particularly limited, compared with 100 mass parts of total amount of vinyl monomer, Preferably 0.001~5.0 mass parts.It should be noted that it is expected promote polymerization speed and less than 70 DEG C as it is low In the case of the lower polymerization of temperature, preferably will the reducing agent such as sodium hydrogensulfite, frerrous chloride, ascorbate, rongalite and Catalysts for radical polymerization shares.

The polymerization of water-disintegrable silicon compound and vinyl monomer can also be implemented respectively, but by the way that implementation can simultaneously Composite is completed, therefore preferably implements the polymerization of water-disintegrable silicon compound and vinyl monomer simultaneously.

The number average bead diameter of copolymer (C) as polymer is not particularly limited, and is preferably 10~300nm.By making altogether The number average bead diameter of polymers (C) is above range, and the weatherability of obtained film, stain resistance tend to further improve.In addition, The grain size of copolymer (C) is more preferably 10~200nm, further preferably 100~200nm.By using above-mentioned number average bead diameter Copolymer (C), the weatherability of obtained film further improves.By making number average bead diameter for more than 10nm, stain resistance Especially good, by making number average bead diameter for below 300nm, the transparency of film is especially good.It is it should be noted that described herein Number average bead diameter wet type grain size analyzer can be used to be measured.

As the appropriate methodology for the copolymer (C) for obtaining such grain size, it can be cited for example that so-called emulsion polymerization, wherein Make water-disintegrable silicon compound and polymerization of vinyl monomer in the presence of the water of sufficient amount of micella is formed for emulsifier.At this In the mode of sample, the suitable examples of the dispersion (CD) as copolymer (C), it can be cited for example that, the dispersion of copolymer (C) (CD) it is dispersion etc. as obtained from least using silane (a) and silane (b) and carry out emulsion polymerization.

It as the specific method of emulsion polymerization, is not particularly limited, it can be cited for example that following methods：Water-disintegrable silication is closed Object and vinyl monomer under original state or after emulsification in the state of, it is disposable or be added dropwise in batches in reaction vessel or It is continuously added dropwise in reaction vessel, in about 30 preferably under the pressure of atmospheric pressure~10MPa in the presence of polymerization catalyst ~150 DEG C of reaction temperature is polymerize.Reaction temperature and reaction pressure can not also be above-mentioned condition according to reaction condition etc.. The solid component content obtained by emulsion polymerization is not particularly limited, be preferably 1.0~50 mass %, more preferably 5.0~ 30 mass %.

Method for manufacturing (CD) ingredient as dispersion, can also be used following methods：In depositing for water and emulsifier Under, as needed in the presence of solvent by (a) ingredient, (b) ingredient, the water-disintegrable silication in addition to (a) ingredient and (b) ingredient After conjunction object and/or vinyl monomer are polymerize, further water is added until polymer becomes lotion.But from being easy to control Viewpoint of grain size of obtained copolymer (C) etc. is set out, preferred emulsion polymerization as described above.

Copolymer (C) is preferably the core/shell structure with core and 1 layer or 2 layers or more of shell.By for core/shell structure, The physical property (weatherability and the balance of stain resistance etc.) of obtained film further improves, therefore preferably core/shell structure.It is right In the confirmation of core/shell structure, can be surveyed for example, by the morphologic observation based on transmission electron microscope etc. or based on viscoplasticity Fixed parsing etc. carries out.

As the method for copolymer (C) of the manufacture with core/shell structure, such as multi-step emulsion polymerizations are useful, but simultaneously It is without being limited thereto.Multi-step emulsion polymerizations described herein refer to following methods：It prepares containing water-disintegrable silicon compound, vinyl monomer The two or more reaction solutions with different compositions, dividing them into the different stages is polymerize.As multistage lotion An example of polymerization, the method for mainly illustrating to synthesize the copolymer (C) with core/shell structure by 2 sections of emulsion polymerizations.As 2 An example of section emulsion polymerization, can enumerate the method with following processes：Make water-disintegrable silication in the presence of water and emulsifier Object and/or polymerization of vinyl monomer are closed, obtains the process (paragraph 1) of seed grain；And depositing in obtained seed grain Under, respectively by the process of water-disintegrable silicon compound and/or polymerization of vinyl monomer (the 2nd section).

The synthesis of copolymer (C) based on 2 sections of emulsion polymerizations is for example carried out by the polymerization process in 2 stages, 2 stage Polymerization process include：Supply (a) ingredient, (b) ingredient carry out the polymerization of the paragraph 1 of emulsion polymerization；And then paragraph 1, it supplies To the water-disintegrable silicon compound and vinyl monomer beyond (b) ingredient, (a) ingredient, (b) ingredient, in an aqueous medium further 2nd section of polymerization of emulsion polymerization.At this point, the solid constituent quality (M1) of paragraph 1 and the 2nd section of solid constituent quality (M2) Mass ratio ((M1)/(M2)) is not particularly limited, and is preferably 7.0/3.0~9.5/0.5, more preferably 7.5/2.5~9.3/ 0.7。

Pass through multi-step emulsion polymerizations as progress, physical property (weatherability and the balance of stain resistance of obtained film Deng) further improve, therefore preferred multi-step emulsion polymerizations.

When implementing 3 sections or more of multi-step emulsion polymerizations, the hop count for equally, increasing polymerization is polymerize with 2 sections.

The content of the water-disintegrable silicon compound comprising (a) ingredient and (b) ingredient in copolymer (C) is not particularly limited, It is preferably more than 75 mass %, more preferably more than 90 mass % with the conversion of hydrolytie polycondensation object.By making comprising (a) ingredient and (b) content of the water-disintegrable silicon compound of ingredient is above range, and the weatherability of film further improves.

The content of copolymer (C) in aqueous coating agent composition is not particularly limited, and is preferably 0.5~10.0 matter Measure %, more preferably 1.0~5.0 mass %.

The content of copolymer (C) in the film formed by aqueous coating agent composition is preferably 10.0~80.0 matter Measure %, more preferably 50.0~75.0 mass %.By making the content of copolymer (C) to be more than above-mentioned lower limiting value, film it is resistance to Time property further improves, and below for above-mentioned upper limit value, stain resistance further improves.

The aqueous coating agent composition of present embodiment can also be further included in addition to copolymer (C) with can The compound of the functional group to react with the functional group contained by above-mentioned polymer.As such compound, without special Limit, it can be cited for example that (more) isocyanate compound, (poly-) epoxide, amino-compound, (more) carboxyl compound, (more) hydroxy compounds, diol compound, silanol compound, silyl compound, alkoxide compound, (methyl) propylene Ester compound etc..These substances can be used alone, and can also share two or more.

Inorganic oxide (D) is the inorganic oxide without photocatalytic activity.It is described herein not have photocatalysis work Property refers to that oxidation reaction and reduction reaction do not occur under light illumination.

It as (D) ingredient, is not particularly limited, it can be cited for example that silica (silica), aluminium oxide (alumina), silicic acid Calcium, magnesia, antimony oxide, zirconium oxide and their composite oxides etc..Among these, from the aspect of more than surface hydroxyl, It is preferred that silica, aluminium oxide, antimony oxide and their composite oxides, more preferable silica.

Inorganic oxide as (D) ingredient exists preferably in the form of the colloidal solid of hydrate etc..That is, by for nothing Machine oxide colloid particle, also can further with copolymer (C) or for (E) ingredient other compositions Composite, as water It is that the stability of coating agent composition further improves.

Silica is preferably cabosil.As cabosil, following cabosils etc. can be enumerated, are Using silica as the aqueous dispersion of the silica of elementary cell or the dispersion of water-soluble solvent.

The manufacturing method of cabosil is not particularly limited, and can also be prepared using such as sol-gel method.In profit When being prepared with sol-gel method, Werner Stober et al. are referred to；Journal of Colloid And Interface Science,vol.26,pp.62-69(1968)；Rickey D.Badley et al.；Langmuir 6, 792-801(1990)；" colorant association will (Se Cai Association Hui Chi) ", 61 [9] 488-493 (1988) etc..

(D) number average bead diameter of ingredient is not particularly limited, be preferably 1.0~400nm, more preferably 1.0~100nm, into One step is preferably 1.0~30nm.It is more than 1nm by the number average bead diameter for making (D) ingredient, makes the storage of aqueous coating agent composition Stability further improves.By making the number average bead diameter of (D) ingredient for below 400nm, the transparency of obtained film is into one Step improves.It should be noted that number average bead diameter can be measured by using wet type grain size analyzer.

Cabosil can be acid, alkalescence any in the state of aqueous liquid dispersion.

As the acidic colloidal silica using water as decentralized medium, commercially available product can also be used.As such commercially available product, It can be cited for example that Nissan Chemical Industries society manufacture " Snowtex (trade mark)-OXS ", " Snowtex-OS ", " Snowtex-O ", " the adelite (trade mark) of " Snowtex-O-40 ", " Snowtex-OL " and " Snowtex-OYL ", Xu electricity Hua Gongyeshe manufacture " Klebosol (trade mark) 20H12 " and " Klebosol 30CAL25 " that AT-20Q ", Clariant (Japan) society manufacture etc..

As the cabosil of alkalescence, can enumerate by adding alkali metal ion, ammonium ion, amine etc. to stabilize Cabosil.These alkaline cabosils can also use commercially available product.As such commercially available product, can enumerate Such as Nissan Chemical Industries society manufacture " Snowtex-XS ", " Snowtex-S ", " Snowtex-30 ", " Snowtex-50 ", “Snowtex-20L”、“Snowtex-XL”、“Snowtex-YL”、“Snowtex-ZL”、“Snowtex-NXS”、“Snowtex- NS”、“Snowtex-N”、“Snowtex-N40”、“Snowtex-CXS”、“Snowtex-C”、“Snowtex-CM”、 " Snowtex-PS-S " and " SnowtexPS-M "；" adelite AT-20 ", " the adelite AT- of Xu electricity Hua Gongyeshe manufactures 30”、“adelite AT-20N”、“adelite AT-30N”、“adelite AT-20A”、“adelite AT-30A”、 " adelite AT-40 " and " adelite AT-50 "；" the Klebosol 30R9 " of the manufacture of Clariant (Japan) society, " Klebosol 30R50 ", " Klebosol 50R50 ", " ludox (trade mark) HS-40 ", " the ludox HS- of the manufacture of society of Du Pont 30 ", " ludox LS " and " ludox SM-30 " etc..

As the cabosil using water-soluble solvent as decentralized medium, commercially available product can also be used.As such city Product are sold, it can be cited for example that " MA-ST-M (the methanol decentralized of 20~25nm of grain size) " of the manufacture of Nissan Chemical Industries society, " IPAST (the isopropanol decentralized of 10~15nm of grain size) ", " EG-ST (the ethylene glycol decentralized of 10~15nm of grain size) ", " EG- ST-ZL (the ethylene glycol decentralized of 70~100nm of grain size) ", " (ethylene glycol monopropyl ether of 10~15nm of grain size disperses NPC-ST Type) " etc..

Above-mentioned cabosil can be used alone, and can also share two or more.Further, as on a small quantity into Point, aluminium oxide or sodium aluminate etc. can also be contained.In addition, cabosil can also contain inorganic base (sodium hydroxide, hydroxide Potassium, lithium hydroxide, ammonia etc.) or organic base (tetramethyl-ammonium etc.) be used as stabilizer.

The content of (D) ingredient in aqueous coating agent composition is not particularly limited, and is preferably 0.1~5.0 mass %, more Preferably 0.2~3.0 mass %.It is above range by the content for making (D) ingredient in aqueous coating agent composition, can obtain Weatherability and the more excellent film of stain resistance.

The content of (D) ingredient in the film obtained by aqueous coating agent composition is not particularly limited, preferably 5.0~ 70.0 mass %, more preferably 10.0~50.0 mass %.By make the content of (D) ingredient in film for above-mentioned lower limiting value with On, the stain resistance of film further improves, and below for above-mentioned upper limit value, the weatherability of film further improves.

The aqueous coating agent composition of present embodiment preferably further includes the inorganic oxide with photocatalytic activity (E).It as a result, can be by showing photocatalytic activity and hydrophily to film irradiation light.

As inorganic oxide (E), as long as to have the inorganic oxide of photocatalytic activity, to its species without spy It does not limit.It as the concrete example of (E) ingredient, is not particularly limited, it can be cited for example that TiO₂、ZnO、SrTiO₃、BaTiO₃、 BaTiO₄、BaTi₄O₉、K₂NbO₃、Nb₂O₅、Fe₂O₃、Ta₂O₅、K₃Ta₃Si₂O₃、WO₃、SnO₂、Bi₂O₃、BiVO₄、NiO、Cu₂O、 RuO₂、CeO₂；With the layered oxide selected from least one of the group being made of Ti, Nb, Ta and V element, (such as Japan is special Open clear 62-074452 publications, Japanese Unexamined Patent Publication 02-172535 publications, Japanese Unexamined Patent Publication 07-024329 publications, Japan Unexamined Patent 08-089799 publications, Japanese Unexamined Patent Publication 08-089800 publications, Japanese Unexamined Patent Publication 08-089804 publications, day This Unexamined Patent 09-248465 publications, Japanese Unexamined Patent Publication 10-099694 publications, Japanese Unexamined Patent Publication 10-244165 publications Deng).

As (E) ingredient, chemically stability, toxicity, environment face etc. are set out, and are preferably TiO₂(titanium dioxide). Can be the crystalline texture of any one of Detitanium-ore-type, rutile-type, brookite type as titanium dioxide.

(E) ingredient be preferably with photocatalytic activity inorganic oxide and its be gold of its particle surface through moditied processing Belong to compound.By carrying out moditied processing, H can be reduced₂O₂Or the yield of OH isoreactivity oxygen kinds, it can further inhibit substrate The damage of film.It as the substance of modification, is not particularly limited, it can be cited for example that silica, aluminium, Cu oxide, iron aoxidize Object etc..Among these, preferred silica.It should be noted that using the complex compounds such as the metals such as Fe, Cu, Al, Pt, chloroplatinic acid into Row modification also can obtain same effect.

On the method that moditied processing is carried out to the surface of (E) ingredient, silica is illustrated as an example.As The method of processing is surface modified to silica, is not particularly limited, it can be cited for example that following methods etc.：In titanium dioxide Slurry in add silicon compound, the hydrous oxide of silicon is precipitated by processes such as neutralisation treatments.

It as silicon compound, is not particularly limited, the water-soluble silicon acid alkali metal salt such as sodium metasilicate can be used.These Among, from the aspect of colourless, TiO 2 sol does not colour, preferred sodium metasilicate.

The treating capacity of the hydrous oxide of silicon preferably 3.0~25 matter on the basis of oxide compared with titanium dioxide Measure %, more preferably 5.0~20 mass %.By the way that treating capacity is made to be more than above-mentioned lower limiting value, the increasing of active oxygen species amount can inhibit Add, therefore can prevent the damage of base coating film.In addition, by the way that treating capacity is made to be below above-mentioned upper limit value, titanium dioxide can inhibit Aggegation, may also suppress colloidal sol viscosity rise, therefore dispersiveness and the transparency further improve.

The content of (E) ingredient in aqueous coating agent composition is not particularly limited, and is preferably 0.1~2.0 mass %, more Preferably 0.2~1.0 mass %.Content by (E) ingredient for making aqueous coating agent is above range, can obtain stain resistance The more excellent film with the transparency.

The content of (E) ingredient in the film obtained by aqueous coating agent composition is not particularly limited, preferably 3.0~ 25.0 mass %, more preferably 5.0~20.0 mass %.By make the content of (E) ingredient in film for above-mentioned lower limiting value with On, the stain resistance of film further improves, and below for above-mentioned upper limit value, the transparency of film further improves.

The aqueous coating agent composition of present embodiment preferably further contains fluorocarbon surfactant (F).It uses as a result, When the aqueous coating of aqueous coating agent composition or use containing said composition of present embodiment carries out application, can further it carry Height can further inhibit the apparent problems such as repulsion to the wetability of organic substrate etc..And then the homogeneity of film is also into one Step improves.It is the reasons why as said effect, still uncertain, thus it is speculated that be because by containing (F) ingredient, aqueous coating agent can be reduced The surface tension of composition (still, the effect of present embodiment is not limited to these).

As (F) ingredient, it is not particularly limited, preferably amphoteric surfactant.As amphoteric surfactant, Ke Yiju Go out such as nonionic surfactant, anionic amphoteric surfactant, cationic amphoteric surfactant. As preferred concrete example, it can be cited for example that the amphoteric surfactant with the perfluoroalkyl that carbon number is 3~20.

As the concrete example of the amphoteric surfactant with the perfluoroalkyl that carbon number is 3~20, can enumerate complete Fluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl amine oxide, perfluoroalkyl ethylene oxide adduct, have anion All-fluoroalkyl compound of property group and cationic groups etc..Among these, go out in terms of the surface tension of coating is reduced Hair, preferably perfluoroalkyl ethylene oxide adduct, the all-fluoroalkyl compound with anionic group and cationic groups.

As perfluoroalkyl carboxylate, such as commercially available product can also be used.As such commercially available product, AGC can be enumerated " the Surflon S-211 " of the manufacture of SEIMI CHEMICAL societies etc..As perfluoroalkyl amine oxide, such as can also use commercially available Product.As such commercially available product, can enumerate " the Surflon S-241 " of the manufacture of AGC SEIMI CHEMICAL societies etc..As Perfluoroalkyl ethylene oxide adduct, such as commercially available product can also be used.As such commercially available product, it can be cited for example that DIC " the MEGAFAC F-444 " of society's manufacture, " the Surflon S-242 " of the manufacture of AGC SEIMI CHEMICAL societies etc..As with The all-fluoroalkyl compound of anionic group and cationic groups, such as commercially available product can also be used.As such city Sell product, can enumerate AGC SEIMI CHEMICAL societies manufacture " Surflon S-231 ", " Surflon S-232 ", " Surflon S-233 " etc..These substances can be used alone, and can also share two or more.

The content of (F) ingredient in aqueous coating agent composition is not particularly limited, and is preferably 0.0001~0.50 matter Measure %, more preferably 0.01~0.10 mass %.It is more than above-mentioned lower limiting value obtained painting by the content for making (F) ingredient The homogeneity of film further improves.It is the weatherability of obtained film below above-mentioned upper limit value by the content for making (F) ingredient It further improves.

The aqueous coating agent composition of present embodiment preferably further contains fadedness pigment (G).Thus can prevent from losing The problems such as holiday fills, repeats application, application is uneven.

As (G) ingredient, preferably eclipsed under the irradiation of sunlight and the aesthetics that does not damage substrate substance.Until The eclipsed time is different according to season and irradiating angle etc., usually visually under confirm it is eclipsed until during be preferably 20 Below day, it is more preferably less than 10 days, further preferably less than 3 days.

As (G) ingredient, it is not particularly limited as long as with eclipsed property under the irradiation of sunlight, as preferred Example, can enumerate selected from by methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosine, famille rose, flame be red, rose-red, 1 kind etc. in the group of acid red and fast green FCF composition.Among these, examined in terms of colour rendering is good, eclipsed speed is also fast Consider, more preferable methylene blue.These substances can be used alone, and can also share two or more.

The content of (G) ingredient in aqueous coating agent composition is not particularly limited, and is preferably 0.0002~0.01 matter Measure %, more preferably 0.001~0.007 mass %.By making the content of (G) ingredient in aqueous coating agent composition to be above-mentioned Scope, the colour rendering and fadedness of film further improve.Colour rendering described herein refers to that colour developing is to according to application face and not The color distortion in application face and can visually distinguish the property of this degree, fadedness refers to, fades to the U.S. for not damaging base material The property of the degree of the color for the property seen.

The content of (G) ingredient in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 0.01 ~0.5 mass %, more preferably 0.05~0.2 mass %, further preferably 0.1~0.2 mass %.By making (G) ingredient Content for more than above-mentioned lower limiting value, the colour rendering of film further improves, below for above-mentioned upper limit value, the colour fading of film Property further improves.

<Cellulose-based thickeners (H)>

The aqueous coating agent composition of present embodiment preferably further contains cellulose-based thickeners (H).Even if as a result, The solid component content of aqueous coating agent composition is low, and when application is hung from above prevented also from liquid.As cellulose-based thickeners (H), it is not particularly limited, it can be cited for example that selected from by methylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxylic first 1 kind in the group of base cellulose, hydroxypropyl methyl cellulose and their modifier composition.Among these, be preferably selected from by 1 kind in the group of hydroxyethyl cellulose, hydroxypropyl methyl cellulose and their modifier composition, more preferable hydroxyethyl cellulose And its modifier.It is separately that these cellulose-based thickeners can be used alone, can also shares two or more.

In addition, in the range of the effect of present embodiment is obtained, other thickeners can also be shared.As other thickenings Agent is not particularly limited, it can be cited for example that polybasic carboxylic acid system thickener, Polyacrylamide thickener, acrylic acid acryloyl Amine copolymer object salt system thickener, it is cellulose-based beyond polysaccharide system thickener, vinyl ethers system thickener etc. goes out.

As hydroxyethyl cellulose, commercially available product can also be used.As such commercially available product, it can be cited for example that Daicel " HEC Daicel SP200 ", " HEC Daicel SP400 ", " HEC Daicel SP500 ", " HEC of finechem societies manufacture Daicel SP550 ", " HEC Daicel SP600 ", " HEC Daicel SP800 ", " HEC Daicel SP850 " and " HEC Daicel SP900 ", " Sanhec (trade mark) HH ", " Sanhec H ", " Sanhec M " and " the Sanhec G＆ of three prosperous society's manufactures L ", Sumitomo refine " HECSZ-25F " etc. of society's manufacture.

The weight average molecular weight of hydroxyethyl cellulose is not particularly limited, and is preferably 700,000~2,000,000, more preferably 1,000,000 ~160 ten thousand.It is more than 700,000 by weight average molecular weight, the liquid that can further inhibit aqueous coating agent composition is hung from above.Pass through Weight average molecular weight is less than 2,000,000, and the transparency of the film obtained by waterborne compositions further improves.Weight average molecular weight can lead to Cross gel permeation chromatography (GPC) measure.

As hydroxypropyl methyl cellulose, commercially available product can also be used.As commercially available product, it can be cited for example that SHIN-ETSU HANTOTAI is chemical " METOLOSE 90SH-04 ", " METOLOSE 90SH-15 ", " METOLOSE 90SH-100 ", " METOLOSE of society's manufacture 90SH-400 ", " METOLOSE 90SH-4000 ", " METOLOSE 90SH-15000 " and " METOLOSE 90SH-100000 ", " NEOVISCO-MC HM4000S ", " NEOVISCO-MC RM4000S ", " NEOVISCO-MC of three prosperous society's manufactures RM15000S ", " NEOVISCO-MC RM30000S " and " NEOVISCO-MC RM50000S " etc..

In the case where sharing other thickeners, it is preferable to use polybasic carboxylic acid system thickener, Polyacrylamide thickener, More preferably use polybasic carboxylic acid system thickener.

As polybasic carboxylic acid system thickener, commercially available product can also be used.As commercially available product, it can be cited for example that East Asia synthesizes " A-20P-X ", " A-7100 ", " A-7185 " etc. of society's manufacture.

The content of (H) ingredient in aqueous coating agent composition is not particularly limited, preferably 0.04~0.30 mass %, More preferably 0.08~0.20 mass %.It is above range by the content for making (H) ingredient in aqueous coating agent composition, it can Obtain the transparency and the more excellent film of weatherability.

The content of (H) ingredient in the film obtained by aqueous coating agent composition is not particularly limited, preferably 2.0~ 15.0 mass %, more preferably 4.0~9.0 mass %.By make the content of (H) ingredient in film for above-mentioned lower limiting value with On, the transparency of film further improves, and below for above-mentioned upper limit value, the weatherability of film further improves.

<Algaecide, mould inhibitor (J)>

The film of present embodiment preferably further contains a kind in the group for being selected from and being made of algaecide and mould inhibitor (J) More than.Even if being difficult to the position being irradiated in light such as sunlights as a result, mildew resistance and/or the excellent painting of anti-algae property can be also formed Film (still, the effect of present embodiment is not limited to these).

It as algaecide and/or mould inhibitor (J), is not particularly limited, it can be cited for example that organic iodine based compound, alcohol system Compound, nitrile compound, disulphide based compound, thiocarbamate based compound, containing azo-cycle compound etc..These it In, preferably containing azo-cycle compound.As containing azo-cycle compound, can enumerate thiazoline based compound, isothiazoline based compound, Triazine based compound, imidazole compound etc..Among these, be preferably selected from by isothiazoline based compound, triazine based compound, One or more of group of imidazole compound composition, is more preferably selected from being made of isothiazoline based compound, triazine based compound One or more of group.The compound excellent as particularly anti-algae property, it can be cited for example that triazine based compound etc..As The particularly excellent compound of mildew resistance, it can be cited for example that thiazoline based compound, isothiazoline based compound, imidazoles system Close object etc..It is of course possible to use the compound for having both anti-algae property and mildew resistance, as such compound, it can be cited for example that point Isothiazoline based compound containing chlorine atom etc. in son.These substances can be used alone, can also share two kinds with On.

As thiazoline based compound, commercially available product can also be used.As such commercially available product, it can be cited for example that Japanese " Amorden ALK " that " Millcut-180 " of Cao Dashe manufactures, " Biocut-LC3 ", big and chemical industry society manufacture etc..

As isothiazoline based compound, commercially available product can also be used.As such commercially available product, it can be cited for example that day This Cao Da societies manufacture " Biocut-TR120 ", Arch Chemicals societies manufacture " PROXEL GXL ", " PROXEL BDN ", Dow Chemical societies manufacture " KLARIX 4000 ", " ROZONE 2000 ", " ROCIMA 252 ", " ROCIMA 200 ", " ROCIMA 345 ", " ROCIMA 350 ", " ROCIMA 553 ", " BIOBAN 551S ", " Skane M-8 " etc..

As triazine based compound, commercially available product can also be used.As commercially available product, it can be cited for example that Cao Da societies of Japan system " Biocut-N35 ", " DP-2159 ", " DP-2615 " made." DP-2619 ", " DP-2623 ", big and chemical industry society manufacture " サ Application ア Le ガ 1907 " that " Amorden NBP-8 ", " Amorden NBPconc ", three chemical conversion societies of association manufacture etc..

As imidazole compound, commercially available product can also be used.As commercially available product, it can be cited for example that Cao Da societies of Japan system " Biocut-N35 " that makes, " Biocut-AF40 ", " DX-2 ", " ROCIMA 363 " etc. of the manufacture of Dow Chemical societies.

The content of (J) ingredient in aqueous coating agent composition is not particularly limited, preferably 0.01~0.80 mass %, More preferably 0.05~0.50 mass %.It is above range by the content for making (J) ingredient in waterborne compositions, can obtain Bright property, weatherability and the more excellent film of microbial resistance.

The content of (J) ingredient in the film obtained by aqueous coating agent composition is not particularly limited, preferably 0.1~ 30.0 mass %, more preferably 1.0~15.0 mass %.By make the content of (J) ingredient in film for above-mentioned lower limiting value with On, the microbial resistance of film further improves, and below for above-mentioned upper limit value, the transparency and weatherability of film are further It improves.

In the range of it can obtain the effect of present embodiment, other antiseptics can also be further shared.As other Antiseptic is not particularly limited, it can be cited for example that silver-colored based compound, copper system compound, zinc based compound etc..

The content (solid component content) of solid constituent in aqueous coating agent composition is not particularly limited, from film It sets out in terms of homogeneity, is preferably 0.5~10.0 mass %, more preferably 1.5~6.0 mass %.By making Water-Based Paint The content of solid constituent in agent composition is more than above-mentioned lower limiting value, stain resistance further improves.By making Water-Based Paint The content of solid constituent in agent composition is below above-mentioned upper limit value, the transparency further improves.Solid described herein into Point content can be obtained by the method described in aftermentioned embodiment.In addition, according to the purposes of film, film is also required sometimes Film thickness it is relatively thin.Even in this case, by the way that the solid component content in aqueous coating agent composition is made to be the above-mentioned upper limit Value is following, can be made into although film thickness it is relatively thin, weatherability and stain resistance etc physical property also excellent film.By making water system Solid component content in coating agent composition is more than above-mentioned lower limiting value, when required dry when can shorten to form film Between, it can further improve operating efficiency.

The aqueous coating agent composition of present embodiment can as needed further in the range of it can obtain its effect Contain other compositions other than the above.It as such other compositions, is not particularly limited, it can be cited for example that antifoaming agent, cold Freeze stabilizer, matting agent, catalyst for cross-linking reaction, pigment, curing catalysts, crosslinking agent, filler, anti skinning agent, dispersant, It is wetting agent, light stabilizer, antioxidant, ultra-violet absorber, coalescents, antirust agent, plasticizer, lubricant, reducing agent, anti- Rotten agent, deodorant, anti-yellowing agent, antistatic agent, charged regulator etc..These can be used alone, and can also share two Kind or more.

Above-mentioned aqueous coating agent composition can be suitble to use in the form of aqueous coating.That is, the water system of present embodiment Coating contains above-mentioned aqueous coating agent composition.For aqueous coating, can further contain antifoaming agent, freeze-stable agent, Matting agent, catalyst for cross-linking reaction, pigment, curing catalysts, crosslinking agent, filler, anti skinning agent, dispersant, wetting agent, light It is stabilizer, antioxidant, ultra-violet absorber, coalescents, antirust agent, plasticizer, lubricant, reducing agent, preservative, mould proof Agent, algaecide, deodorant, anti-yellowing agent, antistatic agent, charged regulator etc. are used as other compositions.

The aqueous coating of present embodiment can suitably according to material etc. of its purposes and coating object with suitable method into Row coating.It as coating method, is not particularly limited, it can be cited for example that spray-on process, flow coat method, rolling method, spread coating, dipping Rubbing method, method of spin coating, silk screen print method, casting method, woodburytype, aniline printing method.

It is dried to remove volatile matter to obtain film by being coated with after the aqueous coating of present embodiment.At this point, Heating or ultraviolet treatment with irradiation at a temperature of 40~120 DEG C or so etc. can be further carried out as needed.

In this way, it can be made into the film containing above-mentioned aqueous coating in present embodiment.The film is obtained by aqueous coating, Can for example base material be formed to be made by the way that above-mentioned aqueous coating to be coated on the surface of various base materials and be dried On film.That is, coated articles can also be made in present embodiment, which contains base material and be formed at the table of base material At least part of above-mentioned film in face.

The material of workable base material is not particularly limited as long as it can be formed on its surface film in present embodiment, can Think any one of organic substrate, inorganic substrate, preferably organic substrate.As the material of base material, it is not particularly limited, it can be with It enumerates such as synthetic resin, natural resin, metal, ceramics, glass, building stones, cement, concrete.These substances can be independent Using one kind, can also share two or more.Particularly, in the present embodiment, it can formed and can remain outer with high level The aspect with the film of stain resistance is seen, even by having the material of -5~20 DEG C of so low glass transition temperatures to form Organic substrate be also suitable.

It as synthetic resin, is not particularly limited, it can be cited for example that thermoplastic resin, curable resin (Thermocurable Resin, light-cured resin, moisture-curable resin etc.).It as the concrete example of synthetic resin, is not particularly limited, Ke Yiju Go out for example organic siliconresin, acrylic resin, methacrylic resin, fluororesin, alkyd resin, amino-alkyd resin, Vinylite, polyester resin, styrene-butadiene resins, vistanex, polystyrene resin, polyketone resin, polyamide Resin, polycarbonate resin, polyacetal resin, polyether-ether-ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulphone resin, Polyether resin, Corvic, polyvinylidene chloride resin, carbamide resin, phenol resin, melmac, epoxy resin, ammonia Carbamate resin, silicone-acrylic resinoid etc..In addition, acrylic resin system coating, silicon by being used for construction exterior etc. The film that ketone-acrylic resin system coating, fluororesin system coating are formed is also contained in synthetic resin.

It as natural resin, is not particularly limited, it can be cited for example that the isoprene such as cellulose-based resin, natural rubber It is the protein such as resin, casein system resin etc..

Base material be used above-mentioned synthetic resin or natural resin when resin base material when, electricity can be implemented with as needed The surface treatments such as corona processing, flame treatment, corona treatment.

The coated articles of present embodiment contain base material and the above-mentioned film being formed on the base material, even if the film conduct Coating etc. is also useful.The film obtained by present embodiment can maintain appearance and anti fouling performance with high level for a long time, Thus, it is also possible to it is suitably used in the prior art in unworkable environment.From this side considerations, as this implementation The concrete example of the coated articles of mode, it can be cited for example that building materials, building exterior, building are built-in, window frame, glass pane, each Architectural Equipments, the cover of vehicle lighting lamp and the glass panes such as kind of lens, structure member, house, mechanical device or article exterior, Dust cover and application, display instrument, its cover, traffic mark, various display devices, advertising tower etc. show object, road is used and railway With sound-proof wall, bridge, the exterior of guardrail and the application waited, tunnel is built-in and application, insulator, solar-electricity pool cover, solar energy Water heater collector mat etc. is in the external electronics used, the particularly externally mounted part of electrical equipment, transparent component, vinyl house, greenhouse Deng exterior.

The manufacturing method of coated articles as present embodiment can enumerate following methods：For example, on the surface of base material At least a portion on be coated with above-mentioned aqueous coating (or aqueous coating agent composition), be dried as needed, so as to Film is formed, but manufacturing method is not limited to this.For example, after the film of present embodiment can be coated on base material, this is applied Film is removed from the base material, is bonded on other base material.Alternatively, the film of present embodiment can also be coated on base material Afterwards, which is bonded in the state closely sealed with the base material on other base material.

The aqueous coating agent composition of present embodiment can be compounded into various aqueous coatings.Such aqueous coating can shape Into the excellent film such as appearance, stain resistance and then the transparency, weatherability, mildew resistance, anti-algae property.In this way, present embodiment Appearance, stain resistance and then the transparency of film, weatherability, mildew resistance, anti-algae property etc. are also excellent, available for including building Outer coatings etc. including extensive purposes in.

Embodiment

The present invention is described in more detail below by way of embodiments and comparative examples, but the present invention is not limited to following embodiments. In embodiment and comparative example various physical property are determined by following methods.

The making of pigment dispersion

Using desk-top sand mill (Kanpehapio societies manufacture, the desk-top sand mill of batch-type), by dispersant (BASF Japan Society manufacture, " Pig.Disperser MD20 ") 5.35g, ammonium hydroxide 0.50g, propylene glycol 23.50g, water 147.50g, titanium dioxide (chlorine method rutile titanium dioxide；Stone originate in industry society manufacture, " Taipake CR-97 ") 333.50g, antifoaming agent (modified silicone System；SANNOPCO societies manufacture, " SN Defoamer 1310 ") mixed thing of 2.85g disperses 20 minutes, obtain pigment dispersion.

The making of enamel-cover coating X

2,2,4- trimethyls -1,3 butylene glycol isobutyrate is added in the polymer emulsion X of the Production Example 1 of 109.0g (Chisso societies manufacture, " CS-12 ") 10.0g, 50 mass parts of ethylene glycol monobutyl ether and 50 mass parts of water mixed liquor 10.0g, on It is the pigment dispersion 51.4g that states, the 10% of thickener (Xu electricity Hua Gongyeshe is manufactured, " ADEKANOL UH-438 ") water-soluble Liquid 0.5g, mixing 1 mix when small, obtain enamel-cover coating X.

The making of the base material X of enamel-cover coating X is coated in advance

Using bar coater No.50, application is above-mentioned on the acidproof aluminium sheet of sulfuric acid of 7cm × 15cm or 5cm × 5cm obtains Enamel-cover coating X, when 50% time 23 DEG C of temperature, relative humidity drying 48 are small, be coated with the base material of enamel-cover coating X in advance X。

The making of enamel-cover coating Y

Without using the polymer emulsion X 109.0g of Production Example 1, and the polymer emulsion Y 109.0g of Production Example 2 are used, In addition, enamel-cover coating Y is obtained in the same manner as enamel-cover coating X.

The making of the base material Y of enamel-cover coating Y is coated in advance

Using bar coater No.50, application is above-mentioned on the acidproof aluminium sheet of sulfuric acid of 7cm × 15cm or 5cm × 5cm obtains Enamel-cover coating Y, when 50% time 23 DEG C of temperature, relative humidity drying 48 are small, be coated with the base material of enamel-cover coating Y in advance Y。

1. the content and solid component content of each ingredient

Materials 2g in aluminium dish, when 150 DEG C of heating 1 are small.The quality of the front and rear sample of heating is measured, is calculated by its difference Go out solid component content (quality %).According to this method, the solid constituent measured respectively in the content and composition of each ingredient contains Amount.

2. number average bead diameter

Addition ion exchange water be diluted so that load factor (loading index) be 1.5~3.0, use wet type Particle Size Analyzer (Ji Zhuan societies manufacture, " microtrack UPA-9230 ") is measured.Determination condition is as follows.

Load factor：1.5~3.0

Minute：60 seconds

Measure number：3 times

3. viscosity

It is measured using BM types viscosimeter (manufacture of Dong Ji industries society).Determination condition is as follows.

Temperature：23℃

Rotor：No.1

Rotating speed：60rpm

4. glass transition temperature

" DCS6220 " manufactured using Seiko Instruments societies, in the measurement strip that heating rate is 10 DEG C/min Part is measured, and glass transition temperature is obtained by the inflection point of obtained DSC curve.It should be noted that determination condition is such as Shown in lower.

Measure pond：Aluminium vessel

The making of test sample：It is added in aluminium vessel as the lotion 40mg for measuring sample, in 130 DEG C of dryings 1 it is small when.

5. atmospheric exposure test：3000 it is small when after gloss retention

On the base material X or base material Y for be coated in advance 7cm × 15cm of enamel-cover coating waterborne compositions are carried out using spraying Application so that the coating weight of the waterborne compositions be 17g/m²Or 50g/m²Ratio.Base material through application is kept horizontal, When 50% time 23 DEG C of temperature, relative humidity standing 48 are small, as breadboard.Using SUGA exercisers manufacture " sunlight is weather-proof Chamber " carries out exposure test (when 63 DEG C of blackboard temperature, rainfall 18 minutes/2 are small).Use gloss meter (BYK Gardner societies system Make, " micro-tri-gloss μ ") to expose to the open air 3000 it is small when after 60 ° of glossiness measure respectively.

Also, gloss retention is calculated based on following formula.It should be noted that the base material only to being coated with enamel-cover coating in advance It is being evaluated as a result, base material X expose to the open air 3000 it is small when after gloss retention for 80%, base material Y expose to the open air 3000 it is small when Gloss retention afterwards is 88%, these values are shown, in the case that the value of gloss retention is big, weatherability is good.

60 ° of glossiness × 100 before 60 ° of glossiness/exposure tests after gloss retention (%)=exposure test

6. stain resistance

On the base material X or base material Y for be coated in advance 7cm × 15cm of enamel-cover coating waterborne compositions are carried out using spraying Application so that the coating weight of the waterborne compositions be 17g/m²Or 50g/m²Ratio.Base material through application is kept horizontal, When 50% time 23 DEG C of temperature, relative humidity standing 48 are small, as breadboard.Breadboard is attached at towards Ordinary Rd (card 500~1000/day of vehicle traffic volume or so) fence, stand 6 months or 1 year.After being stood based on following benchmark visual valuation The pollution level of breadboard.It should be noted that the evaluation result of the base material X or Y only to being coated with enamel-cover coating in advance are, it is quiet Put be within 6 months, 1 year "×" evaluation.

○：Almost without confirming dirt.

△：Confirming slightly has dirt, but is the degree of practical upper no problem.

×：Substantial amounts of dirt is confirmed.

7. fungicidal properties

On the base material X or base material Y for be coated in advance 5cm × 5cm of enamel-cover coating waterborne compositions are carried out using spraying Application so that the coating weight of the waterborne compositions be 17g/m²Or 50g/m²Ratio.Base material through application is kept horizontal, When 50% time 23 DEG C of temperature, relative humidity standing 48 are small, as breadboard.

On condition other than the above, according to " experiments of 8 coating " of JIS Z-2911 (fungus resistance test method), use By aspergillus niger, thermophilic loose mould, Cladosporium cladosporioides, aureobasidium pullulans, green trichoderma bacterium and mutually every the interlinkage mixed substance of spore It is tested.After experiment, based on following benchmark implementation evaluation.

◎：The growth of mycelia is not confirmed on film.

○：The area of the growth part of the mycelia confirmed on film is more than 0 compared with the gross area and is less than 1/3.

△：The area of the growth part of the mycelia confirmed on film is more than 1/3 compared with the gross area and is less than 2/3.

×：The area of the growth part of the mycelia confirmed on film is more than 2/3 compared with the gross area.

8. anti-algae performance

Without using mould, and use quivers chlorella vulgaris and bright green the mixed substance of algae, and uses above-mentioned test film, In addition, the experiment damp process of fibre " 7c) " based on JIS Z-2911 (fungus resistance test method) is tested.Examination After testing, based on following benchmark implementation evaluation.

◎：The growth of algae is not confirmed on film.

○：The area of the growth part of the algae confirmed on film is more than 0 compared with the gross area and is less than 1/3.

△：The area of the growth part of the algae confirmed on film is more than 1/3 compared with the gross area and is less than 2/3.

×：The area of the growth part of the algae confirmed on film is more than 2/3 compared with the gross area.

9. wet type decomposability

On the base material X or base material Y for be coated in advance 7cm × 15cm of enamel-cover coating waterborne compositions are carried out using spraying Application so that the coating weight of the waterborne compositions be 17g/m²Or 50g/m²Ratio.Base material through application is kept horizontal, When 50% time 23 DEG C of temperature, relative humidity standing 48 are small, as breadboard.On the breadboard, based on JIS R1703-2 (the self-cleaning performance test method of fine ceramics-catalysis material-the 2：Wet type decomposability) it is tested, decomposition is obtained Activity index.Degrading activity index is higher, represents that self-cleaning property is better.

[Production Example 1]

The synthesis of polymer emulsion X

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 292g, (ADEKA societies manufacture reactive emulsifier, " Adeka Reasoap SR-1025 "；Solid component content is the water-soluble of 25 mass % Liquid) 8g, the temperature in reactor is heated to 80 DEG C under stirring.The ammonium persulfate that 2 mass % are added into the reactor is water-soluble Liquid 10g after five minutes, was added dropwise with 60 minutes by methyl methacrylate in a state that the temperature in reactor is kept for 80 DEG C It is 15g, cyclohexyl methacrylate 10g, butyl acrylate 65g, methacrylic acid 5g, 2-hydroxyethyl methacry-late 10g, anti- (ADEKA societies manufacture answering property emulsifier, " Adeka Reasoap SR-1025 "；Solid component content is the water-soluble of 25 mass % Liquid) 4g, the ammonium persulfate aqueous solution 15g of 2 mass %, ion exchange water 49g form emulsion mixture.Thereafter, by reactor In temperature maintain 80 DEG C and continue stirring 60 minutes.

Then, it was added dropwise by different dropwise adding tanks with 160 minutes by methyl methacrylate 80g, cyclohexyl methacrylate (ADEKA societies manufacture, " Adeka Reasoap SR- for 90g, butyl acrylate 222g, methacrylic acid 8g, reactive emulsifier 1025”；Solid component content be 25 mass % aqueous solution) 16g, the ammonium persulfate aqueous solution 60g of 2 mass %, ion exchange The emulsion mixture that water 196g is formed；And by 3- methacryloxypropyl trimethoxy silanes 1g, dimethylformamide dimethyl oxygen The mixed liquor that base silane 20g, methyltrimethoxysilane 20g are formed.Thereafter, the temperature in reactor is maintained into 80 DEG C of continuation Stirring 120 minutes.After being cooled to room temperature, the hydrogen ion concentration of the reaction solution in reactor is measured, as a result pH is 2.2.By 25% Ammonia spirit, with the metal mesh filter reaction solution of 100 mesh, obtains enamel-cover coating added to after adjustment pH is 8 in reaction solution Polymer emulsion X.The solid component content of obtained polymer emulsion X is 44.5 mass %.On polymer emulsion X institutes The polymer contained, the glass transition temperature being obtained based on the above method by the inflection point of DSC curve is 1 DEG C.

[Production Example 2]

The synthesis of polymer emulsion Y

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 292g, (ADEKA societies manufacture reactive emulsifier, " Adeka Reasoap SR-1025 "；Solid component content is the water-soluble of 25 mass % Liquid) 8g, the temperature in reactor is heated to 80 DEG C under stirring.The ammonium persulfate that 2 mass % are added into the reactor is water-soluble Liquid 10g after five minutes, was added dropwise with 60 minutes by methyl methacrylate in a state that the temperature in reactor is kept for 80 DEG C It is 15g, cyclohexyl methacrylate 10g, butyl acrylate 65g, methacrylic acid 5g, 2-hydroxyethyl methacry-late 10g, anti- (ADEKA societies manufacture answering property emulsifier, " Adeka Reasoap SR-1025 "；Solid component content is the water-soluble of 25 mass % Liquid) 4g, the ammonium persulfate aqueous solution 15g of 2 mass %, ion exchange water 49g form emulsion mixture.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 60 minutes.

Then, it was added dropwise by different dropwise adding tanks with 160 minutes by methyl methacrylate 150g, cyclohexyl methacrylate (ADEKA societies manufacture, " Adeka Reasoap SR- for 90g, butyl acrylate 152g, methacrylic acid 8g, reactive emulsifier 1025”；Solid component content be 25 mass % aqueous solution) 16g, the ammonium persulfate aqueous solution 60g of 2 mass %, ion exchange The emulsion mixture that water 196g is formed；And by 3- methacryloxypropyl trimethoxy silanes 1g, dimethylformamide dimethyl oxygen The mixed liquor that base silane 20g, methyltrimethoxysilane 20g are formed.Thereafter, the temperature in reactor is maintained into 80 DEG C of continuation Stirring 120 minutes.After being cooled to room temperature, the hydrogen ion concentration of the reaction solution in reactor is measured, as a result pH is 2.2.By 25% Ammonia spirit, with the metal mesh filter reaction solution of 100 mesh, obtains enamel-cover coating added to after adjustment pH is 8 in reaction solution Polymer emulsion Y.The solid component content of obtained polymer emulsion Y is 44.5 mass %.On polymer emulsion Y institutes The polymer contained, the glass transition temperature being obtained based on the above method by the inflection point of DSC curve is 20 DEG C.

[Production Example 3]

The synthesis of the aqueous dispersion (CD-1) of polymer (C-1)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is keeping Temperature in reactor in the state of 80 DEG C with about 2 it is small when be added dropwise into the reactor by dimethyldimethoxysil,ne The mixed liquor that 110.0g, phenyltrimethoxysila,e 73.0g, methyltrimethoxysilane 29.4g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass % is put into Afterwards, by the temperature in reactor maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution of 2 mass % is put into After 6.6g, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by methyl methacrylate 22.5g, n-butyl acrylate 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3- methacryl The mixed liquor that oxygroup propyl trimethoxy silicane 1.1g is formed；And by acrylic acid 0.9g, reactive emulsifier (ADEKA societies system It makes, " Adeka Reasoap SR-1025 "；Solid component content be 25 mass % aqueous solution) 1.2g, reactive emulsifier (the first industrial pharmaceutical society manufactures, " Aquaron KH-1025 "；Solid component content be 25 mass % aqueous solution) 1.2g, mistake The mixed liquor that 2.0 mass % aqueous solutions 30g, the ion exchange water 286.4g of ammonium sulfate are formed.And then by the temperature in reactor Degree maintain 80 DEG C continue stir abouts 1 it is small when after, be cooled to room temperature, by 25% ammonia spirit be added to reaction solution in adjustment pH be After 8, it is filtered with the metal mesh of 100 mesh.Be adjusted with ion exchange water so that solid component content be 10.0 mass %, The aqueous dispersion (CD-1) for the polymer (C-1) that number average bead diameter is 155nm is obtained as polymer.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-1) 36.9 mass % in.

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Condensation product conversion is hydrolyzed in base acryloxypropyl trimethoxy silane, is respectively 7.9 matter in polymer (C-1) %, 30.2 mass % and 0.4 mass % are measured, adds up to 38.5 mass %.

It should be noted that the content to convert for the hydrolytic condensate of above-mentioned each monomer is calculated based on following formula.

Such as in the case of (a) ingredient, the reactive group (alkoxy etc.) of (a) ingredient by hydrolyze or condensation reaction and Silanol bonds are converted to, become the condensation product of structural unit (A), the conversion coefficient of (a) described herein ingredient is its mass ratio (total amount of the total amount of the condensation product/(a) ingredient), can be represented by following formula (i).

In addition, in the case of such as (b) ingredient, the reactive group (alkoxy etc.) of (b) ingredient is by hydrolyzing or being condensed It reacts and is converted to silanol bonds, become the condensation product with structural unit (B), the conversion coefficient of (b) described herein ingredient For its mass ratio (total amount of the total amount of the condensation product/(b) ingredient), can be represented by following formula (ii).

The content (quality %) of structural unit (A) in polymer (C)=[inventory (g) of (a) ingredient × conversion system Number] ÷ total solid content contents (g) × 100

【Number 1】

α：(a) molecular weight of ingredient

r₂：The R of general formula (1)²Molecular weight

γ：The atomic weight of oxygen

The conversion coefficient of each ingredient calculated as described above is as follows.

Dimethyldimethoxysil,ne：0.617

Di ethoxy di methyl-monosilane：0.500

Diisopropyl dimethoxy silane：0.739

Dimethoxydiphenylsilane：0.811

Dimethoxymethylphenylsilane：0.747

The content (quality %) of structural unit (B) in polymer (C)=[inventory (g) of (b) ingredient × conversion system Number] ÷ total solid content contents (g) × 100

【Number 2】

β：(b) molecular weight of ingredient

r₄：The R of general formula (2)⁴Molecular weight

γ：The atomic weight of oxygen

Methyltrimethoxysilane：0.493

Phenyltrimethoxysila,e：0.652

3- methacryloxypropyl trimethoxy silanes：0.722

[Production Example 4]

The synthesis of the aqueous dispersion (CD-2) of polymer (C-2)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 8.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It will reaction Temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 105.0g, phenyltrimethoxysila,e 10.0g, methyltrimethoxysilane 65.7g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 133nm polymer (C-2) Aqueous dispersion (CD-2).

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-2) 47.9 mass % in.

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-2) in 24.0 mass %, 17.7 mass % and 0.6 mass %, add up to 42.3 mass %.

[Production Example 5]

The synthesis of the aqueous dispersion (CD-3) of polymer (C-3)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 8.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 125.0g, phenyltrimethoxysila,e 10.0g, methyltrimethoxysilane 40.0g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 170nm polymer (C-3) Aqueous dispersion (CD-3).

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-3) 57.2 mass % in.

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-3) in 14.6 mass %, 17.8 mass % and 0.6 mass %, add up to 33.0 mass %.

[Production Example 6]

The synthesis of the aqueous dispersion (CD-4) of polymer (C-4)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 810g, After the dodecyl benzene sulfonic acid aqueous solution 7.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyl diethoxysilane into the reactor The mixed liquor that 158.0g, phenyltrimethoxysila,e 16.8g, methyltrimethoxysilane 33.1g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 20.0g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 180nm polymer (C-4) Aqueous dispersion (CD-4).

Condensation product conversion is hydrolyzed in the di ethoxy di methyl-monosilane used during to synthesizing the aqueous dispersion, is polymer (C-4) 59.4 mass % in.

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-4) in 12.3 mass %, 18.0 mass % and 0.6 mass %, add up to 30.9 mass %.

The synthesis of the aqueous dispersion (CD-5) of polymer (C-5)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 830g, After the dodecyl benzene sulfonic acid aqueous solution 7.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by diisopropyl dimethoxy silane into the reactor The mixed liquor that 101.5g, phenyltrimethoxysila,e 10.0g, methyltrimethoxysilane 33.1g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 180nm polymer (C-5) Aqueous dispersion (CD-5).

Condensation product conversion is hydrolyzed in the diisopropyl dimethoxy silane used during to synthesizing the aqueous dispersion, for polymerization 58.1 mass % in object (C-5).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-5) in 12.6 mass %, 18.6 mass % and 0.6 mass %, add up to 31.8 mass %.

[Production Example 8]

The synthesis of the aqueous dispersion (CD-6) of polymer (C-6)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 7.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor 71.3g, dimethoxydiphenylsilane 49.3g, phenyltrimethoxysila,e 36.8g, methyltrimethoxysilane 33.1g are formed Mixed liquor.Thereafter, the temperature in reactor is maintained 80 DEG C and continues stirring 30 minutes.Then, the ten of 10 mass % are put into After dialkyl benzene sulfonic acids aqueous solution 16.8g, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, 2 matter are put into Measure % ammonium persulfate aqueous solution 6.6g input after, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when it is same When the mixed liquor that is made of tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g is added dropwise；With And (ADEKA societies manufacture, " Adeka Reasoap SR-1025 " by acrylic acid 0.9g, reactive emulsifier；Solid component content For the aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Gu Body component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water of ammonium persulfate 170.0g the mixed liquor formed.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, room is cooled to Temperature by 25% ammonia spirit added to after adjustment pH is 8 in reaction solution, is filtered with the metal mesh of 100 mesh.Use ion exchange Water be adjusted so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 180nm polymer (C-6) aqueous dispersion (CD-6).

The dimethyldimethoxysil,ne and dimethoxydiphenylsilane used during to synthesizing the aqueous dispersion respectively into Row complete hydrolysis condensation product converts, and is 31.9 mass % and 29.0 mass % in polymer (C-6).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-6) in 11.8 mass %, 17.4 mass % and 0.6 mass %, add up to 29.8 mass %.

[Production Example 9]

The synthesis of the aqueous dispersion (CD-7) of polymer (C-7)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 7.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethoxymethylphenylsilane into the reactor The mixed liquor that 109.7g, phenyltrimethoxysila,e 10.0g, methyltrimethoxysilane 33.1g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 170nm polymer (C-7) Aqueous dispersion (CD-7).

Condensation product conversion is hydrolyzed in the dimethoxymethylphenylsilane used during to synthesizing the aqueous dispersion, for polymerization 60.3 mass % in object (C-7).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-7) in 12.0 mass %, 17.6 mass % and 0.6 mass %, add up to 30.2 mass %.

[Production Example 10]

The synthesis of the aqueous dispersion (CD-8) of polymer (C-8)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 10.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 140.0g, phenyltrimethoxysila,e 20.0g, methyltrimethoxysilane 5.0g are formed.It thereafter, will be in reactor Temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 119nm polymer (C-8) Aqueous dispersion (CD-8).

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-8) 64.7 mass % in.

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C-8) in 1.8 mass %, 22.8 mass % and 0.6 mass %, add up to 25.2 mass %.

[Production Example 11]

The synthesis of the aqueous dispersion (CD-9) of polymer (C-9)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 10.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 140.0g, methyltrimethoxysilane 40.0g are formed.Thereafter, the temperature in reactor is maintained into 80 DEG C of continuation Stirring 30 minutes.Then, after putting into the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass %, the temperature in reactor is tieed up Hold 80 DEG C continue stirring 2 it is small when.Herein, after putting into the ammonium persulfate aqueous solution 6.6g of 2 mass %, by the temperature in reactor Keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by methyltrimethoxysilane 30.0g, tetraethoxysilane 28.6g, 3- The mixed liquor that methacryloxypropyl trimethoxy silane 1.1g is formed；And by acrylic acid 0.9g, reactive emulsifier (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content be 25 mass % aqueous solution) 2.3g, reaction Property emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid component content is the aqueous solution of 25 mass %) The mixed liquor that 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate are formed.Further by reactor In temperature maintain 80 DEG C continue stir abouts 1 it is small when after, be cooled to room temperature, by 25% ammonia spirit be added to reaction solution in adjust After pH is 8, it is filtered with the metal mesh of 100 mesh.It is adjusted with ion exchange water so that solid component content is 10.0 matter % is measured, the aqueous dispersion (CD-9) for the polymer (C-9) that number average bead diameter is 150nm is obtained as polymer.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-9) 63.9 mass % in.

In addition, the methyltrimethoxysilane that uses of to synthesizing aqueous dispersion when and 3- methacryloxypropyls three Condensation product conversion is hydrolyzed in methoxy silane, is the 25.5 mass % and 0.6 mass % in polymer (C-9), adds up to 26.1 quality %.

[Production Example 12]

The synthesis of the aqueous dispersion (CD-10) of polymer (C-10)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 10.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 140.0g, phenyltrimethoxysila,e 25.0g are formed.Thereafter, the temperature in reactor is maintained into 80 DEG C of continuation Stirring 30 minutes.Then, after putting into the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass %, the temperature in reactor is tieed up Hold 80 DEG C continue stirring 2 it is small when.Herein, after putting into the ammonium persulfate aqueous solution 6.6g of 2 mass %, by the temperature in reactor Keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3- The mixed liquor that methacryloxypropyl trimethoxy silane 1.1g is formed；And by acrylic acid 0.9g, reactive emulsifier (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content be 25 mass % aqueous solution) 2.3g, reaction Property emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid component content is the aqueous solution of 25 mass %) The mixed liquor that 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate are formed.Further by reactor In temperature maintain 80 DEG C continue stir abouts 1 it is small when after, be cooled to room temperature, by 25% ammonia spirit be added to reaction solution in adjust After pH is 8, it is filtered with the metal mesh of 100 mesh.It is adjusted with ion exchange water so that solid component content is 10.0 matter % is measured, the aqueous dispersion (CD-10) for the polymer (C-10) that number average bead diameter is 160nm is obtained as polymer.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer (C-10) 64.3 mass % in.

In addition, the phenyltrimethoxysila,e that uses of to synthesizing aqueous dispersion when and 3- methacryloxypropyls three Condensation product conversion is hydrolyzed in methoxy silane, is the 25.1 mass % and 0.6 mass % in polymer (C-10), adds up to 25.7 quality %.

[Production Example 13]

The synthesis of the aqueous dispersion (C ' D-11) of polymer (C ' -11)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 81.0g, phenyltrimethoxysila,e 124.8g, methyltrimethoxysilane 29.4g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 12.3g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 1.2g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 1.2g, 2.0 mass % aqueous solutions 30g, the ion exchange water 286.4g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 160nm polymer (C '- 11) aqueous dispersion (C ' D-11).

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer 30.1 mass % in (C ' -11).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C ' -11) in 8.7 mass %, 53.8 mass % and 0.5 mass %, add up to 63.0 mass %.

[Production Example 14]

The synthesis of the aqueous dispersion (C ' D-12) of polymer (C ' -12)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 81.0g, phenyltrimethoxysila,e 73.0g, methyltrimethoxysilane 30.0g are formed.It thereafter, will be in reactor Temperature maintain 80 DEG C continue stirring 30 minutes.Then, after putting into the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass %, By in reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, after putting into the ammonium persulfate aqueous solution 6.6g of 2 mass %, By in reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by methyl methacrylate 22.5g, propylene Sour N-butyl 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3- methacryloxypropyl three The mixed liquor that methoxy silane 1.1g is formed；And (ADEKA societies manufacture, " Adeka by acrylic acid 0.9g, reactive emulsifier Reasoap SR-1025”；Solid component content be 25 mass % aqueous solution) 1.2g, reactive emulsifier (first industry system Medicine society manufactures, " Aquaron KH-1025 "；Solid component content be 25 mass % aqueous solution) 1.2g, the 2.0 of ammonium persulfate The mixed liquor that quality % aqueous solutions 30g, ion exchange water 286.4g are formed.Further by reactor temperature maintain 80 DEG C after It after when continuous stir about 1 is small, is cooled to room temperature, 25% ammonia spirit is added in reaction solution and adjusts pH as after 8, with 100 purposes Metal mesh is filtered.Be adjusted with ion exchange water so that solid component content be 10.0 mass %, obtained as polymer To the aqueous dispersion (C ' D-12) for the polymer (C ' -12) that number average bead diameter is 157nm.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer 30.1 mass % in (C ' -12).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C ' -12) in 8.9 mass %, 33.4 mass % and 0.5 mass %, add up to 42.8 mass %.

[Production Example 15]

The synthesis of the aqueous dispersion (C ' D-13) of polymer (C ' -13)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 10.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 168.0g, phenyltrimethoxysila,e 10.0g are formed.Thereafter, the temperature in reactor is maintained into 80 DEG C of continuation Stirring 30 minutes.Then, after putting into the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass %, the temperature in reactor is tieed up Hold 80 DEG C continue stirring 2 it is small when.Herein, after putting into the ammonium persulfate aqueous solution 6.6g of 2 mass %, by the temperature in reactor Keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3- The mixed liquor that methacryloxypropyl trimethoxy silane 1.1g is formed；And by acrylic acid 0.9g, reactive emulsifier (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content be 25 mass % aqueous solution) 2.3g, reaction Property emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid component content is the aqueous solution of 25 mass %) The mixed liquor that 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate are formed.Further by reactor In temperature maintain 80 DEG C continue stir abouts 1 it is small when after, be cooled to room temperature, by 25% ammonia spirit be added to reaction solution in adjust After pH is 8, it is filtered with the metal mesh of 100 mesh.It is adjusted with ion exchange water so that solid component content is 10.0 matter % is measured, the aqueous dispersion (C ' D-13) for the polymer (C ' -13) that number average bead diameter is 146nm is obtained as polymer.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer 73.1 mass % in (C ' -13).

In addition, the phenyltrimethoxysila,e that uses of to synthesizing aqueous dispersion when and 3- methacryloxypropyls three Condensation product conversion is hydrolyzed in methoxy silane, is the 16.9 mass % and 0.6 mass % in polymer (C ' -13), adds up to 17.5 quality %.

[Production Example 16]

The synthesis of the aqueous dispersion (C ' D-14) of polymer (C ' -14)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethyldimethoxysil,ne into the reactor The mixed liquor that 150.0g, phenyltrimethoxysila,e 30.0g, methyltrimethoxysilane 10.0g are formed.Thereafter, by reactor In temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 5.6g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by methyl methacrylate 22.5g, N-butyl acrylate 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3- methacryloxy third The mixed liquor that base trimethoxy silane 1.1g is formed；And by acrylic acid 0.9g, reactive emulsifier (ADEKA societies manufacture, “Adeka Reasoap SR-1025”；Solid component content be 25 mass % aqueous solution) 1.2g, reactive emulsifier (first Industrial pharmaceutical society manufactures, " Aquaron KH-1025 "；Solid component content be 25 mass % aqueous solution) 1.2g, ammonium persulfate 2.0 mass % aqueous solutions 30g, ion exchange water 286.4g form mixed liquor.Further the temperature in reactor is maintained It after when 80 DEG C of continuation stir abouts 1 are small, is cooled to room temperature, by 25% ammonia spirit added to after adjustment pH is 8 in reaction solution, uses The metal mesh of 100 mesh is filtered.It is adjusted with ion exchange water so that solid component content is 10.0 mass %, as poly- It closes object and obtains the aqueous dispersion (C ' D-14) for the polymer (C ' -14) that number average bead diameter is 163nm.

Condensation product conversion is hydrolyzed in the dimethyldimethoxysil,ne used during to synthesizing the aqueous dispersion, is polymer 54.2 mass % in (C ' -14).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C ' -14) in 2.9 mass %, 16.1 mass % and 0.5 mass %, add up to 19.5 mass %.

[Production Example 17]

The synthesis of the aqueous dispersion (C ' D-15) of polymer (C ' -15)

Put into the reactor with reflux condenser, dropwise adding tank, thermometer and agitating device ion exchange water 850g, After the dodecyl benzene sulfonic acid aqueous solution 7.0g of 10 mass %, the temperature in reactor is heated to 80 DEG C under stirring.It is anti-inciting somebody to action Answer temperature in device kept for 80 DEG C in the state of with about 2 it is small when be added dropwise by dimethoxymethylphenylsilane into the reactor The mixed liquor that 140.0g, phenyltrimethoxysila,e 8.0g, methyltrimethoxysilane 10.0g are formed.It thereafter, will be in reactor Temperature maintain 80 DEG C continue stirring 30 minutes.Then, the dodecyl benzene sulfonic acid aqueous solution 16.8g of 10 mass % is put into Afterwards, by reactor temperature maintain 80 DEG C continue stirring 2 it is small when.Herein, the ammonium persulfate aqueous solution 6.6g of 2 mass % is put into Afterwards, by reactor temperature keep 80 DEG C in the state of with about 2 it is small when simultaneously be added dropwise by phenyltrimethoxysila,e The mixed liquor that 26.8g, tetraethoxysilane 28.6g, 3- methacryloxypropyl trimethoxy silane 1.1g are formed；And By acrylic acid 0.9g, reactive emulsifier, (ADEKA societies manufacture, " Adeka Reasoap SR-1025 "；Solid component content is The aqueous solution of 25 mass %) 2.3g, reactive emulsifier (the first industrial pharmaceutical society manufacture, " Aquaron KH-1025 "；Solid Component content be 25 mass % aqueous solution) 2.3g, 2.0 mass % aqueous solutions 30g, the ion exchange water 170.0g of ammonium persulfate The mixed liquor of composition.After when further maintaining 80 DEG C of continuation stir abouts 1 small temperature in reactor, it is cooled to room temperature, it will 25% ammonia spirit is filtered added to after adjustment pH is 8 in reaction solution with the metal mesh of 100 mesh.With ion exchange water into Row adjust so that solid component content be 10.0 mass %, as polymer obtain number average bead diameter be 178nm polymer (C '- 15) aqueous dispersion (C ' D-15).

Condensation product conversion is hydrolyzed in the dimethoxymethylphenylsilane used during to synthesizing the aqueous dispersion, for polymerization 71.7 mass % in object (C ' -15).

In addition, methyltrimethoxysilane, phenyltrimethoxysila,e and 3- first that synthesizing aqueous dispersion when uses Base acryloxypropyl trimethoxy silane be hydrolyzed condensation product conversion, be polymer (C ' -15) in 3.4 mass %, 15.6 mass % and 0.5 mass %, add up to 19.5 mass %.

Each polymer is listed in table 1 into being grouped into.

【Table 1】

[Production Example 18]

The synthesis of inorganic oxide (E-1) with photocatalytic activity

Silica modified rutile-type titanium dioxide

While the pH of reaction solution is maintained 5~9, add with TiO₂It is water-soluble to count the titanium tetrachloride that concentration is 200g/L Liquid 700mL and with Na₂The sodium hydrate aqueous solution that O meter concentration is 100g/L.Thereafter, after the pH for adjusting reaction solution is 7, filtering, Cleaning is carried out until the electrical conductivity of filtrate is 100 μ S/cm, obtains the wet filter of titanium dioxide that solid component content is 28.3 mass % Cake 1.The titanium dioxide wet cake 1 includes the particle with Rutile structure, and the number average bead diameter of 1 particle is 8nm.

Obtained titanium dioxide wet cake 1 is diluted with pure water, prepares the slurry of 1 mol/L.By slurry 1L Input further adds the nitric acid of 1 equivalent so that the molar ratio of titanium dioxide/nitric acid is heated to 95 for 1/1 into the flask of 3L DEG C temperature, the temperature maintain 2 it is small when, carry out sour heating.Slurry after acid is heated is cooled to room temperature, uses It is 6.7 that 28% ammonium hydroxide, which is neutralized to pH, is filtered.Thereafter, cleaning is carried out until the electrical conductivity of filtrate is 100 μ S/cm, consolidate Body component content is the titanium dioxide wet cake 2 of 25 mass %.

The sodium hydrate aqueous solution of 10% concentration is added into obtained titanium dioxide wet cake 2, carries out repulping, Afterwards, with supersonic wave cleaning machine disperse 3 it is small when, obtain pH10.5, the alkaline TiO 2 sol of 10 mass % of solid component content. Alkalescence TiO 2 sol 2L is put into the flask of 3L, 70 DEG C of temperature is warming up to, adds with SiO₂Counting concentration is The sodium silicate aqueous solution 69.4mL of 432g/L, be warming up to thereafter 90 DEG C and maintain 1 it is small when after, add 10% sulfuric acid adjustment pH be 6, it is utilized the TiO 2 sol that the hydrous oxide of silicon is surface-treated the surface of titanium dioxide.

Obtained TiO 2 sol is cooled to room temperature, adds the pure water of 5.4L, is carried out using desalination and concentration device miscellaneous The removing and concentration of matter obtain pH7.3,29 mass % of solid component content, the neutral rutile-type of electrical conductivity 1.18mS/cm TiO 2 sol.The neutrality rutile titanium dioxide colloidal sol is compared with TiO₂With SiO₂On the basis of the silicon containing 15 mass % Hydrous oxide.The number average bead diameter of 1 particle of the titanium dioxide in the colloidal sol is 9nm.

[Production Example 19]

The synthesis of inorganic oxide (E-2) with photocatalytic activity

Silica modifies anatase titanium dioxide

Heating hydrolysis is carried out to titanium ore and the obtained titanium sulfate solution of sulfuric acid reaction, by the aggegation metatitanic acid system of generation Into with TiO₂It is scaled the aqueous slurry of 30 mass %.Add ammonium hydroxide in the slurry, be neutralized to pH as 7, thereafter by filtering, It cleans to remove sulfate ion, obtains dewatered cake.Peptization is carried out by adding in nitric acid in obtained dewatered cake Processing obtains being made of the titanium dioxide fine particles (number average bead diameter of 1 particle is 7nm) with Detitanium-ore-type crystalline texture The acidic titania colloidal sol of pH1.5.

Obtained acidic titania colloidal sol with pure water is diluted, TiO is made₂Converted score is the titanium dioxide of 200g/L After colloidal sol 600mL, 70 DEG C are warming up to, by SiO₂The sodium silicate aqueous solution 20.8mL and 20% sulfuric acid that converted score is 432g/L are same When be added.Thereafter, cure 30 minutes.Next, after addition 10% sodium hydrate aqueous solution adjustment pH is 8, with 2% sulfuric acid Aqueous solution adjustment pH is 6, is filtered, cleans, obtains wet cake.By after the wet cake repulping in pure water, ultrasound is carried out Wavelength-division dissipates, and obtains the anatase type TiO 2 sol (20 mass %, pH7.5 of solid component content) of neutral region stabilization.Its In, aggegation silica is coated in the state of Porous on the surface of titanium dioxide fine particles, and content is compared with TiO₂100 mass Part is with SiO₂It is scaled 7 mass parts.

[embodiment 1]

Mixed number is equal in aqueous dispersion (CD-1) 180.0g (10.0 mass % of solid component content) of polymer (C-1) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 60.0g, ethyl alcohol 50.0g and ion exchange water 210.0g, and be stirred, so as to obtain solid component content as 6.0 The aqueous coating agent composition (K-1) of quality %.The viscosity of the aqueous coating agent composition (K-1) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-1) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 1).The aqueous coating agent composition (K-1), the various physical property of film and breadboard (L-1) and evaluation result are listed in table 2.

[embodiment 2]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-2) (CD-2) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-2) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-2) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-2) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 2).The aqueous coating agent composition (K-2), the various physical property of film and breadboard (L-2) and evaluation result are listed in table 2.

[embodiment 3]

Mixed number is equal in aqueous dispersion (CD-2) 180.0g (10.0 mass % of solid component content) of polymer (C-2) The moisture of grain size 8nm dissipates cabosil (D-2), and (Nissan Chemical Industries society manufactures, " Snowtex O "；Solid component content 30 Quality %) 40.0g, ethyl alcohol 50.0g and ion exchange water 230.0g, and be stirred, so as to obtain solid component content as 6.0 The aqueous coating agent composition (K-3) of quality %.The viscosity of the aqueous coating agent composition (K-3) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-3) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 3).The aqueous coating agent composition (K-3), the various physical property of film and breadboard (L-3) and evaluation result are listed in table 2.

[embodiment 4]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-3) (CD-3) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-4) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-4) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-4) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 4).The aqueous coating agent composition (K-4), the various physical property of film and breadboard (L-4) and evaluation result are listed in table 2.

[embodiment 5]

On the single side (face for being coated with enamel-cover coating in advance) of 7cm × 15cm base materials Y of enamel-cover coating is coated in advance Using spraying come application aqueous coating agent composition (K-4) so that coating weight is 17g/m².Base material through application is kept into water It is flat, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtain being formed with the breadboard (L-5) of film on base material.It will The various physical property and evaluation result of breadboard (L-5) are listed in table 2.

[embodiment 6]

Mixed number is equal in aqueous dispersion (CD-3) 180.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 25nm dissipates cabosil (D-3), and (Nissan Chemical Industries society manufactures, " Snowtex O-40 "；Solid constituent contains Measure 40 mass %) 30.0g, ethyl alcohol 50.0g and ion exchange water 240.0g, and be stirred, so as to obtain solid component content For the aqueous coating agent composition (K-6) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-6) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-6) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 6).The aqueous coating agent composition (K-6), the various physical property of film and breadboard (L-6) and evaluation result are listed in table 2.

[embodiment 7]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-4) (CD-4) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-7) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-7) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-7) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 7).The aqueous coating agent composition (K-7), the various physical property of film and breadboard (L-7) and evaluation result are listed in table 2.

[embodiment 8]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-5) (CD-5) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-8) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-8) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-8) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 8).The aqueous coating agent composition (K-8), the various physical property of film and breadboard (L-8) and evaluation result are listed in table 2.

[embodiment 9]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-6) (CD-6) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-9) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-9) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-9) so that coating weight be 17g/m².Base material through application is protected Water holding is put down, and when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard (L- of film on base material 9).The aqueous coating agent composition (K-9), the various physical property of film and breadboard (L-9) and evaluation result are listed in table 2.

[embodiment 10]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-7) (CD-7) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-10) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-10) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-10) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-10).The aqueous coating agent composition (K-10), the various physical property of film and breadboard (L-10) and evaluation result are listed in Table 2.

[embodiment 11]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-8) (CD-8) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-11) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-11) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-11) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-11).The aqueous coating agent composition (K-11), the various physical property of film and breadboard (L-11) and evaluation result are listed in Table 2.

[embodiment 12]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-9) (CD-9) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-12) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-12) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-12) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-12).The aqueous coating agent composition (K-12), the various physical property of film and breadboard (L-12) and evaluation result are listed in Table 2.

[embodiment 13]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C-10) (CD-10) 180.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 1 in addition For the aqueous coating agent composition (K-13) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-13) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-13) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-13).The aqueous coating agent composition (K-13), the various physical property of film and breadboard (L-13) and evaluation result are listed in Table 2.

[embodiment 14]

Mixed number is equal in aqueous dispersion (CD-2) 240.0g (10.0 mass % of solid component content) of polymer (C-2) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 30.0g, ethyl alcohol 50.0g and ion exchange water 180.0g, and be stirred, so as to obtain solid component content as 6.0 The aqueous coating agent composition (K-14) of quality %.The viscosity of the aqueous coating agent composition (K-14) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-14) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-14).The aqueous coating agent composition (K-14), the various physical property of film and breadboard (L-14) and evaluation result are listed in Table 3.

[embodiment 15]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 45.0g, ethyl alcohol 50.0g and ion exchange water 195.0g, and be stirred, so as to obtain solid component content as 6.0 The aqueous coating agent composition (K-15) of quality %.The viscosity of the aqueous coating agent composition (K-15) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-15) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-15).The aqueous coating agent composition (K-15), the various physical property of film and breadboard (L-15) and evaluation result are listed in Table 3.

[embodiment 16]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 37.5g, there is inorganic oxide (E-1) 5.2g (29 mass % of solid component content) of photocatalytic activity, ethyl alcohol 50.0g and ion exchange water 197.3g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 6.0 mass % Agent composition (K-16).The viscosity of the aqueous coating agent composition (K-16) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-16) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-16).The aqueous coating agent composition (K-16), the various physical property of film and breadboard (L-16) and evaluation result are arranged In table 3.

[embodiment 17]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 30.0g, there is inorganic oxide (E-1) 10.3g (29 mass % of solid component content) of photocatalytic activity, ethyl alcohol 50.0g and ion exchange water 199.7g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 6.0 mass % Agent composition (K-17).The viscosity of the aqueous coating agent composition (K-17) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-17) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-17).The aqueous coating agent composition (K-17), the various physical property of film and breadboard (L-17) and evaluation result are arranged In table 3.

[embodiment 18]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 22.5g, there is inorganic oxide (E-1) 15.5g (29 mass % of solid component content) of photocatalytic activity, ethyl alcohol 50.0g and ion exchange water 202.0g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 6.0 mass % Agent composition (K-18).The viscosity of the aqueous coating agent composition (K-18) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-18) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-18).The aqueous coating agent composition (K-18), the various physical property of film and breadboard (L-18) and evaluation result are arranged In table 3.

[embodiment 19]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 37.5g, there is inorganic oxide (E-2) 7.5g (20 mass % of solid component content) of photocatalytic activity, ethyl alcohol 50.0g and ion exchange water 195.0g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 6.0 mass % Agent composition (K-19).The viscosity of the aqueous coating agent composition (K-19) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-19) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-19).The aqueous coating agent composition (K-19), the various physical property of film and breadboard (L-19) and evaluation result are arranged In table 3.

[embodiment 20]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 30.0g, have photocatalytic activity inorganic oxide (E-1) 10.3g (29 mass % of solid component content), fluorine carbon Surfactant (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, ethyl alcohol 50.0g and ion exchange water 199.5g, and It is stirred, so as to obtain the aqueous coating agent composition (K-20) that solid component content is 6.0 mass %.The aqueous coating agent The viscosity of composition (K-20) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-20) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-20).The aqueous coating agent composition (K-20), the various physical property of film and breadboard (L-20) and evaluation result are arranged In table 3.

[embodiment 21]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 30.0g, have photocatalytic activity inorganic oxide (E-1) 10.3g (29 mass % of solid component content), fluorine carbon (AGC SEIMI CHEMICAL societies manufacture surfactant (F-2), " Surflon S-232 "；30 matter of solid component content Measure %) 0.7g, ethyl alcohol 50.0g and ion exchange water 199.0g, and be stirred, so as to obtain solid component content as 6.0 matter Measure the aqueous coating agent composition (K-21) of %.The viscosity of the aqueous coating agent composition (K-21) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-21) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-21).The aqueous coating agent composition (K-21), the various physical property of film and breadboard (L-21) and evaluation result are arranged In table 3.

[embodiment 22]

Mixed number is equal in aqueous dispersion (CD-3) 210.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 30.0g, have photocatalytic activity inorganic oxide (E-1) 10.3g (29 mass % of solid component content), fluorine carbon Surfactant (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, it is adjusted using ion exchange water so that solid Fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 3.0g that component content is 1.0 mass %, Ethyl alcohol 50.0g and ion exchange water 196.5g, and be stirred, so as to obtain the water system that solid component content is 6.0 mass % Coating agent composition (K-22).The viscosity of the aqueous coating agent composition (K-22) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-22) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-22).The aqueous coating agent composition (K-22), the various physical property of film and breadboard (L-22) and evaluation result are arranged In table 3.

[embodiment 23]

Without using be adjusted using ion exchange water so that solid component content be 1.0 mass % fadedness pigment (G-1) (Kishida Chemical manufacture, " methylene blue ") 3.0g, and using being adjusted using ion exchange water so that solid Fadedness pigment (G-2) (hodogaya chemical industry society manufacture, " acid red ") 3.0g that body ingredient is 1.0 mass %, except this with The outer aqueous coating agent composition (K-23) for obtaining 6.0 mass % of solid component content similarly to Example 21.The water system applies The viscosity of layer agent composition (K-23) is 2mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-23) of application so that coating weight be 17g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-23).The aqueous coating agent composition (K-23), the various physical property of film and breadboard (L-23) and evaluation result are arranged In table 3.

[embodiment 24]

The mixing number average bead diameter in aqueous dispersion (CD-3) 60.0g (10.0 mass % of solid constituent) of polymer (C-3) The moisture of 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；20 matter of solid component content Measure %) 7.5g, have photocatalytic activity inorganic oxide (E-1) 5.2g (29 mass % of solid component content), fluorocarbon surface Activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, it is adjusted using ion exchange water so that solid constituent Fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g that content is 1.0 mass %, utilization Ion exchange water is adjusted so that solid component content is cellulose-based thickeners (H-1) (Daicel of 1.0 mass % Finechem societies manufacture, " HEC Daicel SP900 ") 40.0g, ethyl alcohol 50.0g and ion exchange water 336.1g, and stirred It mixes, so as to obtain the aqueous coating agent composition (K-24) that solid component content is 1.9 mass %.The aqueous coating agent composition (K-24) viscosity is 15mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-24) of application so that coating weight be 50g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-24).The aqueous coating agent composition (K-24), the various physical property of film and breadboard (L-24) and evaluation result are arranged In table 3.

[embodiment 25]

On the single side (face for being coated with enamel-cover coating in advance) of 7cm × 15cm base materials Y of enamel-cover coating is coated in advance Using spraying come application aqueous coating agent composition (K-24) so that coating weight is 50g/m².Base material through application is kept into water It is flat, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtain being formed with the breadboard (L-25) of film on base material. The various physical property of breadboard (L-25) and evaluation result are listed in table 3.

[embodiment 26]

Mixed number is equal in aqueous dispersion (CD-3) 60.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 7.5g, have photocatalytic activity inorganic oxide (E-1) 5.2g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into Divide fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g, profit that content is 1.0 mass % It is adjusted with ion exchange water so that solid component content is cellulose-based thickeners (H-1) (Daicel of 1.0 mass % Finechem societies manufacture, " HEC Daicel SP900 ") 80.0g, ethyl alcohol 50.0g and ion exchange water 296.1g, and stirred It mixes, so as to obtain the aqueous coating agent composition (K-26) that solid component content is 2.0 mass %.The aqueous coating agent composition (K-26) viscosity is 28mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-26) of application so that coating weight be 50g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-26).The aqueous coating agent composition (K-26), the various physical property of film and breadboard (L-26) and evaluation result are arranged In table 3.

[embodiment 27]

Without using aqueous dispersion (CD-3) 60.0g of polymer (C-3), and use the aqueous dispersion of polymer (C-7) (CD-7) 60.0g (10.0 mass % of solid component content), obtains solid component content similarly to Example 25 in addition The aqueous coating agent composition (K-27) of 2.0 mass %.The viscosity of the aqueous coating agent composition (K-27) is 26mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-27) of application so that coating weight be 50g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-27).The aqueous coating agent composition (K-27), the various physical property of film and breadboard (L-27) and evaluation result are arranged In table 4.

[embodiment 28]

Mixed number is equal in aqueous dispersion (CD-3) 60.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 7.5g, have photocatalytic activity inorganic oxide (E-1) 5.2g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into Divide fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g, profit that content is 1.0 mass % It is adjusted with ion exchange water so that cellulose-based thickeners (H-2) (SHIN-ETSU HANTOTAI's chemistry that solid component content is 1.0 mass % Industrial society's manufacture, " METOLOSE 90SH-30000 ") 80.0g, ethyl alcohol 50.0g and ion exchange water 296.1g, and stirred It mixes, so as to obtain the aqueous coating agent composition (K-28) that solid component content is 2.0 mass %.The aqueous coating agent composition (K-28) viscosity is 25mPas.

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come the above-mentioned aqueous coating agent composition (K-28) of application so that coating weight be 50g/m².It will be through application Base material keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the experiment of film on base material Plate (L-28).The aqueous coating agent composition (K-28), the various physical property of film and breadboard (L-28) and evaluation result are arranged In table 4.

[embodiment 29]

Mixed number is equal in aqueous dispersion (CD-3) 205.8g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 29.4g, have photocatalytic activity inorganic oxide (E-1) 10.1g (29 mass % of solid component content), fluorine carbon Surfactant (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, it is adjusted using ion exchange water so that solid Fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 3.0g that component content is 1.0 mass %, (Dow Chemical societies manufacture anti-algae/mould inhibitor (J-1), " KLARIX4000 ", isothiazoline based compound；4 matter of active ingredient Measure %) 15.0g, ethyl alcohol 50.0g and ion exchange water 186.5g, and be stirred, so as to obtain solid component content as 6.0 matter Measure the aqueous coating agent composition (K-29) of %.The viscosity of the aqueous coating agent composition (K-29) is 2mPas.

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-29) of application so that coating weight be 17g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-29) of film.By the aqueous coating agent composition (K-29), film and breadboard (L-29) various physical property and Evaluation result is listed in table 4.

[embodiment 30]

Mixed number is equal in aqueous dispersion (CD-3) 207.2g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 29.6g, have photocatalytic activity inorganic oxide (E-1) 10.2g (29 mass % of solid component content), fluorine carbon Surfactant (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, it is adjusted using ion exchange water so that solid Fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 3.0g that component content is 1.0 mass %, (Dow Chemical societies manufacture anti-algae/mould inhibitor (J-2), " ROCIMA345 ", isothiazoline based compound and triazine system chemical combination The mixture of object；12 mass % of active ingredient) 3.0g, ethyl alcohol 50.0g and ion exchange water 196.8g, and be stirred, so as to Obtain the aqueous coating agent composition (K-30) that solid component content is 6.0 mass %.The aqueous coating agent composition (K-30) Viscosity be 2mPas.

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-30) of application so that coating weight be 17g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-30) of film.By the aqueous coating agent composition (K-30), film and breadboard (L-30) various physical property and Evaluation result is listed in table 4.

[embodiment 31]

Mixed number is equal in aqueous dispersion (CD-3) 197.4g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 28.2g, have photocatalytic activity inorganic oxide (E-1) 9.7g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into It is fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 3.0g that point content is 1.0 mass %, anti- Algae/mould inhibitor (J-3) (Japanese Cao Da societies manufacture, the mixing of " Biocut-N35 ", imidazole compound and triazine based compound Object；35 mass % of active ingredient) 5.0g, ethyl alcohol 50.0g and ion exchange water 206.5g, and be stirred, so as to obtain solid Component content is the aqueous coating agent composition (K-31) of 6.0 mass %.The viscosity of the aqueous coating agent composition (K-31) is 2mPa·s。

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-31) of application so that coating weight be 17g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-31) of film.By the aqueous coating agent composition (K-31), film and breadboard (L-31) various physical property and Evaluation result is listed in table 4.

[embodiment 32]

Mixed number is equal in aqueous dispersion (CD-3) 58.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 7.3g, have photocatalytic activity inorganic oxide (E-1) 5.0g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into Divide fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g, profit that content is 1.0 mass % It is adjusted with ion exchange water so that solid component content is cellulose-based thickeners (H-1) (Daicel of 1.0 mass % Finechem societies manufacture, " HEC Daicel SP900 ") 80.0g, anti-algae/mould inhibitor (J-1) (Dow Chemical societies manufacture, " KLARIX4000 ", isothiazoline based compound；4 mass % of active ingredient) 10.0g, ethyl alcohol 50.0g and ion exchange water 288.5g, and be stirred, so as to obtain the aqueous coating agent composition (K-32) that solid component content is 2.0 mass %.It should The viscosity of aqueous coating agent composition (K-32) is 28mPas.

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-32) of application so that coating weight be 50g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-32) of film.By the aqueous coating agent composition (K-32), film and breadboard (L-32) various physical property and Evaluation result is listed in table 4.

[embodiment 33]

Mixed number is equal in aqueous dispersion (CD-3) 60.0g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 7.5g, have photocatalytic activity inorganic oxide (E-1) 5.2g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into Divide fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g, profit that content is 1.0 mass % It is adjusted with ion exchange water so that solid component content is cellulose-based thickeners (H-1) (Daicel of 1.0 mass % Finechem societies manufacture, " HEC Daicel SP900 ") 80.0g, anti-algae/mould inhibitor (J-2) (Dow Chemical societies manufacture, The mixture of " ROCIMA345 ", isothiazoline based compound and triazine based compound；12 mass % of active ingredient) 1.3g, ethyl alcohol 50.0g and ion exchange water 294.9g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 2.0 mass % Agent composition (K-33).The viscosity of the aqueous coating agent composition (K-33) is 27mPas.

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-33) of application so that coating weight be 50g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-33) of film.By the aqueous coating agent composition (K-33), film and breadboard (L-33) various physical property and Evaluation result is listed in table 4.

[embodiment 34]

Mixed number is equal in aqueous dispersion (CD-3) 54.4g (10.0 mass % of solid component content) of polymer (C-3) The moisture of grain size 8nm dissipates cabosil (D-1), and (Nissan Chemical Industries society manufactures, " Snowtex OS "；Solid component content 20 Quality %) 6.8g, have photocatalytic activity inorganic oxide (E-1) 4.7g (29 mass % of solid component content), fluorine carbon table Face activating agent (F-1) (DIC societies manufacture, " MEGAFAC F-444 ") 0.2g, be adjusted using ion exchange water so that solid into Divide fadedness pigment (G-1) (Kishida Chemical societies manufacture, " methylene blue ") 1.0g, profit that content is 1.0 mass % It is adjusted with ion exchange water so that solid component content is cellulose-based thickeners (H-1) (Daicel of 1.0 mass % Finechem societies manufacture, " HEC Daicel SP900 ") 80.0g, anti-algae/mould inhibitor (J-3) (manufacture of Japanese Cao Da societies, The mixture of " Biocut-N35 ", imidazole compound and triazine based compound；35 mass % of active ingredient) 2.8g, ethyl alcohol 50.0g and ion exchange water 300.2g, and be stirred, so as to obtain the Water-Based Paint that solid component content is 2.0 mass % Agent composition (K-34).The viscosity of the aqueous coating agent composition (K-34) is 28mPas.

Then, (it is coated in advance in the single side for 7cm × 15cm or 5cm × 5cm the base material X for being coated with enamel-cover coating in advance The face of enamel-cover coating) on using spraying come the above-mentioned aqueous coating agent composition (K-34) of application so that coating weight be 50g/m²。 Base material through application is kept horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed on base material The breadboard (L-34) of film.By the aqueous coating agent composition (K-34), film and breadboard (L-34) various physical property and Evaluation result is listed in table 4.

[comparative example 1]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C ' -11) (C ' D-11) 180.0g (10.0 mass % of solid component content), obtains solid constituent and contains similarly to Example 1 in addition Measure the aqueous coating agent composition (K-35) for 6.0 mass %.The viscosity of the aqueous coating agent composition (K-35) is 2mPa s。

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-35) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-35).The aqueous coating agent composition (K-35), the various physical property of film and breadboard (L-35) and evaluation result are listed in Table 4.

[comparative example 2]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C ' -12) (C ' D-12) 180.0g (10.0 mass % of solid component content), obtains solid constituent and contains similarly to Example 1 in addition Measure the aqueous coating agent composition (K-36) for 6.0 mass %.The viscosity of the aqueous coating agent composition (K-36) is 2mPa s。

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-36) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-36).The aqueous coating agent composition (K-36), the various physical property of film and breadboard (L-36) and evaluation result are listed in Table 4.

[comparative example 3]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C ' -13) (C ' D-13) 180.0g (10.0 mass % of solid component content), obtains solid constituent and contains similarly to Example 1 in addition Measure the aqueous coating agent composition (K-37) for 6.0 mass %.The viscosity of the aqueous coating agent composition (K-37) is 2mPa s。

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-37) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-37).The aqueous coating agent composition (K-37), the various physical property of film and breadboard (L-37) and evaluation result are listed in Table 4.

[comparative example 4]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C ' -14) (C ' D-14) 180.0g (10.0 mass % of solid component content), obtains solid constituent and contains similarly to Example 1 in addition Measure the aqueous coating agent composition (K-38) for 6.0 mass %.The viscosity of the aqueous coating agent composition (K-38) is 2mPa s。

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-38) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-38).The aqueous coating agent composition (K-38), the various physical property of film and breadboard (L-38) and evaluation result are listed in Table 4.

[comparative example 5]

Without using aqueous dispersion (CD-1) 180.0g of polymer (C-1), and use the aqueous dispersion of polymer (C ' -15) (C ' D-15) 180.0g (10.0 mass % of solid component content), obtains solid constituent and contains similarly to Example 1 in addition Measure the aqueous coating agent composition (K-39) for 6.0 mass %.The viscosity of the aqueous coating agent composition (K-39) is 2mPa s。

Then, in the single side for the 7cm × 15cm base materials X for being coated with enamel-cover coating in advance (enamel-cover coating is coated in advance Face) on using spraying come application aqueous coating agent composition (K-39) so that coating weight be 17g/m².By the base material through application It keeps horizontal, when 50% time 23 DEG C of temperature, relative humidity standing 48 are small, obtains being formed with the breadboard of film on base material (L-39).The aqueous coating agent composition (K-39), the various physical property of film and breadboard (L-39) and evaluation result are listed in Table 4.

By above-mentioned it has been confirmed that the aqueous coating agent composition of the present embodiment, which can be formed, to maintain appearance with high level With the film of stain resistance.

Industrial applicibility

Aqueous coating agent composition, film and the coated articles of the present invention can be used as construction exterior purposes, exterior to show Various parts such as the optical components such as purposes, automotive part, display screen or lens etc. are utilized.

Claims

1. a kind of aqueous coating agent composition, contains：

The dispersion (CD) of copolymer (C), the copolymer (C) include structural unit (A) and structural unit (B), the structure list First (A) is derived from as the silane (a) shown in the following general formula (1), and the structural unit (B) is derived from by the following general formula (2) Suo Shi Silane (b)；With

Inorganic oxide (D)；

The content of the structural unit (A) in the copolymer (C) is scaled the matter of 47 mass %~70 with hydrolytic condensate Measure %,

The content of the structural unit (B) in the copolymer (C) is scaled the matter of 23 mass %~45 with hydrolytic condensate Measure %,

(R¹)₂-Si-(R²)₂···(1)

In formula (1), R¹Each independently represent hydrogen atom, the aliphatic alkyl that carbon number is 1~16, carbon number are 6~10 Aryl, carbon number be 5~6 cycloalkyl, carbon number be 1~10 acrylic acid alkyl ester group or carbon number be 1 ~10 alkyl methacrylate base, R²Each independently represent carbon number be 1~8 alkoxy, acetoxyl group or Hydroxyl,

R³-Si-(R⁴)₃···(2)

In formula (2), R³Represent that aliphatic alkyl, carbon number that hydrogen atom, carbon number are 1~16 are 6~10 aryl, carbon original The methyl that the acrylic acid alkyl ester group or carbon number that cycloalkyl that subnumber is 5~6, carbon number are 1~10 are 1~10 Acrylic acid alkyl ester group, R⁴Each independently represent alkoxy, acetoxyl group or the hydroxyl that carbon number is 1~8.

2. aqueous coating agent composition as described in claim 1, wherein, the dispersion (CD) of the copolymer (C) is to pass through At least using the silane (a) and the silane (b) and obtained from carrying out emulsion polymerization.

3. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the inorganic oxide (D) is silica.

4. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains urges with light Change the inorganic oxide (E) of activity.

5. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains fluorocarbon surface Activating agent (F).

6. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains fadedness color Plain (G).

7. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition is further containing cellulose-based Thickener (H).

8. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition, which further contains, to be selected from by preventing The substance of one or more of the group of algae agent and mould inhibitor (J) composition.

9. a kind of aqueous coating contains claim 1~8 any one of them aqueous coating agent composition.

10. a kind of film, is obtained as the aqueous coating described in claim 9.

11. a kind of coated articles, containing the film described in base material and claim 10, which is formed at the table of the base material At least a portion in face.

12. coated articles as claimed in claim 11, wherein, the base material is organic substrate.