CN105086819A - Aqueous coating agent composition, coating film and coating product - Google Patents

Aqueous coating agent composition, coating film and coating product Download PDF

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Publication number
CN105086819A
CN105086819A CN201510259262.4A CN201510259262A CN105086819A CN 105086819 A CN105086819 A CN 105086819A CN 201510259262 A CN201510259262 A CN 201510259262A CN 105086819 A CN105086819 A CN 105086819A
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quality
agent composition
coating agent
aqueous coating
film
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CN105086819B (en
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月森康之
青柳尚久
小迫勲
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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Abstract

The invention provides aqueous coating agent composition, a coating film and a coating product. The aqueous coating agent composition can form a coating film having appearance maintenance and stain resistance for long term at high level; the aqueous coating agent composition has dispersoid (CD) of a copolymer (C) and inorganic oxide (D); the copolymer (C) comprises a structure unit (A) and a structure unit (B); the structure unit (A) is silane (a) having a specific structure; the structure unit (B) is silane (b) having a specific structure; the content of the structure unit (A) in the copolymer (C) takes up of 32 to 70% by weight according to hydrolytic condensation conversion; and the content of the structure unit (B) in the copolymer (C) takes up of 23 to 45% by weight according to hydrolytic condensation conversion.

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 construction things such as construction exterior, bridge, tank has coating etc., but its film coated surface is by the dust in air, coal smoke, sand etc.; By the dirt composition of stripping in sealing material; And the pollution substance etc. of to be discharged by the relief outlet of buildings polluted.The pollution of such film is generally light/dark balance, remarkable crime of injuries by explosive substances to buildings and goods therein and outdoor construction thing attractive in appearance.
As coating layer agent composition in the water-based of suppression painting fouling membrane as described above, applicant proposed a kind of double-deck film, it possesses undercoat and is arranged at the upper coating on this undercoat, the film that above-mentioned undercoat is formed for making the dried coating film of the primary coat coating agent composition (I) containing polymer emulsion particles (A), the method for the operation that this polymer emulsion particles (A) makes vinyl monomer and water-disintegrable silicon compound be polymerized respectively under utilizing and being included in the existence of water and emulsifying agent obtains; The film that above-mentioned upper coating is formed for making the dried coating film of upper painting coating agent composition (II), on this, painting coating agent composition (II) comprises metal oxide particle (B), polymer emulsion particles (C) and the colloided silica (D) with photocatalytic activity, and the method for the operation that this polymer emulsion particles (C) makes vinyl monomer and water-disintegrable silicon compound be polymerized respectively under utilizing and being included in the existence of water and emulsifying agent obtains (see patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-005595 publication
Summary of the invention
Invent problem to be solved
In the technology that patent documentation 1 is recorded, employ the high material of second-order transition temperature as undercoat, even if be therefore the upper coating formed by upper painting coating agent composition, also can obtain sufficient stain resistance and weathering resistance.So, the technology of patent documentation 1 is excellent technology, but the present inventor attempts carrying out further improvement to develop more excellent technology.Such as, by record in patent documentation 1 such upper painting coating agent composition is applied in construction exterior etc. general employ on base material that second-order transition temperature is the material of about-5 ~ 20 DEG C time, the upper coating formed by upper painting coating agent composition sometimes fully can not be followed the change being subject to outside temperature etc. and flexible base material occurs.Under such circumstances, in upper coating, produce cracking etc. sometimes, also sometimes damage outward appearance because this cracking causes gloss to reduce.And then, also adhere to dust, coal smoke, sand etc. in the part of cracking sometimes and contaminated.If the above-mentioned aspect of film can be improved, then can not by the restriction of base material, and can expect to realize the long-term excellent film of a kind of various physical property headed by outward appearance and stain resistance.
The present invention completes in view of the foregoing, and object is to provide and a kind ofly forms the aqueous coating agent composition that can maintain the film of outward appearance and stain resistance for a long time with high level.
The means of dealing with problems
Present inventor has performed further investigation, found that, by using following aqueous coating agent composition, solve the problems referred to above, thus complete the present invention, described aqueous coating agent composition contains dispersion (CD) and the inorganic oxide (D) of multipolymer (C), this multipolymer (C) comprises structural unit (A) and structural unit (B), described structural unit (A) derives from the silane (a) with ad hoc structure, described structural unit (B) derives from the silane (b) with ad hoc structure, the content of the structural unit (B) in the content of the structural unit (A) in multipolymer (C) and multipolymer (C) is in specific scope.
That is, the present invention is as described below.
[1]
A kind of aqueous coating agent composition, it contains:
The dispersion (CD) of multipolymer (C), this multipolymer (C) comprises structural unit (A) and structural unit (B), described structural unit (A) derives from by the silane (a) shown in following general formula (1), and described structural unit (B) derives from by the silane (b) shown in following general formula (2); With
Inorganic oxide (D);
The content of the said structure unit (A) in above-mentioned multipolymer (C) is scaled 32 ~ 70 quality % with hydrolytic condensate,
The content of the said structure unit (B) in above-mentioned multipolymer (C) is scaled 23 ~ 45 quality % with hydrolytic condensate.
(R 1) 2-Si-(R 2) 2···(1)
(R 1represent independently of one another hydrogen atom, carbonatoms be 1 ~ 16 aliphatic alkyl, the carbonatoms aryl that is 6 ~ 10, the carbonatoms cycloalkyl that is 5 ~ 6, phenyl, carbonatoms be 1 ~ 10 acrylic acid alkyl ester group or carbonatoms be 1 ~ 10 alkyl methacrylate base, R 2represent that carbonatoms is alkoxyl group, acetoxyl group or the hydroxyl of 1 ~ 8 independently of one another.)
R 3-Si-(R 4) 3···(2)
(R 3represent hydrogen atom, carbonatoms be 1 ~ 16 aliphatic alkyl, carbonatoms be 6 ~ 10 aryl, carbonatoms be 5 ~ 6 cycloalkyl, phenyl, carbonatoms be 1 ~ 10 acrylic acid alkyl ester group or carbonatoms be 1 ~ 10 alkyl methacrylate base, R 4represent that carbonatoms is alkoxyl group, acetoxyl group or the hydroxyl of 1 ~ 8 independently of one another.)
[2]
Aqueous coating agent composition as described in [1], wherein, the dispersion (CD) of above-mentioned multipolymer (C) is by least using above-mentioned silane (a) with above-mentioned silane (b) and carrying out letex polymerization and obtain.
[3]
Aqueous coating agent composition as described in [1] or [2], wherein, above-mentioned inorganic oxide (D) is silicon-dioxide.
[4]
Aqueous coating agent composition as described in any one of [1] ~ [3], wherein, described composition is further containing the inorganic oxide (E) with photocatalytic activity.
[5]
Aqueous coating agent composition as described in any one of [1] ~ [4], wherein, described composition is further containing fluorocarbon surfactant (F).
[6]
Aqueous coating agent composition as described in any one of [1] ~ [5], wherein, described composition is further containing fadedness pigment (G).
[7]
Aqueous coating agent composition as described in any one of [1] ~ [6], wherein, described composition is further containing cellulose-based thickeners (H).
[8]
Aqueous coating agent composition as described in any one of [1] ~ [7], wherein, described composition is further containing the material of more than a kind be selected from the group that is made up of algaecide and mould inhibitor (J).
[9]
A kind of aqueous coating, it contains [1] ~ any one of [8] described in aqueous coating agent composition.
[10]
A kind of film, it is obtained by the aqueous coating described in [9].
[11]
A kind of coated articles, it contains base material and the film described in [10], and this film 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
According to the present invention, can provide a kind of aqueous coating agent composition, said composition can form the film that can maintain outward appearance and stain resistance for a long time with high level.
Embodiment
Below this embodiment (hereinafter referred to as " present embodiment ") is described.Following present embodiment is for illustration of illustration of the present invention, and not intended to be limits the invention to following content.The present invention can suitably be out of shape and implement in the scope of its main points.It should be noted that, only otherwise special declaration, " (methyl) acrylate " refers to " acrylate " and " methacrylic ester " corresponding with it, and " (methyl) vinylformic acid " refers to " vinylformic acid " and " methacrylic acid " corresponding with it.
[waterborne compositions]
The waterborne compositions of present embodiment contains dispersion (CD) and the inorganic oxide (D) of multipolymer (C), and this multipolymer (C) comprises and derives from by the structural unit (A) of the silane (a) shown in general formula (1) and derive from by the structural unit (B) of the silane (b) shown in general formula (2).And, in aqueous coating agent composition, the content of the structural unit (A) in multipolymer (C) is scaled 32 ~ 70 quality % with hydrolytic condensate, and the content of the structural unit (B) in multipolymer (C) is scaled 23 ~ 45 quality % with hydrolytic condensate.
< dispersion (CD) >
The dispersion that dispersion (CD) is multipolymer (C).As the dispersion of multipolymer (C), be not particularly limited, from the viewpoint of for water system, be preferably water dispersion.As such water dispersion, can enumerate such as, the water dispersion (CD) etc. of the multipolymer (C) using (a) composition, (b) composition and the water-disintegrable silicon compound except (a) composition and (b) composition added as required and/or vinyl monomer etc. to carry out letex polymerization and obtain.
Multipolymer (C) is containing counting the structural unit (A) of 32 ~ 70 quality % with hydrolytic condensate conversion composition, count the structural unit (B) of the ratio of 23 ~ 45 quality % with hydrolytic condensate conversion composition.When the content of the content and structure of unit (B) of the structural unit (A) in multipolymer (C) is outside above-mentioned scope, the weathering resistance of film and stain resistance become insufficient.It should be noted that, said hydrolytic condensate refers to that the reactive group (such as alkoxyl group etc.) of (a) composition contained in such as system and (b) composition is converted to the condenses of silanol bonds by hydrolysis and condensation reaction herein.The content (quality %) that the hydrolytic condensate of structural unit (A) and structural unit (B) converts according to the charging capacity of the content (total solids component content) of the multipolymer (C) obtained as (CD) the adding thermal residue of composition, (a) composition, (b) composition, can utilize calculating to obtain.Specifically, method described in embodiment described later can be utilized to obtain.In addition, the structural unit (A) in multipolymer (C) and the content (quality %) of structural unit (B) also can utilize Si solid NMR directly to measure.
The lower value of the content of the structural unit (A) in multipolymer (C) is more than 32 quality %, is preferably more than 47 quality %.The higher limit of the content of the structural unit (A) in multipolymer (C) is below 70 quality %, is preferably below 65 quality %.
The lower value of the content of the structural unit (B) in multipolymer (C) is more than 23 quality %, is preferably more than 25 quality %.The higher limit of the content of the structural unit (B) in multipolymer (C) is below 45 quality %, is preferably below 39 quality %, is more preferably below 35 quality %.
As the concrete example of the silane (a) shown in general formula (1), dimethyldimethoxysil,ne can be enumerated, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diη-propyl dimethoxysilane, diη-propyl diethoxy silane, diisopropyl dimethoxy silane, diisopropyldiethoxysilane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-n-butyl diethoxy silane, two n-pentyl dimethoxysilane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxysilane, di-n-hexyl diethoxy silane, two n-heptyl dimethoxysilane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxysilane, di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxysilane, two positive cyclohexyl diethoxy silanes, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diphenyl diethoxy silane, 3-(methyl) acryloxypropyl dimethoxysilane etc.
Among these, from the weathering resistance of obtained film and the aspect of stain resistance, preferred dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, more preferably dimethyldimethoxysil,ne, dimethoxymethylphenylsilane, further preferred dimethyldimethoxysil,ne.These can be used alone one, also can share two or more.
As the concrete example of the silane (b) shown in general formula (2), methyltrimethoxy silane can be enumerated, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, n-butyltrimethoxysilane, ne-butyltriethoxysilaneand, n-pentyl Trimethoxy silane, n-hexyl Trimethoxy silane, n-heptyl Trimethoxy silane, n-octyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, 3-(methyl) acryloxypropyl three positive propoxy silane, 3-(methyl) acryloxypropyl three isopropoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane etc.Among these, from hydrolysis rate during polymerization etc. and the weathering resistance of film obtained and the aspect of stain resistance, preferable methyl Trimethoxy silane, phenyltrimethoxysila,e, 3-(methyl) acryloxypropyl Trimethoxy silane.These can be used alone one, also can share two or more.
As the water-disintegrable silicon compound except (a) composition and (b) composition for the manufacture of multipolymer (C), be not particularly limited, preferably enumerate the compound shown in following general formula (3) and their condenses etc.
SiW xR y···(3)
In formula, W represent alkoxyl group, hydroxyl, carbonatoms that to be selected from by carbonatoms be 1 ~ 20 be 1 ~ 20 acetoxyl group, halogen atom, hydrogen atom, carbonatoms be at least one in the group that forms of oximido, alkene oxygen (エ ノ キ シ) base, aminooxy and amide group of 1 ~ 20.The alkoxyl group that R represents cycloalkyl that alkyl, carbonatoms that to be selected from by the carbonatoms of straight-chain or branched be 1 ~ 30 are 5 ~ 20, carbonatoms is 1 ~ 20, the carbonatoms replaced with halogen atom are at least one group in the group that forms of aryl of 6 ~ 20.X is the integer of less than more than 14, and y is the integer of less than more than 03, meets the relation of x+y=4.When W is more than 2, when R is more than 2, each W with R mutually can be identical, also can be different.
As the silicon alkoxide of a mode of the water-disintegrable silicon compound shown in general formula (3), as long as the material beyond (a) composition and (b) composition is just not particularly limited, the tetraalkoxysilane classes such as such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane can be enumerated.In tetraalkoxysilane, from the aspect of hydrolysis rate during polymerization, preferred tetramethoxy-silicane, tetraethoxysilane.These can be used alone one, also can share two or more.
As the concrete example of the vinyl monomer that can use in the manufacture of multipolymer (C), the vinyl monomer containing functional group such as vinyl compound, the vinyl compound containing glycidyl, the vinyl compound with secondary amide base and/or teritary amide base, anionic vinyl based compound of (methyl) acrylate, aromatic ethenyl compound, vinyl cyanide compound, carboxylic vinyl compound, hydroxyl can be enumerated such as.
As the concrete example of (methyl) acrylate, be not particularly limited, can enumerate and such as there is (methyl) alkyl acrylate that carbonatoms is the alkyl of 1 ~ 50, there is (gathering) oxygen ethene two (methyl) acrylate etc. that carbonatoms is the oxyethylene group of 1 ~ 100.
As the concrete example of (methyl) acrylate, be not particularly limited, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) cyclohexyl acrylate, (methyl) lauryl acrylate, (methyl) dodecylacrylate etc. can be enumerated such as.
As the concrete example of (gathering) oxygen ethene two (methyl) acrylate, be not particularly limited, such as two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid glycol ether ester, methoxyl group (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid Tetraglycol 99 ester etc. can be enumerated.
As the concrete example of aromatic ethenyl compound, be not particularly limited, such as vinylbenzene, alpha-methyl styrene, p-tert-butylstyrene, chloro-styrene, Vinyl toluene etc. can be enumerated.
As the concrete example of vinyl cyanide compound, be not particularly limited, such as vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile etc. can be enumerated.
As the concrete example of carboxylic vinyl compound, be not particularly limited, the half ester of the such as diprotic acid such as vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride or methylene-succinic acid, toxilic acid, fumaric acid can be enumerated.By using the vinyl monomer containing carboxyl, carboxyl can be imported in structural unit (A).So, can further improve as emulsion intercalation method, infer can have high resistibility (but the effect of present embodiment is not limited to these) to the dispersion destroys effect from outside.Now, part or all of the carboxyl of importing also can neutralize with alkali such as amine, NaOH, KOH such as ammonia, triethylamine, dimethylethanolamines.The consumption of the carboxylic vinyl monomer in the total amount of above-mentioned vinyl monomer is preferably 0 ~ 10 quality % from the aspect of water tolerance, but is not limited to this.
As the concrete example of the vinyl compound of hydroxyl, be not particularly limited, (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-3-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester can be enumerated such as; The number of two-2-hydroxyethyl fumarates, list-2-hydroxyethyl monobutyl fumarate, vinyl carbinol or oxyethylene group is (gathering) oxygen ethene list (methyl) acrylate of 1 ~ 100; The number of oxypropylene group is (gathering) oxypropylene list (methyl) acrylate of 1 ~ 100, and " PRAXCELLFM, FA monomer " (trade(brand)name of caprolactone addition monomer that DaicelChemical society manufactures), other α, β-ethylenic unsaturated carboxylic acid hydroxyalkyl acrylate class.
As the concrete example of (gathering) oxygen ethene (methyl) acrylate, be not particularly limited, (methyl) vinylformic acid glycol ester, methoxyl group (methyl) vinylformic acid glycol ester, (methyl) vinylformic acid glycol ether ester, methoxyl group (methyl) vinylformic acid glycol ether ester, (methyl) vinylformic acid Tetraglycol 99 ester, methoxyl group (methyl) vinylformic acid Tetraglycol 99 ester etc. can be enumerated such as.
The concrete example of (gathering) oxypropylene (methyl) acrylate, be not particularly limited, (methyl) vinylformic acid propylene glycol ester, methoxyl group (methyl) vinylformic acid propylene glycol ester, (methyl) vinylformic acid dipropylene glycol ester, methoxyl group (methyl) vinylformic acid dipropylene glycol ester, (methyl) vinylformic acid four propylene glycol ester, methoxyl group (methyl) vinylformic acid four propylene glycol ester etc. can be enumerated such as.
As the concrete example of the vinyl compound containing glycidyl, be not particularly limited, (methyl) glycidyl acrylate, the sweet base ether of allyl glycidyl, allyl dimethyl base glycidyl ether etc. can be enumerated such as.
As the concrete example of vinyl monomer with secondary amide base and/or teritary amide base, be not particularly limited, can enumerate that such as N-alkyl replaces (methyl) acrylamide, N-alkylidene group replaces (methyl) acrylamide etc.
The concrete example of (methyl) acrylamide is replaced as N-alkyl, be not particularly limited, such as N-methyl (methyl) acrylamide can be enumerated, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-acrylamide, N-methyl-N ethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-n-propyl (methyl) acrylamide, N-methyl-N-n-propyl (methyl) acrylamide, N-methyl-N-isopropyl (methyl) acrylamide, N-(methyl) acryloyl tetramethyleneimine, N-(methyl) Antiepilepsirin, N-acryloyl hexahydro-azepine, N-(methyl) acryloyl morpholine, NVP, N-caprolactam, N, N '-methylene-bis (methyl) acrylamide, N-vinyl acetamide, two acetone (methyl) acrylamide, N-methylol (methyl) acrylamide etc.
As the concrete example of the vinyl monomer beyond above-mentioned substance, the olefines such as (methyl) acrylamide, ethene, propylene, iso-butylene can be enumerated such as; The dienes such as divinyl; The haloalkene hydro carbons such as ethylene chloride, vinylidene chloride, ethylene fluoride, tetrafluoroethylene, trifluorochloroethylene; The vinyl esters of carboxylic acids classes such as vinyl-acetic ester, propionate, vinyl propionate, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate, new vinyl acetate acid, 2 ethyl hexanoic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate base; The carboxylic acid pseudoallyl ester classes such as isopropyl acetate alkenyl esters, propionic acid pseudoallyl ester; The vinyl ethers such as ethyl vinyl ether, IVE, cyclohexyl vinyl ether; The aromatic ethenyl compound such as vinylbenzene, Vinyl toluene; The allyl ester classes such as allyl acetate, phenylformic acid allyl ester; The allyl ether series such as allyl group ether, allyl group phenylate; 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine, 4-(methyl) acryloxy-1,2,2,6,6-pentamethvl, perfluoro-methyl (methyl) acrylate, perfluoro propyl (methyl) acrylate, perfluoro propyl methyl (methyl) acrylate, vinyl pyrrolidone, trimethylolpropane tris (methyl) acrylate, (methyl) allyl acrylate etc.These materials all can be used alone one, also can share two or more.
When manufacturing multipolymer (C) by polyreaction in present embodiment, in order to control the molecular weight of the polymerisate of used vinyl monomer, can usage chain transfer agent.
As the concrete example of chain-transfer agent, be not particularly limited, the alkyl mercapto alcohols such as such as n octylmercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan can be enumerated; The aromatic mercaptans class that benzyl sulfhydrate, dodecyl benzyl sulfhydrate are such; The thiocarboxylic acids such as thiomalic acid or their salt or their alkyl esters; Polythiol class; The disulfides such as dithiodiisopropyl xanthate, curing two (methylene tri hydroxymethyl-propane) xanthate; The allylic cpds etc. such as the dipolymer of THIOGLYCOL, alpha-methyl styrene.These materials can be used alone one, also can share two or more.
Total consumption of chain-transfer agent is preferably 0.001 ~ 1.0 quality % relative to the total amount of above-mentioned vinyl monomer.
As the emulsifying agent that can use in the manufacture of multipolymer (C), be not particularly limited, the aniorfic surfactant such as ammonium salt, fatty acid soaps of the acid emulsifying agents such as such as alkyl benzene sulphonate (ABS), alkylsulphonic acid, alkyl sulfosuccinate, polyxyethylated sulfuric acid, polyxyethylated aromatic sulfuric acid, polyoxyethylene diphenylethyllene phenyl ether sulfonic acid, basic metal (Li, Na, K etc.) salt of acid emulsifying agent, acid emulsifying agent can be enumerated; The nonionic surface active agent such as cationic surfactant, polyoxyethylene alkylaryl ether, Polyoxyethylene Sorbitan acid esters, polyoxyethylene oxypropylene segmented copolymer, polyoxyethylene diphenylethyllene phenyl ether of the quaternary ammonium salts such as such as alkyl trimethyl ammonium bromide, cetylpyridinium bromide, tetrahydroglyoxaline lauroleate, pyridinium salt, imidazoline salt form; There is the reactive emulsifier etc. of free-radical polymerised double bond.
In these emulsifying agents, preferably there is the reactive emulsifier (reactive emulsifier) of free-radical polymerised double bond.By using such reactive emulsifier, the dispersion stability of polymer beads is very good, and the water tolerance of the film obtained also improves further.
For the anionic emulsifier as reactive emulsifier, the ethylenically unsaturated monomers etc. such as with sulfonic group, sulfonate group or sulfate group and their salt can be enumerated, preferably there is the compound of sulfonic group or the group (sulfonic acid ammonium or alkali metal sulfamate alkali) as its ammonium salt or an alkali metal salt.Specifically can enumerate such as polyoxyethylene base sulfosuccinate (such as Sanyo can be enumerated and change into society's manufacture, " ELEMINOL (trade mark) JS-20 ", such as Hua Wang society manufactures, " LATEMUL (trade mark) S-120 ", " LATEMULS-180A ", " LATEMULS-180 " etc.), such as polyxyethylated allyl phenyl ether sulfuric acid (can be enumerated such as the first industrial pharmaceutical society to manufacture, " Aquaron (trade mark) HS-10 " etc.), such as α-[1-[(allyloxy) methyl]-2-(Nonylphenoxy) ethyl]-ω-polyoxyethylene sulfates (can be enumerated such as ADEKA society to manufacture, " AdekaReasoap (trade mark) SE-10N " etc.), such as ammonium-α-sulfonate radical closes-ω-1-(allyloxy methyl) alkyl oxy polyoxyethylene and (can enumerate such as the first industrial pharmaceutical society to manufacture, " AquaronKH-1025 " etc.), such as styrene sulfonate (can be enumerated such as Dong Cao organic chemistry society to manufacture, " Supinoma (trade mark) NaSS " etc.), such as α-[2-[(allyloxy)-1-(alkyl oxy methyl) ethyl]-ω-polyoxyethylene sulfates (can be enumerated such as ADEKA society to manufacture, " AdekaReasoap (trade mark) SR-1025 " etc.), the sulfuric acid of such as polyoxyethylene polybutylene (3-methyl-3-butenyl) ether (can be enumerated such as Hua Wang society to manufacture, " LATEMUL (trade mark) PD-104 " etc.) etc.Among these, preferred ammonium-α-sulfonate radical closes-ω-1-(allyloxy methyl) alkyl oxy polyoxyethylene, α-[2-[(allyloxy)-1-(alkyl oxy methyl) ethyl]-ω-polyoxyethylene sulfates.
In addition, for the nonionic emulsifier as reactive emulsifier, such as α-[1-[(allyloxy) methyl]-2-(Nonylphenoxy) ethyl]-ω-hydroxyl polyoxyethylene can be enumerated and ((ADEKA society manufacture can be enumerated such as, " AdekaReasoapNE-20 ", " AdekaReasoapNE-30 ", " AdekaReasoapNE-40 " etc.), such as polyxyethylated allyl phenyl ether (can be enumerated such as the first industrial pharmaceutical society to manufacture, " AquaronRN-10 ", " AquaronRN-20 ", " AquaronRN-30 ", " AquaronRN-50 " etc.), such as α-[2-[(allyloxy)-1-(alkyl oxy methyl) ethyl]-ω-hydroxyl polyoxyethylene (can be enumerated such as ADEKA society to manufacture, " AdekaReasoap (trade mark) ER-10 " etc.), such as polyoxyethylene polybutylene (3-methyl-3-butenyl) ether (can be enumerated such as Hua Wang society to manufacture, " LATEMUL (trade mark) PD-420 " etc.) etc.
The consumption of emulsifying agent is preferably below 10 mass parts relative to total amount 100 mass parts of raw material i.e. (a) composition of the multipolymer (C) as polymkeric substance, (b) composition, water-disintegrable silicon compound except (a) composition and (b) composition and vinyl monomer, is more preferably 0.001 ~ 5 mass parts.By making the consumption of emulsifying agent be above-mentioned scope, polymerization stability improves further, the water tolerance of film is better.
A the polyreaction of () composition, (b) composition, water-disintegrable silicon compound except (a) composition and (b) composition and vinyl monomer etc. is preferably implemented under polymerizing catalyst exists.As used polymerizing catalyst, the such as hydrogen halide such as hydrochloric acid, hydrofluoric acid class can be enumerated; The carboxylic-acids such as acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, lactic acid; The sulphonic acids such as sulfuric acid, tosic acid; The acid emulsifying agent classes such as alkyl benzene sulphonate (ABS), alkylsulphonic acid, alkyl sulfosuccinate, polyxyethylated sulfuric acid, polyxyethylated aromatic sulfuric acid, polyoxyethylene diphenylethyllene phenyl ether sulfonic acid; Acid or weakly acidic inorganic salt; The acidic cpd classes such as phthalic acid, phosphoric acid, nitric acid; The basic cpd classes such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethyl ammonium chloride, Tetramethylammonium hydroxide, Tributylamine, diazabicyclo undecylene, quadrol, diethylenetriamine, ethanolamines, gamma-amino propyl trimethoxy silicane, γ-(2-amino-ethyl)-TSL 8330; The tin compounds etc. such as dibutyl stannous octoate, dibutyl tin laurate.
Among these, as the polymerizing catalyst of water-disintegrable silicon compound, as the effect of polymerizing catalyst, also there is effect as emulsifying agent, preferred acidic emulsifying agent class from the viewpoint of not only having.As acid emulsifying agent class, more preferably carbonatoms is the alkyl benzene sulphonate (ABS) (such as Witco 1298 Soft Acid etc.) of 5 ~ 30.
As the polymerizing catalyst of vinyl monomer, being not particularly limited, causing the catalysts for radical polymerization of the addition polymerization of vinyl monomer preferably by self there is free radical decomposition under the effect of heat or reducing substances etc.As such catalysts for radical polymerization, be not particularly limited, such as persulphate, superoxide, azo two compound etc. can be enumerated.These can be water-soluble substances, also can be oil-soluble substance.
As the concrete example of catalysts for radical polymerization, be not particularly limited, such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, tertbutyl peroxide, peroxidized t-butyl perbenzoate, 2 can be enumerated, 2-Diisopropyl azodicarboxylate, 2,2-azo two (2-diaminopropanes) hydrochloride, 2,2-azo two (2,4-methyl pentane nitrile) etc.
The combined amount of catalysts for radical polymerization is not particularly limited, and relative to total amount 100 mass parts of vinyl monomer, is preferably 0.001 ~ 5.0 mass parts.It should be noted that, when expecting the polymerization under promotion polymerization velocity and low temperature such below 70 DEG C, preferably the reductive agents such as such as sodium bisulfite, iron protochloride, ascorbate salt, rongalite and catalysts for radical polymerization being share.
The polymerization of water-disintegrable silicon compound and vinyl monomer also can be implemented respectively, but by implementing to complete Composite simultaneously, therefore preferably implements the polymerization of water-disintegrable silicon compound and vinyl monomer simultaneously.
Number average bead diameter as the multipolymer (C) of polymkeric substance is not particularly limited, and is preferably 10 ~ 300nm.By making the number average bead diameter of multipolymer (C) be above-mentioned scope, the weathering resistance of the film obtained, stain resistance are tending towards further raising.In addition, the particle diameter of multipolymer (C) is more preferably 10 ~ 200nm, more preferably 100 ~ 200nm.By using the multipolymer (C) of above-mentioned number average bead diameter, the weathering resistance of the film obtained improves further.By making number average bead diameter be more than 10nm, stain resistance is good especially, and by making number average bead diameter be below 300nm, the transparency of film is good especially.It should be noted that, said number average bead diameter can use wet type grain size analyser to measure herein.
As the appropriate methodology of multipolymer (C) obtaining such particle diameter, such as so-called letex polymerization can be enumerated, wherein formed for emulsifying agent micella q.s water existence under make water-disintegrable silicon compound and polymerization of vinyl monomer.In such mode, as the suitable examples of the dispersion (CD) of multipolymer (C), can enumerate such as, the dispersion (CD) of multipolymer (C) is for by least using silane (a) and silane (b) and the dispersion etc. of carrying out letex polymerization and obtaining.
As the concrete grammar of letex polymerization, be not particularly limited, such as following method can be enumerated: under water-disintegrable silicon compound and vinyl monomer state under original state or after emulsification, disposable or drop in reaction vessel in batches or drop to continuously in reaction vessel, preferably be polymerized in the temperature of reaction of about 30 ~ 150 DEG C under the pressure of normal atmosphere ~ 10MPa under the existence of polymerizing catalyst.Temperature of reaction and reaction pressure also can not be above-mentioned condition according to reaction conditions etc.The solid component content obtained by letex polymerization is not particularly limited, and is preferably 1.0 ~ 50 quality %, is more preferably 5.0 ~ 30 quality %.
For the method manufactured as (CD) composition of dispersion, also can adopt following method: under the existence of water and emulsifying agent, in the presence of solvent (a) composition, (b) composition, water-disintegrable silicon compound except (a) composition and (b) composition and/or vinyl monomer are polymerized as required after, add water further until polymkeric substance becomes emulsion.But the viewpoint etc. of the particle diameter of obtained multipolymer (C) easy to control is set out calmly, preferred emulsion polymerization described above.
Multipolymer (C) preferably has the core/shell structure of the shell of core and more than 1 layer or 2 layers.By being core/shell structure, the physical property (balance etc. of weathering resistance and stain resistance) of the film obtained improves further, is therefore preferably core/shell structure.For the confirmation of core/shell structure, can by such as based on the morphologic observation of transmission electron microscope etc. or carry out based on the parsing etc. of determination of viscoelasticity.
As manufacturing the method with the multipolymer (C) of core/shell structure, such as multi-step emulsion polymerizations is useful, but is not limited to this.Said multi-step emulsion polymerizations refers to following method herein: they are divided into the different stages to be polymerized by the two or more reaction soln with different composition of preparation containing water-disintegrable silicon compound, vinyl monomer.As an example of multi-step emulsion polymerizations, the method for being synthesized the multipolymer (C) with core/shell structure by 2 sections of letex polymerizations is mainly described.As an example of 2 sections of letex polymerizations, the method with following operation can be enumerated: under the existence of water and emulsifying agent, make water-disintegrable silicon compound and/or polymerization of vinyl monomer, obtain the operation (the 1st section) of seed grain; And, under the existence of obtained seed grain, respectively by the operation (the 2nd section) of water-disintegrable silicon compound and/or polymerization of vinyl monomer.
Synthesis example such as the polymerization process by 2 stages based on the multipolymer (C) of 2 sections of letex polymerizations carries out, and the polymerization process in this 2 stage comprises: supply (a) composition, (b) composition carry out the polymerization of the 1st section of letex polymerization; And, then the 1st section, the water-disintegrable silicon compound beyond supply (b) composition, (a) composition, (b) composition and vinyl monomer, the polymerization of the 2nd section of letex polymerization further in an aqueous medium.Now, the solids component quality (M1) of the 1st section is not particularly limited with the mass ratio ((M1)/(M2)) of the solids component quality (M2) of the 2nd section, is preferably 7.0/3.0 ~ 9.5/0.5, is more preferably 7.5/2.5 ~ 9.3/0.7.
By carrying out such multi-step emulsion polymerizations, the physical property (balance etc. of weathering resistance and stain resistance) of the film obtained improves further, therefore preferred multi-step emulsion polymerizations.
When the multi-step emulsion polymerizations of enforcement more than 3 sections, be polymerized same with 2 sections, increase the hop count of polymerization.
The content comprising the water-disintegrable silicon compound of (a) composition and (b) composition in multipolymer (C) is not particularly limited, and converts and is preferably more than 75 quality %, is more preferably more than 90 quality % with hydrolytie polycondensation thing.By making the content of the water-disintegrable silicon compound comprising (a) composition and (b) composition be above-mentioned scope, the weathering resistance of film improves further.
The content of the multipolymer (C) in aqueous coating agent composition is not particularly limited, and is preferably 0.5 ~ 10.0 quality %, is more preferably 1.0 ~ 5.0 quality %.
The content of the multipolymer (C) in the film formed by aqueous coating agent composition is preferably 10.0 ~ 80.0 quality %, is more preferably 50.0 ~ 75.0 quality %.By making the content of multipolymer (C) be more than above-mentioned lower value, the weathering resistance of film improves further, and by for below above-mentioned higher limit, stain resistance improves further.
The aqueous coating agent composition of present embodiment, except multipolymer (C), can also comprise the compound with the functional group that can react with the functional group contained by above-mentioned polymkeric substance further.As such compound, be not particularly limited, (many) isocyanate compounds, (gathering) epoxy compounds, aminocompound, (many) carboxylic compounds, (many) oxy-compound, diol compound, silanol compound, silyl compound, alkoxy compound, (methyl) acrylic compound etc. can be enumerated such as.These materials can be used alone one, also can share two or more.
< inorganic oxide (D) >
Inorganic oxide (D) is the inorganic oxide without photocatalytic activity.Said herein do not have photocatalytic activity and refer to, oxidizing reaction and reduction reaction all do not occur under light illumination.
As (D) composition, be not particularly limited, such as silicon-dioxide (silica), aluminum oxide (alumina), Calucium Silicate powder, magnesium oxide, weisspiessglanz, zirconium white and their composite oxides etc. can be enumerated.Among these, many from the viewpoint of surface hydroxyl, preferred silicon-dioxide, aluminum oxide, weisspiessglanz and their composite oxides, more preferably silicon-dioxide.
The inorganic oxide being used as (D) composition preferably exists with the form of the colloidal solid of hydrate etc.That is, by being inorganic oxide colloid particle, also can further with multipolymer (C) or other composition Composites being called (E) composition, the stability as aqueous coating agent composition improves further.
Silicon-dioxide is preferably colloided silica.As colloided silica, can enumerate following colloided silica etc., it is take silicon-dioxide as the water dispersion of silicon oxide or the dispersion of water-soluble solvent of elementary cell.
The manufacture method of colloided silica is not particularly limited, and such as sol-gel method also can be utilized to prepare.When utilizing sol-gel method to prepare, can with reference to WernerStoberetal.; JournalofColloidAndInterfaceScience, vol.26, pp.62-69 (1968); RickeyD.Badleyetal.; Langmuir6,792-801 (1990); " colorant association will (Se Cai Association Hui Chi) ", 61 [9] 488-493 (1988) etc.
(D) number average bead diameter of composition is not particularly limited, and is preferably 1.0 ~ 400nm, is more preferably 1.0 ~ 100nm, more preferably 1.0 ~ 30nm.By making the number average bead diameter of (D) composition be more than 1nm, the storage stability of aqueous coating agent composition is improved further.By making the number average bead diameter of (D) composition be below 400nm, the transparency of the film obtained improves further.It should be noted that, number average bead diameter measures by using wet type grain size analyser.
Colloided silica can be acid, alkaline any one in the state of aqueous liquid dispersion.
As the acidic colloidal silicon oxide taking water as dispersion medium, also commercially available product can be used.As such commercially available product, " Snowtex (trade mark)-OXS ", " Snowtex-OS ", " Snowtex-O ", " Snowtex-O-40 ", " Snowtex-OL " and " Snowtex-OYL ", " adelite (trade mark) AT-20Q " of Xu electricity Hua Gongyeshe manufacture, " Klebosol (trade mark) 20H12 " and " Klebosol30CAL25 " of Clariant (Japan) society manufacture etc. that such as Nissan Chemical Industries society manufactures can be enumerated.
As the colloided silica of alkalescence, the colloided silica by adding alkalimetal ion, ammonium ion, amine etc. and stabilization can be enumerated.These alkalescence colloided silica also can use commercially available product.As such commercially available product, " Snowtex-XS ", " Snowtex-S ", " Snowtex-30 " of such as Nissan Chemical Industries society manufacture, " 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 " can be enumerated; " adeliteAT-20 ", " adeliteAT-30 ", " adeliteAT-20N " that Xu electricity Hua Gongyeshe manufactures, " adeliteAT-30N ", " adeliteAT-20A ", " adeliteAT-30A ", " adeliteAT-40 " and " adeliteAT-50 "; " ludox (trade mark) HS-40 ", " ludoxHS-30 ", " ludoxLS " and " ludoxSM-30 " etc. that " Klebosol30R9 ", " Klebosol30R50 ", " Klebosol50R50 " that Clariant (Japan) society manufactures, society of Du Pont manufacture.
As the colloided silica taking water-soluble solvent as dispersion medium, also commercially available product can be used.As such commercially available product, " MA-ST-M (the methyl alcohol decentralized of particle diameter 20 ~ 25nm) ", " IPAST (the Virahol decentralized of particle diameter 10 ~ 15nm) ", " EG-ST (the ethylene glycol decentralized of particle diameter 10 ~ 15nm) ", " EG-ST-ZL (the ethylene glycol decentralized of particle diameter 70 ~ 100nm) ", " NPC-ST (the ethylene glycol list propyl ether decentralized of particle diameter 10 ~ 15nm) " etc. that such as Nissan Chemical Industries society manufactures can be enumerated.
Above-mentioned colloided silica can be used alone one, also can share two or more.Further, as a small amount of composition, also aluminum oxide or sodium aluminate etc. can be contained.In addition, colloided silica also can contain mineral alkali (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia etc.) or organic bases (tetramethyl-ammonium etc.) as stablizer.
The content of (D) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.1 ~ 5.0 quality %, is more preferably 0.2 ~ 3.0 quality %.By making the content of (D) composition in aqueous coating agent composition be above-mentioned scope, weathering resistance and the more excellent film of stain resistance can be obtained.
The content of (D) composition in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 5.0 ~ 70.0 quality %, is more preferably 10.0 ~ 50.0 quality %.By making the content of (D) composition in film be more than above-mentioned lower value, the stain resistance of film improves further, and by for below above-mentioned higher limit, the weathering resistance of film improves further.
< has inorganic oxide (E) > of photocatalytic activity
The aqueous coating agent composition of present embodiment preferably comprises the inorganic oxide (E) with photocatalytic activity further.Thus, photocatalytic activity and wetting ability is manifested by irradiating light to film.
As inorganic oxide (E), as long as the inorganic oxide for having photocatalytic activity, its kind is not particularly limited.As the concrete example of (E) composition, be not particularly limited, such as TiO can be enumerated 2, ZnO, SrTiO 3, BaTiO 3, BaTiO 4, BaTi 4o 9, K 2nbO 3, Nb 2o 5, Fe 2o 3, Ta 2o 5, K 3ta 3si 2o 3, WO 3, SnO 2, Bi 2o 3, BiVO 4, NiO, Cu 2o, RuO 2, CeO 2, have and be selected from by Ti, Nb, layered oxide (the such as Japanese Laid-Open Patent Publication 62-074452 publication of at least one element in the group of Ta and V composition, Japanese Unexamined Patent Publication 02-172535 publication, Japanese Unexamined Patent Publication 07-024329 publication, Japanese Unexamined Patent Publication 08-089799 publication, Japanese Unexamined Patent Publication 08-089800 publication, Japanese Unexamined Patent Publication 08-089804 publication, Japanese Unexamined Patent Publication 09-248465 publication, Japanese Unexamined Patent Publication 10-099694 publication, Japanese Unexamined Patent Publication 10-244165 publication etc.).
As (E) composition, chemically set out in the aspect such as stability, toxicity, environment face, is preferably TiO 2(titanium dioxide).As titanium dioxide, can be the crystalline texture of any one in Detitanium-ore-type, rutile-type, brookite type.
(E) composition preferably has the inorganic oxide of photocatalytic activity and it is the metallic compound of the modified process of its particle surface.By carrying out moditied processing, H can be reduced 2o 2or the generation of OH isoreactivity oxygen kind, the damage of base coating film can be suppressed further.As the material modified, be not particularly limited, such as silicon oxide, aluminium, copper oxide, ferriferous oxide etc. can be enumerated.Among these, preferential oxidation silicon.It should be noted that, utilize the complex compounds such as metal, Platinic chloride such as Fe, Cu, Al, Pt to carry out modifying and also can obtain same effect.
About the method for the surface of (E) composition being carried out to moditied processing, silicon oxide is illustrated as an example.As the method for silicon oxide being carried out to finishing process, be not particularly limited, such as following method etc. can be enumerated: in the slurry of titanium dioxide, add silicon compound, through operations such as neutralizing treatment, the hydrous oxide of silicon is separated out.
As silicon compound, be not particularly limited, the water-soluble silicon acid alkali metal salts such as such as water glass can be used.Among these, do not occur painted from the viewpoint of colourless, TiO 2 sol, preferred water glass.
The treatment capacity of the hydrous oxide of silicon is that benchmark is preferably 3.0 ~ 25 quality %, is more preferably 5.0 ~ 20 quality % relative to titanium dioxide with oxide compound.By making treatment capacity be more than above-mentioned lower value, can the increase of inhibit activities oxygen kind amount, therefore can prevent the damage of base coating film.In addition, by making treatment capacity be below above-mentioned higher limit, can suppress the aggegation of titanium dioxide, the viscosity of colloidal sol also can be suppressed to rise, therefore dispersed the and transparency improves further.
The content of (E) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.1 ~ 2.0 quality %, is more preferably 0.2 ~ 1.0 quality %.Be above-mentioned scope by the content of (E) composition making aqueous coating agent, stain resistance and the more excellent film of the transparency can be obtained.
The content of (E) composition in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 3.0 ~ 25.0 quality %, is more preferably 5.0 ~ 20.0 quality %.By making the content of (E) composition in film be more than above-mentioned lower value, the stain resistance of film improves further, and by for below above-mentioned higher limit, the transparency of film improves further.
< fluorocarbon surfactant (F) >
The aqueous coating agent composition of present embodiment is preferably further containing fluorocarbon surfactant (F).Thus, when using the aqueous coating agent composition of present embodiment or use the aqueous coating containing said composition to carry out application, can further improve the wettability to organic substrate etc., the apparent problems such as repulsion can be suppressed further.And then the homogeneity of film also improves further.As the reason of above-mentioned effect, still uncertain, supposition is because by containing (F) composition, can reduce the surface tension (but the effect of present embodiment is not limited to these) of aqueous coating agent composition.
As (F) composition, be not particularly limited, preferred amphoterics.As amphoterics, such as nonionic tensio-active agent, anionic amphoterics, cationic amphoterics etc. can be enumerated.As preferred concrete example, can enumerate and such as there is the amphoterics that carbonatoms is the perfluoroalkyl of 3 ~ 20.
As having the concrete example that carbonatoms is the amphoterics of the perfluoroalkyl of 3 ~ 20, fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl amine oxide, perfluoroalkyl ethylene oxide adduct can be enumerated, there is the all-fluoroalkyl compound etc. of anionic property group and cationic groups.Among these, from reducing the capillary aspect of coating, preferred perfluoroalkyl ethylene oxide adduct, there is the all-fluoroalkyl compound of anionic property group and cationic groups.
As perfluoroalkyl carboxylate, such as, also commercially available product can be used.As such commercially available product, " SurflonS-211 " of AGCSEIMICHEMICAL society manufacture etc. can be enumerated.As perfluoroalkyl amine oxide, such as, also commercially available product can be used.As such commercially available product, " SurflonS-241 " of AGCSEIMICHEMICAL society manufacture etc. can be enumerated.As perfluoroalkyl ethylene oxide adduct, such as, also commercially available product can be used.As such commercially available product, " MEGAFACF-444 " that such as DIC society manufactures can be enumerated, " SurflonS-242 " that AGCSEIMICHEMICAL society manufactures etc.As the all-fluoroalkyl compound with anionic property group and cationic groups, such as, also commercially available product can be used.As such commercially available product, " SurflonS-231 ", " SurflonS-232 ", " SurflonS-233 " etc. that AGCSEIMICHEMICAL society manufactures can be enumerated.These materials can be used alone one, also can share two or more.
The content of (F) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.0001 ~ 0.50 quality %, is more preferably 0.01 ~ 0.10 quality %.By making the content of (F) composition be more than above-mentioned lower value, the homogeneity of the film obtained improves further.By making the content of (F) composition be below above-mentioned higher limit, the weathering resistance of the film obtained improves further.
< fadedness pigment (G) >
The aqueous coating agent composition of present embodiment is preferably further containing fadedness pigment (G).Can prevent from thus omitting application, repeating application, the unequal problem of application.
As (G) composition, preferably eclipsed under the irradiation of sunlight and do not damage the material of the aesthetic property of substrate.Until the eclipsed time is different according to season and irradiating angle etc., usually confirm under visual eclipsed till during be preferably less than 20 days, be more preferably less than 10 days, more preferably less than 3 days.
As (G) composition, as long as there is character eclipsed under the irradiation of sunlight be just not particularly limited, as preference, a kind of being selected from group that, Xylene Red red, rose-red by methylene blue, Viola crystallina, malachite green, brilliant blue FCF, tetraiodofluorescein, famille rose, flame and fast green FCF form etc. can be enumerated.Among these, good from the viewpoint of color developing, eclipsed speed is also fast, more preferably methylene blue.These materials can be used alone one, also can share two or more.
The content of (G) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.0002 ~ 0.01 quality %, is more preferably 0.001 ~ 0.007 quality %.By making the content of (G) composition in aqueous coating agent composition be above-mentioned scope, color developing and the fadedness of film improve further.Said color developing refers to herein, and colour developing can the character of this degree of visual differentiation to the color distortion according to application face and non-application face, and fadedness refers to, fades to the character of the degree of the color of the aesthetic property not damaging base material.
The content of (G) composition in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 0.01 ~ 0.5 quality %, is more preferably 0.05 ~ 0.2 quality %, more preferably 0.1 ~ 0.2 quality %.By making the content of (G) composition be more than above-mentioned lower value, the color developing of film improves further, and by for below above-mentioned higher limit, the fadedness of film improves further.
< cellulose-based thickeners (H) >
The aqueous coating agent composition of present embodiment is preferably further containing cellulose-based thickeners (H).Thus, even if the solid component content of aqueous coating agent composition is low, during application, also can prevent liquid from hanging from above.As cellulose-based thickeners (H), be not particularly limited, a kind in the group being such as selected from and being made up of methylcellulose gum, Walocel MT 20.000PV, Natvosol, carboxymethyl cellulose, Vltra tears and their modifier can be enumerated.Among these, be preferably selected from a kind in the group be made up of Natvosol, Vltra tears and their modifier, more preferably Natvosol and modifier thereof.Be separately that these cellulose-based thickeners can be used alone one, also can share two or more.
In addition, in the scope of effect obtaining present embodiment, also other thickening materials can be share.As other thickening materials, be not particularly limited, can enumerate such as polycarboxylic acid system thickening material, Polyacrylamide thickening material, acrylic acid acrylamide copolymer salt system thickening material, cellulose-based beyond polyose system thickening material, vinyl ether system thickening material etc. go out.
As Natvosol, also commercially available product can be used.As such commercially available product, " HECDaicelSP200 ", " HECDaicelSP400 ", " HECDaicelSP500 " that such as Daicelfinechem society manufactures can be enumerated, " HECSZ-25F " that society's manufacture is refined in " Sanhec (trade mark) HH ", " SanhecH ", " SanhecM " that " HECDaicelSP550 ", " HECDaicelSP600 ", " HECDaicelSP800 ", " HECDaicelSP850 " and " HECDaicelSP900 ", three prosperous societies manufacture and " SanhecG & L ", Sumitomo etc.
The weight-average molecular weight of Natvosol is not particularly limited, and is preferably 700,000 ~ 2,000,000, is more preferably 1,000,000 ~ 1,600,000.Be more than 700,000 by weight-average molecular weight, the liquid of aqueous coating agent composition can be suppressed further to hang from above.Be less than 2,000,000 by weight-average molecular weight, the transparency of the film obtained by waterborne compositions improves further.Weight-average molecular weight measures by gel permeation chromatography (GPC).
As Vltra tears, also commercially available product can be used.As commercially available product, " NEOVISCO-MCHM4000S ", " NEOVISCO-MCRM4000S ", " NEOVISCO-MCRM15000S ", " NEOVISCO-MCRM30000S " and " NEOVISCO-MCRM50000S " etc. of " METOLOSE90SH-04 ", " METOLOSE90SH-15 ", " METOLOSE90SH-100 " of such as SHIN-ETSU HANTOTAI's chemistry society manufacture, " METOLOSE90SH-400 ", " METOLOSE90SH-4000 ", " METOLOSE90SH-15000 " and " METOLOSE90SH-100000 ", the manufacture of three prosperous societies can be enumerated.
When share other thickening materials, preferably using polycarboxylic acid system thickening material, Polyacrylamide thickening material, more preferably using polycarboxylic acid system thickening material.
As polycarboxylic acid system thickening material, also commercially available product can be used.As commercially available product, " A-20P-X ", " A-7100 ", " A-7185 " etc. that such as East Asia synthesis society manufactures can be enumerated.
The content of (H) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.04 ~ 0.30 quality %, is more preferably 0.08 ~ 0.20 quality %.By making the content of (H) composition in aqueous coating agent composition be above-mentioned scope, transparent and that weathering resistance is more excellent film can be obtained.
The content of (H) composition in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 2.0 ~ 15.0 quality %, is more preferably 4.0 ~ 9.0 quality %.By making the content of (H) composition in film be more than above-mentioned lower value, the transparency of film improves further, and by for below above-mentioned higher limit, the weathering resistance of film improves further.
< algaecide, mould inhibitor (J) >
The film of present embodiment is preferably further containing more than a kind that is selected from the group that is made up of algaecide and mould inhibitor (J).Thus, even if be difficult to the position be irradiated at light such as sunlights, the film (but the effect of present embodiment is not limited to these) of mildew resistance and/or anti-algae property excellence also can be formed.
As algaecide and/or mould inhibitor (J), be not particularly limited, can enumerate such as organic iodine based compound, alcohol based compound, nitrile compound, disulphide based compound, thiocarbamate based compound, containing azo-cycle compound etc.Among these, preferably containing azo-cycle compound.As containing azo-cycle compound, thiazoline based compound, isothiazoline based compound, triazine based compound, imidazole compound etc. can be enumerated.Among these, be preferably selected from more than a kind in the group be made up of isothiazoline based compound, triazine based compound, imidazole compound, be more preferably selected from more than a kind in the group be made up of isothiazoline based compound, triazine based compound.As the compound of particularly anti-algae property excellence, such as triazine based compound etc. can be enumerated.As the compound of particularly mildew resistance excellence, such as thiazoline based compound, isothiazoline based compound, imidazole compound etc. can be enumerated.Certainly can use the compound having anti-algae property and mildew resistance concurrently, as such compound, the isothiazoline based compound etc. containing chlorine atom in such as molecule can be enumerated.These materials can be used alone one, also can share two or more.
As thiazoline based compound, also commercially available product can be used.As such commercially available product, " Millcut-180 ", " Biocut-LC3 " that such as Japanese Cao Da society manufactures can be enumerated, " AmordenALK " that large and chemical industry society manufactures etc.
As isothiazoline based compound, also commercially available product can be used.As such commercially available product, " Biocut-TR120 ", " PROXELGXL ", " PROXELBDN " of the manufacture of ArchChemicals society, " KLARIX4000 ", " ROZONE2000 ", " ROCIMA252 ", " ROCIMA200 ", " ROCIMA345 ", " ROCIMA350 ", " ROCIMA553 ", " BIOBAN551S ", " SkaneM-8 " etc. of DowChemical society manufacture that such as Japanese Cao Da society manufactures can be enumerated.
As triazine based compound, also commercially available product can be used.As commercially available product, " Biocut-N35 ", " DP-2159 ", " DP-2615 " that such as Japanese Cao Da society manufactures can be enumerated." AmordenNBP-8 ", " AmordenNBPconc " that " DP-2619 ", " DP-2623 ", large and chemical industry society manufacture, three associations change into " the サ Application ア Le ガ 1907 " that society manufactures etc.
As imidazole compound, also commercially available product can be used.As commercially available product, such as " Biocut-N35 ", " Biocut-AF40 ", " DX-2 " of the manufacture of Japanese Cao Da society, " ROCIMA363 " of DowChemical society manufacture etc. can be enumerated.
The content of (J) composition in aqueous coating agent composition is not particularly limited, and is preferably 0.01 ~ 0.80 quality %, is more preferably 0.05 ~ 0.50 quality %.By making the content of (J) composition in waterborne compositions be above-mentioned scope, the film that the transparency, weathering resistance and microbial resistance are more excellent can be obtained.
The content of (J) composition in the film obtained by aqueous coating agent composition is not particularly limited, and is preferably 0.1 ~ 30.0 quality %, is more preferably 1.0 ~ 15.0 quality %.By making the content of (J) composition in film be more than above-mentioned lower value, the microbial resistance of film improves further, and by for below above-mentioned higher limit, the transparency and the weathering resistance of film improve further.
In the scope of effect that can obtain present embodiment, also can share other antiseptic-germicides further.As other antiseptic-germicides, be not particularly limited, such as silver-colored based compound, copper based compound, zinc based compound etc. can be enumerated.
The content (solid component content) of the solids component in aqueous coating agent composition is not particularly limited, and from the aspect of the homogeneity of film, is preferably 0.5 ~ 10.0 quality %, is more preferably 1.5 ~ 6.0 quality %.By making the content of the solids component in aqueous coating agent composition be more than above-mentioned lower value, stain resistance improves further.By making the content of the solids component in aqueous coating agent composition be below above-mentioned higher limit, the transparency improves further.Said solid component content is obtained by the method recorded in embodiment described later herein.In addition, according to the purposes of film, sometimes also require that the thickness of film is thinner.Even if in this case, by making the solid component content in aqueous coating agent composition be below above-mentioned higher limit, although the film that the physical property that can be made into the thinner weathering resistance of thickness and stain resistance and so on is also excellent.By making the solid component content in aqueous coating agent composition be more than above-mentioned lower value, time of drying required when forming film can be shortened, can further improve operating efficiency.
The aqueous coating agent composition of present embodiment can as required further containing other compositions other than the above in the scope that can obtain its effect.As other such compositions, be not particularly limited, such as defoamer, freeze-stable agent, delustering agent, catalyst for cross-linking reaction, pigment, curing catalysts, linking agent, weighting agent, anti skinning agent, dispersion agent, wetting agent, photostabilizer, antioxidant, UV light absorber, film coalescence aid, rust-preventive agent, softening agent, lubricant, reductive agent, sanitas, reodorant, anti-yellowing agent, static inhibitor, charged adjusting agent etc. can be enumerated.These can be used alone one, also can share two or more.
Above-mentioned aqueous coating agent composition can be applicable to using with the form of aqueous coating.That is, the aqueous coating of present embodiment contains above-mentioned aqueous coating agent composition.For aqueous coating, defoamer, freeze-stable agent, delustering agent, catalyst for cross-linking reaction, pigment, curing catalysts, linking agent, weighting agent, anti skinning agent, dispersion agent, wetting agent, photostabilizer, antioxidant, UV light absorber, film coalescence aid, rust-preventive agent, softening agent, lubricant, reductive agent, sanitas, mould inhibitor, algaecide, reodorant, anti-yellowing agent, static inhibitor, charged adjusting agent etc. can be contained further and be used as other compositions.
The aqueous coating of present embodiment can suitably be coated with the method be applicable to according to the material etc. of its purposes and coating object.As coating process, be not particularly limited, such as spray method, flow coat method, rolling method, spread coating, Dipcoat method, method of spin coating, silk screen print method, teeming practice, woodburytype, flexographic printing method can be enumerated.
Carry out drying after aqueous coating by coating present embodiment and obtain film to remove volatile matter.Now, heat treated or uviolizing process etc. at about 40 ~ 120 DEG C temperature can be carried out as required further.
So, can be made into the film containing above-mentioned aqueous coating in present embodiment.This film is obtained by aqueous coating, also can such as by the surface of above-mentioned aqueous coating being coated various base material is carried out drying and made the film be formed on base material.That is, also can make coated articles in present embodiment, this coated articles contains base material and is formed at the above-mentioned film at least partially on surface of base material.
As long as in present embodiment, the material of spendable base material just can be not particularly limited at its surface formation film, can be any one in organic substrate, inorganic substrate, preferred organic substrate.As the material of base material, be not particularly limited, such as synthetic resins, natural resin, metal, pottery, glass, building stones, cement, concrete etc. can be enumerated.These materials can be used alone one, also can share two or more.Particularly, in the present embodiment, can be formed can maintain with high level the film of outward appearance and stain resistance in, even the organic substrate be made up of the material of the second-order transition temperature with-5 ~ 20 DEG C low so is also applicable.
As synthetic resins, be not particularly limited, such as thermoplastic resin, curable resin (heat-curing resin, light-cured resin, moisture-curable resin etc.) can be enumerated.As the concrete example of synthetic resins, be not particularly limited, such as silicone resin can be enumerated, acrylic resin, methacrylic resin, fluoro-resin, Synolac, amino-alkyd resin, Vinylite, vibrin, styrene-butadiene resins, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether-ether-ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulphone resin, polyether resin, polyvinyl chloride (PVC) RESINS, polyvinylidene chloride resin, urea resin, phenol resins, melamine resin, epoxy resin, carbamate resins, silicone-acrylic resinoid etc.In addition, be also contained in synthetic resins by the film formed for the acrylic resin system coating of construction exterior etc., silicone-acrylic resinoid system coating, fluoro-resin system coating.
As natural resin, be not particularly limited, the protein system resins etc. such as isoprene resin, the caseins such as such as cellulose-based resin, natural rubber can be enumerated.
When base material is the resin base material employing above-mentioned synthetic resins or natural resin etc., the surface treatments such as Corona discharge Treatment, flame treating, Cement Composite Treated by Plasma can be implemented as required.
The coated articles of present embodiment contains base material and is formed at the above-mentioned film on this base material, even if this film is also useful as coating etc.The film obtained by present embodiment can maintain outward appearance and anti fouling performance with high level for a long time, therefore, also can use in unworkable environment in the prior art aptly.From this side considerations, as the concrete example of the coated articles of present embodiment, such as building materials can be enumerated, buildings is exterior, buildings is in-built, window frame, window glass, various lens, structure unit, the Architectural Equipments such as house, the cover of vehicle lighting lamp and window glass, mechanism or article exterior, dw and application, display instrument, its cover, traffic mark, various display unit, the display object such as advertising tower, the sound-proof wall of road use and railway use etc., bridge, exterior and the application of guardrail, in-built and the application in tunnel, insulator, solar-electricity pool cover, the electronics that solar water heater heat-collecting cover etc. use in outside, the externally mounted part of electric installation, particularly transparent component, plastic greenhouse, greenhouse etc. exterior.
As the manufacture method of the coated articles of present embodiment, following method can be enumerated: such as, the surface of base material at least partially on be coated with above-mentioned aqueous coating (or aqueous coating agent composition), carry out drying etc. as required, thus formation film, but manufacture method is not limited to this.Such as, after the film of present embodiment can being coated with on base material, this film is peeled off from this base material, be bonded on other base material.Or, after also can being coated with the film of present embodiment on base material, this film is bonded on other base material with the state closely sealed with this base material.
The aqueous coating agent composition of present embodiment mixture can become various aqueous coating.Such aqueous coating can form the excellent film such as outward appearance, stain resistance and then the transparency, weathering resistance, mildew resistance, anti-algae property.So, the outward appearance of the film of present embodiment, stain resistance and then the transparency, weathering resistance, mildew resistance, anti-algae property etc. are also excellent, can be used for comprising in the purposes widely of the outer coatings of buildings etc.
Embodiment
Illustrate in greater detail the present invention below by way of embodiments and comparative examples, but the present invention is not limited to following examples.Various physical property is determined by following method in embodiment and comparative example.
< is coated with the making > of the base material X of enamel-cover coating in advance
The making of pigment dispersion
(Kanpehapio society manufactures to utilize desk-top sand mill, the desk-top sand mill of batch-type), by dispersion agent (BASFJapan society manufactures, " Pig.DisperserMD20 ") 5.35g, ammoniacal liquor 0.50g, propylene glycol 23.50g, water 147.50g, titanium dioxide (chlorine method rutile titanium dioxide; Stone originate in industry society manufacture, " TaipakeCR-97 ") 333.50g, defoamer (modified silicone system; SANNOPCO society manufactures, " SNDefoamer1310 ") mixed thing of 2.85g disperses 20 minutes, obtains pigment dispersion.
The making of enamel-cover coating X
2 are added in the polymer emulsion X of the Production Example 1 of 109.0g, 2,4-trimethylammonium-1, (Chisso society manufactures 3-butyleneglycol isobutyrate, " CS-12 ") 10.0g, ethylene glycol monobutyl ether 50 mass parts and water 50 mass parts mixed solution 10.0g, pigment dispersion 51.4g obtained above, (Xu electricity Hua Gongyeshe manufactures thickening material, " ADEKANOLUH-438 ") 10% aqueous solution 0.5g, mix mixing in 1 hour, obtain enamel-cover coating X.
Be coated with the making of the base material X of enamel-cover coating X in advance
Use line rod coating machine No.50, application enamel-cover coating obtained above X on the acidproof aluminium sheet of the sulfuric acid of 7cm × 15cm or 5cm × 5cm, in temperature 23 DEG C, relative humidity 50% time drying 48 hours, is coated with the base material X of enamel-cover coating X in advance.
< is coated with the making > of the base material Y of enamel-cover coating in advance
The making of enamel-cover coating Y
Do not use the polymer emulsion X109.0g of Production Example 1, and use the polymer emulsion Y109.0g of Production Example 2, in addition, obtain enamel-cover coating Y in the same manner as enamel-cover coating X.
Be coated with the making of the base material Y of enamel-cover coating Y in advance
Use line rod coating machine No.50, application enamel-cover coating obtained above Y on the acidproof aluminium sheet of the sulfuric acid of 7cm × 15cm or 5cm × 5cm, in temperature 23 DEG C, relative humidity 50% time drying 48 hours, is coated with the base material Y of enamel-cover coating Y in advance.
1. the content of each composition and solid component content
Materialsed 2g in aluminium dish, 150 DEG C of heating 1 hour.Measure the quality of the sample before and after heating, calculate solid component content (quality %) by its difference.According to the method, measure the solid component content in the content of each composition and composition respectively.
2. number average bead diameter
Add ion exchanged water to carry out diluting to make load factor (loadingindex) be 1.5 ~ 3.0, use wet type grain size analyser (Ji Zhuan society manufactures, " microtrackUPA-9230 ") to measure.Condition determination is as follows.
Load factor: 1.5 ~ 3.0
Minute: 60 seconds
Measure number of times: 3 times
3. viscosity
BM type viscometer (manufacture of Dong Ji industry society) is used to measure.Condition determination is as follows.
Temperature: 23 DEG C
Rotor: No.1
Rotating speed: 60rpm
4. second-order transition temperature
Use " DCS6220 " that SeikoInstruments society manufactures, the condition determination being 10 DEG C/min at heat-up rate measures, and obtains second-order transition temperature by obtained DSC point of inflexion on a curve.It should be noted that, condition determination is as follows.
Mensuration pond: aluminium vessel
The making of test sample: add the emulsion 40mg as measuring sample in aluminium vessel, 130 DEG C of dryings 1 hour.
5. atmospheric exposure test: the gloss retention after 3000 hours
The base material X of 7cm × 15cm being coated with enamel-cover coating in advance or base material Y utilize spraying carry out the application of waterborne compositions, to make the glue spread of this waterborne compositions for 17g/m 2or 50g/m 2ratio.Base material through application is kept level, leaves standstill 48 hours, as test board 50% time in temperature 23 DEG C, relative humidity." the sunlight weather resistance test case " that use SUGA tester to manufacture carries out exposure test (blackboard temperature 63 DEG C, rainfall 18 minutes/2 hours).Glossmeter (BYKGardner society manufactures, " micro-tri-gloss μ ") is used to measure respectively 60 ° of glossiness after exposing 3000 hours to the open air.
Further, gloss retention is calculated based on following formula.It should be noted that, to the result that the base material being coated with enamel-cover coating is in advance evaluated be only, base material X expose 3000 hours to the open air after gloss retention be 80%, the gloss retention exposed to the open air after 3000 hours of base material Y is 88%, these values demonstrate, when the value of gloss retention is large, weathering resistance is good.
60 ° of glossiness × 100 before 60 ° of glossiness/exposure tests after gloss retention (%)=exposure test
6. stain resistance
The base material X of 7cm × 15cm being coated with enamel-cover coating in advance or base material Y utilize spraying carry out the application of waterborne compositions, to make the glue spread of this waterborne compositions for 17g/m 2or 50g/m 2ratio.Base material through application is kept level, leaves standstill 48 hours, as test board 50% time in temperature 23 DEG C, relative humidity.Test board is attached at the fence towards Ordinary Rd (truck traffic volume about 500 ~ 1000/day), leaves standstill 6 months or 1 year.The pollution level of the test board after leaving standstill based on following benchmark visual valuation.It should be noted that, to the evaluation result of base material X or Y being coated with enamel-cover coating be in advance only, leave standstill 6 months, within 1 year, be the evaluation of "×".
Zero: almost do not confirm dirt.
△: confirm and have dirt a little, but the degree being practical upper no problem.
×: confirm a large amount of dirts.
7. fungicidal properties
The base material X of 5cm × 5cm being coated with enamel-cover coating in advance or base material Y utilize spraying carry out the application of waterborne compositions, to make the glue spread of this waterborne compositions for 17g/m 2or 50g/m 2ratio.Base material through application is kept level, leaves standstill 48 hours, as test board 50% time in temperature 23 DEG C, relative humidity.
About condition other than the above, according to " tests of 8 coating " of JISZ-2911 (mould resistance test method), use by aspergillus niger, addicted to loose mould, Cladosporium cladosporioides, aureobasidium pullulans, green trichoderma bacterium with test every the mixed material of interlinkage spore mutually.After test, based on following benchmark implementation evaluation.
◎: growth film not confirming mycelia.
Zero: the area of the growth part of the mycelia that film confirms relative to the total area more than 0 and be less than 1/3.
△: the area of the growth part of the mycelia that film confirms relative to the total area more than 1/3 and be less than 2/3.
×: the area of the growth part of the mycelia that film confirms relative to the total area more than 2/3.
8. anti-algae performance
The base material X of 5cm × 5cm being coated with enamel-cover coating in advance or base material Y utilize spraying carry out the application of waterborne compositions, to make the glue spread of this waterborne compositions for 17g/m 2or 50g/m 2ratio.Base material through application is kept level, leaves standstill 48 hours, as test board 50% time in temperature 23 DEG C, relative humidity.
Do not use mould, and use the mixed material of algae that Chlorella vulgaris and bright green to be quivered, and use above-mentioned test film, in addition, the test damp process of fibre product " 7c) " based on JISZ-2911 (mould resistance test method) tests.After test, based on following benchmark implementation evaluation.
◎: growth film not confirming algae.
Zero: the area of the growth part of the algae that film confirms relative to the total area more than 0 and be less than 1/3.
△: the area of the growth part of the algae that film confirms relative to the total area more than 1/3 and be less than 2/3.
×: the area of the growth part of the algae that film confirms relative to the total area more than 2/3.
9. wet type decomposability
The base material X of 7cm × 15cm being coated with enamel-cover coating in advance or base material Y utilize spraying carry out the application of waterborne compositions, to make the glue spread of this waterborne compositions for 17g/m 2or 50g/m 2ratio.Base material through application is kept level, leaves standstill 48 hours, as test board 50% time in temperature 23 DEG C, relative humidity.About this test board, test based on JISR1703-2 (the self-cleaning performance test method-2 of fine ceramics-photocatalyst material: wet type decomposability), obtain degrading activity index.Degrading activity index is higher, represents that self-cleaning property is better.
[Production Example 1]
The synthesis of polymer emulsion X
In the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts, drop into ion exchanged water 292g, (ADEKA society manufactures reactive emulsifier, " AdekaReasoapSR-1025 "; Solid component content is the aqueous solution of 25 quality %) 8g, by the heating temperatures to 80 in reactor DEG C under stirring.The ammonium persulfate aqueous solution 10g of 2 quality % is added in this reactor, after 5 minutes, dripped by methyl methacrylate 15g, cyclohexyl methacrylate 10g, butyl acrylate 65g, methacrylic acid 5g, 2-hydroxyethyl methacrylate 10g, reactive emulsifier (manufacture of ADEKA society, " AdekaReasoapSR-1025 " with 60 minutes under the state that the temperature in reactor is kept 80 DEG C; Solid component content is the aqueous solution of 25 quality %) 4g, 2 quality % ammonium persulfate aqueous solution 15g, ion exchanged water 49g form emulsion mixture.Thereafter, the temperature in reactor maintained 80 DEG C and continue stirring 60 minutes.
Then, dripped by methyl methacrylate 80g, cyclohexyl methacrylate 90g, butyl acrylate 222g, methacrylic acid 8g, reactive emulsifier (manufacture of ADEKA society, " AdekaReasoapSR-1025 " by different dropwise adding tanks with 160 minutes; Solid component content is the aqueous solution of 25 quality %) 16g, 2 quality % ammonium persulfate aqueous solution 60g, ion exchanged water 196g form emulsion mixture; And the mixed solution to be made up of 3-methacryloxypropyl trimethoxy silane 1g, dimethyldimethoxysil,ne 20g, methyltrimethoxy silane 20g.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 120 minutes.After cool to room temperature, the hydrogen ion concentration of the reaction solution in assaying reaction device, result pH is 2.2.Being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, with 100 object metal mesh filter reaction solutions, obtains the polymer emulsion X of enamel-cover coating.The solid component content of the polymer emulsion X obtained is 44.5 quality %.About the polymkeric substance contained by this polymer emulsion X, the second-order transition temperature obtained by DSC point of inflexion on a curve based on aforesaid method is 1 DEG C.
[Production Example 2]
The synthesis of polymer emulsion Y
In the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts, drop into ion exchanged water 292g, (ADEKA society manufactures reactive emulsifier, " AdekaReasoapSR-1025 "; Solid component content is the aqueous solution of 25 quality %) 8g, by the heating temperatures to 80 in reactor DEG C under stirring.The ammonium persulfate aqueous solution 10g of 2 quality % is added in this reactor, after 5 minutes, dripped by methyl methacrylate 15g, cyclohexyl methacrylate 10g, butyl acrylate 65g, methacrylic acid 5g, 2-hydroxyethyl methacrylate 10g, reactive emulsifier (manufacture of ADEKA society, " AdekaReasoapSR-1025 " with 60 minutes under the state that the temperature in reactor is kept 80 DEG C; Solid component content is the aqueous solution of 25 quality %) 4g, 2 quality % ammonium persulfate aqueous solution 15g, ion exchanged water 49g form emulsion mixture.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 60 minutes.
Then, dripped by methyl methacrylate 150g, cyclohexyl methacrylate 90g, butyl acrylate 152g, methacrylic acid 8g, reactive emulsifier (manufacture of ADEKA society, " AdekaReasoapSR-1025 " by different dropwise adding tanks with 160 minutes; Solid component content is the aqueous solution of 25 quality %) 16g, 2 quality % ammonium persulfate aqueous solution 60g, ion exchanged water 196g form emulsion mixture; And the mixed solution to be made up of 3-methacryloxypropyl trimethoxy silane 1g, dimethyldimethoxysil,ne 20g, methyltrimethoxy silane 20g.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 120 minutes.After cool to room temperature, the hydrogen ion concentration of the reaction solution in assaying reaction device, result pH is 2.2.Being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, with 100 object metal mesh filter reaction solutions, obtains the polymer emulsion Y of enamel-cover coating.The solid component content of the polymer emulsion Y obtained is 44.5 quality %.About the polymkeric substance contained by this polymer emulsion Y, the second-order transition temperature obtained by DSC point of inflexion on a curve based on aforesaid method is 20 DEG C.
[Production Example 3]
The synthesis of the water dispersion (CD-1) of polymkeric substance (C-1)
Drop into the Witco 1298 Soft Acid aqueous solution 5.6g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 110.0g, phenyltrimethoxysila,e 73.0g, methyltrimethoxy silane 29.4g in this reactor under the state that the temperature kept in reactor is 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 5.6g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after the ammonium persulfate aqueous solution 6.6g of input 2 quality %, with within about 2 hours, dripping the mixed solution be made up of methyl methacrylate 22.5g, n-butyl acrylate 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 1.2g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 1.2g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 286.4g form mixed solution.And then continue stir abouts after 1 hour the temperature in reactor being maintained 80 DEG C, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-1) of the polymkeric substance (C-1) that number average bead diameter is 155nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 36.9 quality % in polymkeric substance (C-1).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, be respectively 7.9 quality % in polymkeric substance (C-1), 30.2 quality % and 0.4 quality %, add up to 38.5 quality %.
It should be noted that, the content that the hydrolytic condensate for above-mentioned each monomer converts calculates based on following formula.
Such as when (a) composition, a the reactive group (alkoxyl group etc.) of () composition is converted to silanol bonds by hydrolysis or condensation reaction, become the condenses of structural unit (A), the reduction factor of said (a) composition is its mass ratio (total amount of total amount/this (a) composition of this condenses) herein, can be represented by following formula (i).
In addition, such as when (b) composition, b the reactive group (alkoxyl group etc.) of () composition is converted to silanol bonds by hydrolysis or condensation reaction, become the condenses with structural unit (B), the reduction factor of said (b) composition is its mass ratio (total amount of total amount/this (b) composition of this condenses) herein, can be represented by following formula (ii).
Content (quality %)=[charging capacity (the g) × reduction factor of (a) composition] ÷ total solids component content (g) × 100 of structural unit (A) in polymkeric substance (C)
[several 1]
α: the molecular weight of (a) composition
R 2: the R of general formula (1) 2molecular weight
γ: the nucleidic mass of oxygen
The reduction factor of each composition calculated as mentioned 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
Content (quality %)=[charging capacity (the g) × reduction factor of (b) composition] ÷ total solids component content (g) × 100 of structural unit (B) in polymkeric substance (C)
[several 2]
β: the molecular weight of (b) composition
R 4: the R of general formula (2) 4molecular weight
γ: the nucleidic mass of oxygen
The reduction factor of each composition calculated as mentioned above is as follows.
Methyltrimethoxy silane: 0.493
Phenyltrimethoxysila,e: 0.652
3-methacryloxypropyl trimethoxy silane: 0.722
[Production Example 4]
The synthesis of the water dispersion (CD-2) of polymkeric substance (C-2)
Drop into the Witco 1298 Soft Acid aqueous solution 8.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 105.0g, phenyltrimethoxysila,e 10.0g, methyltrimethoxy silane 65.7g in this reactor under the state that temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-2) of the polymkeric substance (C-2) that number average bead diameter is 133nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 47.9 quality % in polymkeric substance (C-2).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 24.0 quality % in polymkeric substance (C-2), 17.7 quality % and 0.6 quality %, add up to 42.3 quality %.
[Production Example 5]
The synthesis of the water dispersion (CD-3) of polymkeric substance (C-3)
Drop into the Witco 1298 Soft Acid aqueous solution 8.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 125.0g, phenyltrimethoxysila,e 10.0g, methyltrimethoxy silane 40.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-3) of the polymkeric substance (C-3) that number average bead diameter is 170nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 57.2 quality % in polymkeric substance (C-3).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 14.6 quality % in polymkeric substance (C-3), 17.8 quality % and 0.6 quality %, add up to 33.0 quality %.
[Production Example 6]
The synthesis of the water dispersion (CD-4) of polymkeric substance (C-4)
Drop into the Witco 1298 Soft Acid aqueous solution 7.0g of ion exchanged water 810g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldiethoxysilane 158.0g, phenyltrimethoxysila,e 16.8g, methyltrimethoxy silane 33.1g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 20.0g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-4) of the polymkeric substance (C-4) that number average bead diameter is 180nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the di ethoxy di methyl-monosilane that uses during this water dispersion of synthesis, is 59.4 quality % in polymkeric substance (C-4).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 12.3 quality % in polymkeric substance (C-4), 18.0 quality % and 0.6 quality %, add up to 30.9 quality %.
The synthesis of the water dispersion (CD-5) of polymkeric substance (C-5)
Drop into the Witco 1298 Soft Acid aqueous solution 7.0g of ion exchanged water 830g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of diisopropyl dimethoxy silane 101.5g, phenyltrimethoxysila,e 10.0g, methyltrimethoxy silane 33.1g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-5) of the polymkeric substance (C-5) that number average bead diameter is 180nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the diisopropyl dimethoxy silane that uses during this water dispersion of synthesis, is 58.1 quality % in polymkeric substance (C-5).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 12.6 quality % in polymkeric substance (C-5), 18.6 quality % and 0.6 quality %, add up to 31.8 quality %.
[Production Example 8]
The synthesis of the water dispersion (CD-6) of polymkeric substance (C-6)
Drop into the Witco 1298 Soft Acid aqueous solution 7.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 71.3g, dimethoxydiphenylsilane 49.3g, phenyltrimethoxysila,e 36.8g, methyltrimethoxy silane 33.1g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g input of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-6) of the polymkeric substance (C-6) that number average bead diameter is 180nm as polymkeric substance.
Carrying out the conversion of complete hydrolysis condenses respectively to the dimethyldimethoxysil,ne used during this water dispersion of synthesis and dimethoxydiphenylsilane, is 31.9 quality % in polymkeric substance (C-6) and 29.0 quality %.
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 11.8 quality % in polymkeric substance (C-6), 17.4 quality % and 0.6 quality %, add up to 29.8 quality %.
[Production Example 9]
The synthesis of the water dispersion (CD-7) of polymkeric substance (C-7)
Drop into the Witco 1298 Soft Acid aqueous solution 7.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethoxymethylphenylsilane 109.7g, phenyltrimethoxysila,e 10.0g, methyltrimethoxy silane 33.1g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-7) of the polymkeric substance (C-7) that number average bead diameter is 170nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethoxymethylphenylsilane that uses during this water dispersion of synthesis, is 60.3 quality % in polymkeric substance (C-7).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 12.0 quality % in polymkeric substance (C-7), 17.6 quality % and 0.6 quality %, add up to 30.2 quality %.
[Production Example 10]
The synthesis of the water dispersion (CD-8) of polymkeric substance (C-8)
Drop into the Witco 1298 Soft Acid aqueous solution 10.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 140.0g, phenyltrimethoxysila,e 20.0g, methyltrimethoxy silane 5.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-8) of the polymkeric substance (C-8) that number average bead diameter is 119nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 64.7 quality % in polymkeric substance (C-8).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 1.8 quality % in polymkeric substance (C-8), 22.8 quality % and 0.6 quality %, add up to 25.2 quality %.
[Production Example 11]
The synthesis of the water dispersion (CD-9) of polymkeric substance (C-9)
Drop into the Witco 1298 Soft Acid aqueous solution 10.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 140.0g, methyltrimethoxy silane 40.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of methyltrimethoxy silane 30.0g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-9) of the polymkeric substance (C-9) that number average bead diameter is 150nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 63.9 quality % in polymkeric substance (C-9).
In addition, the methyltrimethoxy silane that uses during this water dispersion of synthesis and the 3-methacryloxypropyl trimethoxy silane condenses that is hydrolyzed is converted, for 25.5 quality % in polymkeric substance (C-9) and 0.6 quality %, add up to 26.1 quality %.
[Production Example 12]
The synthesis of the water dispersion (CD-10) of polymkeric substance (C-10)
Drop into the Witco 1298 Soft Acid aqueous solution 10.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 140.0g, phenyltrimethoxysila,e 25.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (CD-10) of the polymkeric substance (C-10) that number average bead diameter is 160nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 64.3 quality % in polymkeric substance (C-10).
In addition, the phenyltrimethoxysila,e that uses during this water dispersion of synthesis and the 3-methacryloxypropyl trimethoxy silane condenses that is hydrolyzed is converted, for 25.1 quality % in polymkeric substance (C-10) and 0.6 quality %, add up to 25.7 quality %.
[Production Example 13]
The synthesis of the water dispersion of polymkeric substance (C '-11) (C ' D-11)
Drop into the Witco 1298 Soft Acid aqueous solution 5.6g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 81.0g, phenyltrimethoxysila,e 124.8g, methyltrimethoxy silane 29.4g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 5.6g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 1.2g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 1.2g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 286.4g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (C ' D-11) of the polymkeric substance (C '-11) that number average bead diameter is 160nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 30.1 quality % in polymkeric substance (C '-11).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 8.7 quality %, 53.8 quality % and 0.5 quality % in polymkeric substance (C '-11), add up to 63.0 quality %.
[Production Example 14]
The synthesis of the water dispersion of polymkeric substance (C '-12) (C ' D-12)
Drop into the Witco 1298 Soft Acid aqueous solution 5.6g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 81.0g, phenyltrimethoxysila,e 73.0g, methyltrimethoxy silane 30.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 5.6g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of methyl methacrylate 22.5g, n-butyl acrylate 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 1.2g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 1.2g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 286.4g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (C ' D-12) of the polymkeric substance (C '-12) that number average bead diameter is 157nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 30.1 quality % in polymkeric substance (C '-12).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 8.9 quality %, 33.4 quality % and 0.5 quality % in polymkeric substance (C '-12), add up to 42.8 quality %.
[Production Example 15]
The synthesis of the water dispersion of polymkeric substance (C '-13) (C ' D-13)
Drop into the Witco 1298 Soft Acid aqueous solution 10.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 168.0g, phenyltrimethoxysila,e 10.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (C ' D-13) of the polymkeric substance (C '-13) that number average bead diameter is 146nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 73.1 quality % in polymkeric substance (C '-13).
In addition, the phenyltrimethoxysila,e that uses during this water dispersion of synthesis and the 3-methacryloxypropyl trimethoxy silane condenses that is hydrolyzed is converted, for 16.9 quality % in polymkeric substance (C '-13) and 0.6 quality %, add up to 17.5 quality %.
[Production Example 16]
The synthesis of the water dispersion of polymkeric substance (C '-14) (C ' D-14)
Drop into the Witco 1298 Soft Acid aqueous solution 5.6g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethyldimethoxysil,ne 150.0g, phenyltrimethoxysila,e 30.0g, methyltrimethoxy silane 10.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 5.6g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of methyl methacrylate 22.5g, n-butyl acrylate 11.2g, phenyltrimethoxysila,e 12.3g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 1.2g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 1.2g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 286.4g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (C ' D-14) of the polymkeric substance (C '-14) that number average bead diameter is 163nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethyldimethoxysil,ne that uses during this water dispersion of synthesis, is 54.2 quality % in polymkeric substance (C '-14).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 2.9 quality %, 16.1 quality % and 0.5 quality % in polymkeric substance (C '-14), add up to 19.5 quality %.
[Production Example 17]
The synthesis of the water dispersion of polymkeric substance (C '-15) (C ' D-15)
Drop into the Witco 1298 Soft Acid aqueous solution 7.0g of ion exchanged water 850g, 10 quality % in the reactor with reflux exchanger, dropwise adding tank, thermometer and whipping appts after, by the heating temperatures to 80 in reactor DEG C under stirring.With within about 2 hours, dripping the mixed solution be made up of dimethoxymethylphenylsilane 140.0g, phenyltrimethoxysila,e 8.0g, methyltrimethoxy silane 10.0g in this reactor under the state that the temperature in reactor is kept 80 DEG C.Thereafter, the temperature in reactor is maintained 80 DEG C and continue stirring 30 minutes.Then, after dropping into the Witco 1298 Soft Acid aqueous solution 16.8g of 10 quality %, the temperature in reactor is maintained 80 DEG C and continue stirring 2 hours.Herein, after dropping into the ammonium persulfate aqueous solution 6.6g of 2 quality %, with within about 2 hours, dripping the mixed solution be made up of phenyltrimethoxysila,e 26.8g, tetraethoxysilane 28.6g, 3-methacryloxypropyl trimethoxy silane 1.1g simultaneously under the state that the temperature in reactor is kept 80 DEG C; And (ADEKA society manufactures, " AdekaReasoapSR-1025 " by vinylformic acid 0.9g, reactive emulsifier; Solid component content is the aqueous solution of 25 quality %) 2.3g, reactive emulsifier (first industrial pharmaceutical society manufacture, " AquaronKH-1025 "; Solid component content is the aqueous solution of 25 quality %) 2.3g, ammonium persulphate 2.0 quality % aqueous solution 30g, ion exchanged water 170.0g form mixed solution.Further the temperature in reactor is maintained 80 DEG C and continue stir abouts after 1 hour, be cooled to room temperature, being added in reaction solution by 25% ammonia soln and adjusting pH is after 8, filters with 100 object wire nettings.Carry out adjusting to make solid component content be 10.0 quality % with ion exchanged water, obtain the water dispersion (C ' D-15) of the polymkeric substance (C '-15) that number average bead diameter is 178nm as polymkeric substance.
Converting to the condenses that is hydrolyzed of the dimethoxymethylphenylsilane that uses during this water dispersion of synthesis, is 71.7 quality % in polymkeric substance (C '-15).
In addition, the condenses that is hydrolyzed of the methyltrimethoxy silane, phenyltrimethoxysila,e and the 3-methacryloxypropyl trimethoxy silane that use during this water dispersion of synthesis is converted, for 3.4 quality %, 15.6 quality % and 0.5 quality % in polymkeric substance (C '-15), add up to 19.5 quality %.
The one-tenth of each polymkeric substance is grouped into lists in table 1.
[table 1]
[Production Example 18]
There is the synthesis of the inorganic oxide (E-1) of photocatalytic activity
Silicon oxide modified rutile-type titanium dioxide
The pH of reaction solution is maintained while 5 ~ 9, add with TiO 2meter concentration be 200g/L titanium tetrachloride aqueous solution 700mL and with Na 2it is the aqueous sodium hydroxide solution of 100g/L that O counts concentration.Thereafter, the pH of adjustment reaction solution is after 7, filters, carries out cleaning until the specific conductivity of filtrate is 100 μ S/cm, obtain the titanium dioxide wet cake 1 that solid component content is 28.3 quality %.This titanium dioxide wet cake 1 comprises the particulate with rutile-type structure, and the number average bead diameter of its 1 particle is 8nm.
With pure water, obtained titanium dioxide wet cake 1 is diluted, prepare the slurry of 1 mol/L.Be fed in the flask of 3L by this slurry 1L, the nitric acid adding 1 equivalent further, to make the mol ratio of titanium dioxide/nitric acid for 1/1, is heated to the temperature of 95 DEG C, maintains 2 hours in this temperature, carry out sour heat treated.By the slurry cool to room temperature after sour heat treated, be 6.7 with 28% ammonia neutralization to pH, filter.Thereafter, carry out cleaning until the specific conductivity of filtrate is 100 μ S/cm, obtain the titanium dioxide wet cake 2 that solid component content is 25 quality %.
In the titanium dioxide wet cake 2 obtained, add the aqueous sodium hydroxide solution of 10% concentration, carry out slurrying again, thereafter, disperse 3 hours with Ultrasonic Cleaners, obtain the alkaline TiO 2 sol of pH10.5, solid component content 10 quality %.This alkaline TiO 2 sol 2L is put in the flask of 3L, is warming up to the temperature of 70 DEG C, adds with SiO 2meter concentration is the sodium silicate aqueous solution 69.4mL of 432g/L, is warming up to thereafter 90 DEG C and after maintaining 1 hour, the sulfuric acid adjustment pH adding 10% is 6, obtains utilizing the hydrous oxide of silicon to carry out surface-treated TiO 2 sol to the surface of titanium dioxide.
By the TiO 2 sol cool to room temperature obtained, add the pure water of 5.4L, use desalination and concentration device carry out the removing of impurity and concentrate, obtain the neutral rutile titanium dioxide colloidal sol of pH7.3, solid component content 29 quality %, specific conductivity 1.18mS/cm.This neutral rutile titanium dioxide colloidal sol is relative to TiO 2with SiO 2the hydrous oxide of the silicon of 15 quality % is contained for benchmark.The number average bead diameter of 1 particle of the titanium dioxide in this colloidal sol is 9nm.
[Production Example 19]
There is the synthesis of the inorganic oxide (E-2) of photocatalytic activity
Silicon oxide modifies anatase titanium dioxide
Heating hydrolysis is carried out to the titanium sulfate solution that titanium ore and sulfuric acid reaction obtain, the aggegation metatitanic acid of generation is made with TiO 2be scaled the water paste of 30 quality %.In this slurry, add ammoniacal liquor, being neutralized to pH is 7, removes sulfate ion thereafter, obtain dewatered cake by filtering, cleaning.Carrying out peptization process by adding nitric acid in obtained dewatered cake, obtaining the acidic titania colloidal sol of the pH1.5 be made up of the titanium dioxide fine particles with Detitanium-ore-type crystalline texture (number average bead diameter of 1 particle is 7nm).
The acidic titania colloidal sol pure water obtained is diluted, makes TiO 2converted score is after the TiO 2 sol 600mL of 200g/L, is warming up to 70 DEG C, by SiO 2converted score is that the sodium silicate aqueous solution 20.8mL of 432g/L and 20% sulfuric acid add simultaneously.Thereafter, slaking 30 minutes.Next, adding 10% aqueous sodium hydroxide solution adjustment pH is after 8, and adjusting pH with 2% aqueous sulfuric acid is 6, carries out filtering, cleaning, obtains wet cake.By after this wet cake again slurrying in pure water, carry out ultrasonic wave dispersion, obtain the stable anatase type TiO 2 sol of neutral region (solid component content 20 quality %, pH7.5).Wherein, aggegation silicon oxide is overlayed on the surface of titanium dioxide fine particles with the state of Porous, and its content is relative to TiO 2100 mass parts are with SiO 2be scaled 7 mass parts.
[embodiment 1]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-1) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-1); Solid component content 20 quality %) 60.0g, ethanol 50.0g and ion exchanged water 210.0g, and stir, thus obtain the aqueous coating agent composition (K-1) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-1) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-1) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-1) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-1), film and test board (L-1) and evaluation result are listed in table 2.
[embodiment 2]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-2) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-2), obtain the aqueous coating agent composition (K-2) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-2) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-2) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-2) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-2), film and test board (L-2) and evaluation result are listed in table 2.
[embodiment 3]
Water-dispersion colloided silica (D-2) (manufacture of Nissan Chemical Industries society, " SnowtexO " of mixing number average bead diameter 8nm in water dispersion (CD-2) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-2); Solid component content 30 quality %) 40.0g, ethanol 50.0g and ion exchanged water 230.0g, and stir, thus obtain the aqueous coating agent composition (K-3) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-3) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-3) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-3) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-3), film and test board (L-3) and evaluation result are listed in table 2.
[embodiment 4]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-3) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), obtain the aqueous coating agent composition (K-4) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-4) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-4) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-4) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-4), film and test board (L-4) and evaluation result are listed in table 2.
[embodiment 5]
The one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material Y being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-4) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-5) being formed with film on base material.The various physical property of test board (L-5) and evaluation result are listed in table 2.
[embodiment 6]
Water-dispersion colloided silica (D-3) (manufacture of Nissan Chemical Industries society, " SnowtexO-40 " of mixing number average bead diameter 25nm in water dispersion (CD-3) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 40 quality %) 30.0g, ethanol 50.0g and ion exchanged water 240.0g, and stir, thus obtain the aqueous coating agent composition (K-6) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-6) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-6) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-6) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-6), film and test board (L-6) and evaluation result are listed in table 2.
[embodiment 7]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-4) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-4), obtain the aqueous coating agent composition (K-7) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-7) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-7) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-7) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-7), film and test board (L-7) and evaluation result are listed in table 2.
[embodiment 8]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-5) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-5), obtain the aqueous coating agent composition (K-8) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-8) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-8) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-8) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-8), film and test board (L-8) and evaluation result are listed in table 2.
[embodiment 9]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-6) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-6), obtain the aqueous coating agent composition (K-9) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-9) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-9) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-9) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-9), film and test board (L-9) and evaluation result are listed in table 2.
[embodiment 10]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-7) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-7), obtain the aqueous coating agent composition (K-10) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-10) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-10) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-10) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-10), film and test board (L-10) and evaluation result are listed in table 2.
[embodiment 11]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-8) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-8), obtain the aqueous coating agent composition (K-11) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-11) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-11) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-11) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-11), film and test board (L-11) and evaluation result are listed in table 2.
[embodiment 12]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-9) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-9), obtain the aqueous coating agent composition (K-12) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-12) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-12) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-12) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-12), film and test board (L-12) and evaluation result are listed in table 2.
[embodiment 13]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (CD-10) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C-10), obtain the aqueous coating agent composition (K-13) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-13) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-13) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-13) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-13), film and test board (L-13) and evaluation result are listed in table 2.
[embodiment 14]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-2) 240.0g (solid component content 10.0 quality %) of polymkeric substance (C-2); Solid component content 20 quality %) 30.0g, ethanol 50.0g and ion exchanged water 180.0g, and stir, thus obtain the aqueous coating agent composition (K-14) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-14) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-14) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-14) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-14), film and test board (L-14) and evaluation result are listed in table 3.
[embodiment 15]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 45.0g, ethanol 50.0g and ion exchanged water 195.0g, and stir, thus obtain the aqueous coating agent composition (K-15) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-15) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-15) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-15) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-15), film and test board (L-15) and evaluation result are listed in table 3.
[embodiment 16]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 37.5g, there is inorganic oxide (E-1) 5.2g (solid component content 29 quality %), the ethanol 50.0g and ion exchanged water 197.3g of photocatalytic activity, and stir, thus obtain the aqueous coating agent composition (K-16) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-16) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-16) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-16) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-16), film and test board (L-16) and evaluation result are listed in table 3.
[embodiment 17]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 30.0g, there is inorganic oxide (E-1) 10.3g (solid component content 29 quality %), the ethanol 50.0g and ion exchanged water 199.7g of photocatalytic activity, and stir, thus obtain the aqueous coating agent composition (K-17) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-17) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-17) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-17) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-17), film and test board (L-17) and evaluation result are listed in table 3.
[embodiment 18]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 22.5g, there is inorganic oxide (E-1) 15.5g (solid component content 29 quality %), the ethanol 50.0g and ion exchanged water 202.0g of photocatalytic activity, and stir, thus obtain the aqueous coating agent composition (K-18) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-18) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-18) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-18) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-18), film and test board (L-18) and evaluation result are listed in table 3.
[embodiment 19]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 37.5g, there is inorganic oxide (E-2) 7.5g (solid component content 20 quality %), the ethanol 50.0g and ion exchanged water 195.0g of photocatalytic activity, and stir, thus obtain the aqueous coating agent composition (K-19) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-19) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-19) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-19) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-19), film and test board (L-19) and evaluation result are listed in table 3.
[embodiment 20]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 30.0g, inorganic oxide (E-1) 10.3g (solid component content 29 quality %) with photocatalytic activity, fluorocarbon surfactant (F-1) (DIC society manufacture, " MEGAFACF-444 ") 0.2g, ethanol 50.0g and ion exchanged water 199.5g, and stir, thus obtain the aqueous coating agent composition (K-20) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-20) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-20) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-20) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-20), film and test board (L-20) and evaluation result are listed in table 3.
[embodiment 21]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3); Solid component content 20 quality %) 30.0g, inorganic oxide (E-1) 10.3g (solid component content 29 quality %) with photocatalytic activity, fluorocarbon surfactant (F-2) (AGCSEIMICHEMICAL society manufacture, " SurflonS-232 "; Solid component content 30 quality %) 0.7g, ethanol 50.0g and ion exchanged water 199.0g, and stir, thus obtain the aqueous coating agent composition (K-21) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-21) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-21) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-21) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-21), film and test board (L-21) and evaluation result are listed in table 3.
[embodiment 22]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 210.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 30.0g, there is inorganic oxide (E-1) 10.3g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 3.0g, ethanol 50.0g and ion exchanged water 196.5g, and stir, thus obtain the aqueous coating agent composition (K-22) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-22) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-22) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-22) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-22), film and test board (L-22) and evaluation result are listed in table 3.
[embodiment 23]
Do not use and utilize ion exchanged water to carry out adjusting making solid component content to be that (KishidaChemical manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 3.0g, and use and utilize ion exchanged water to carry out adjusting making solids component to be that (hodogaya chemical industry society manufactures for the fadedness pigment (G-2) of 1.0 quality %, " Xylene Red ") 3.0g, obtain the aqueous coating agent composition (K-23) of solid component content 6.0 quality % in addition similarly to Example 21.The viscosity of this aqueous coating agent composition (K-23) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-23) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-23) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-23), film and test board (L-23) and evaluation result are listed in table 3.
[embodiment 24]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 60.0g (solids component 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 7.5g, there is inorganic oxide (E-1) 5.2g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (Daicelfinechem society manufactures for the cellulose-based thickeners (H-1) of 1.0 quality %, " HECDaicelSP900 ") 40.0g, ethanol 50.0g and ion exchanged water 336.1g, and stir, thus obtain the aqueous coating agent composition (K-24) that solid component content is 1.9 quality %.The viscosity of this aqueous coating agent composition (K-24) is 15mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-24) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-24) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-24), film and test board (L-24) and evaluation result are listed in table 3.
[embodiment 25]
The one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material Y being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-24) to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-25) being formed with film on base material.The various physical property of test board (L-25) and evaluation result are listed in table 3.
[embodiment 26]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 60.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 7.5g, there is inorganic oxide (E-1) 5.2g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (Daicelfinechem society manufactures for the cellulose-based thickeners (H-1) of 1.0 quality %, " HECDaicelSP900 ") 80.0g, ethanol 50.0g and ion exchanged water 296.1g, and stir, thus obtain the aqueous coating agent composition (K-26) that solid component content is 2.0 quality %.The viscosity of this aqueous coating agent composition (K-26) is 28mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-26) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-26) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-26), film and test board (L-26) and evaluation result are listed in table 3.
[embodiment 27]
Do not use water dispersion (CD-3) 60.0g of polymkeric substance (C-3), and use water dispersion (CD-7) 60.0g (solid component content 10.0 quality %) of polymkeric substance (C-7), obtain the aqueous coating agent composition (K-27) of solid component content 2.0 quality % in addition similarly to Example 25.The viscosity of this aqueous coating agent composition (K-27) is 26mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-27) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-27) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-27), film and test board (L-27) and evaluation result are listed in table 4.
[embodiment 28]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 60.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 7.5g, there is inorganic oxide (E-1) 5.2g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (chemical industry society of SHIN-ETSU HANTOTAI manufactures for the cellulose-based thickeners (H-2) of 1.0 quality %, " METOLOSE90SH-30000 ") 80.0g, ethanol 50.0g and ion exchanged water 296.1g, and stir, thus obtain the aqueous coating agent composition (K-28) that solid component content is 2.0 quality %.The viscosity of this aqueous coating agent composition (K-28) is 25mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-28) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-28) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-28), film and test board (L-28) and evaluation result are listed in table 4.
[embodiment 29]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 205.8g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 29.4g, there is inorganic oxide (E-1) 10.1g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 3.0g, (DowChemical society manufactures anti-algae/mould inhibitor (J-1), " KLARIX4000 ", isothiazoline based compound, effective constituent 4 quality %) 15.0g, ethanol 50.0g and ion exchanged water 186.5g, and stir, thus obtain the aqueous coating agent composition (K-29) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-29) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-29) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-29) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-29), film and test board (L-29) and evaluation result are listed in table 4.
[embodiment 30]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 207.2g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 29.6g, there is inorganic oxide (E-1) 10.2g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 3.0g, (DowChemical society manufactures anti-algae/mould inhibitor (J-2), " ROCIMA345 ", the mixture of isothiazoline based compound and triazine based compound, effective constituent 12 quality %) 3.0g, ethanol 50.0g and ion exchanged water 196.8g, and stir, thus obtain the aqueous coating agent composition (K-30) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-30) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-30) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-30) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-30), film and test board (L-30) and evaluation result are listed in table 4.
[embodiment 31]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 197.4g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 28.2g, there is inorganic oxide (E-1) 9.7g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 3.0g, (Japanese Cao Da society manufactures anti-algae/mould inhibitor (J-3), " Biocut-N35 ", the mixture of imidazole compound and triazine based compound, effective constituent 35 quality %) 5.0g, ethanol 50.0g and ion exchanged water 206.5g, and stir, thus obtain the aqueous coating agent composition (K-31) that solid component content is 6.0 quality %.The viscosity of this aqueous coating agent composition (K-31) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-31) of application to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-31) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-31), film and test board (L-31) and evaluation result are listed in table 4.
[embodiment 32]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 58.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 7.3g, there is inorganic oxide (E-1) 5.0g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (Daicelfinechem society manufactures for the cellulose-based thickeners (H-1) of 1.0 quality %, " HECDaicelSP900 ") 80.0g, (DowChemical society manufactures anti-algae/mould inhibitor (J-1), " KLARIX4000 ", isothiazoline based compound, effective constituent 4 quality %) 10.0g, ethanol 50.0g and ion exchanged water 288.5g, and stir, thus obtain the aqueous coating agent composition (K-32) that solid component content is 2.0 quality %.The viscosity of this aqueous coating agent composition (K-32) is 28mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-32) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-32) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-32), film and test board (L-32) and evaluation result are listed in table 4.
[embodiment 33]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 60.0g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 7.5g, there is inorganic oxide (E-1) 5.2g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (Daicelfinechem society manufactures for the cellulose-based thickeners (H-1) of 1.0 quality %, " HECDaicelSP900 ") 80.0g, (DowChemical society manufactures anti-algae/mould inhibitor (J-2), " ROCIMA345 ", the mixture of isothiazoline based compound and triazine based compound, effective constituent 12 quality %) 1.3g, ethanol 50.0g and ion exchanged water 294.9g, and stir, thus obtain the aqueous coating agent composition (K-33) that solid component content is 2.0 quality %.The viscosity of this aqueous coating agent composition (K-33) is 27mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-33) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-33) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-33), film and test board (L-33) and evaluation result are listed in table 4.
[embodiment 34]
Water-dispersion colloided silica (D-1) (manufacture of Nissan Chemical Industries society, " SnowtexOS " of mixing number average bead diameter 8nm in water dispersion (CD-3) 54.4g (solid component content 10.0 quality %) of polymkeric substance (C-3), solid component content 20 quality %) 6.8g, there is inorganic oxide (E-1) 4.7g (solid component content 29 quality %) of photocatalytic activity, (DIC society manufactures fluorocarbon surfactant (F-1), " MEGAFACF-444 ") 0.2g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (KishidaChemical society manufactures for the fadedness pigment (G-1) of 1.0 quality %, " methylene blue ") 1.0g, ion exchanged water is utilized to carry out adjusting making solid component content to be that (Daicelfinechem society manufactures for the cellulose-based thickeners (H-1) of 1.0 quality %, " HECDaicelSP900 ") 80.0g, (Japanese Cao Da society manufactures anti-algae/mould inhibitor (J-3), " Biocut-N35 ", the mixture of imidazole compound and triazine based compound, effective constituent 35 quality %) 2.8g, ethanol 50.0g and ion exchanged water 300.2g, and stir, thus obtain the aqueous coating agent composition (K-34) that solid component content is 2.0 quality %.The viscosity of this aqueous coating agent composition (K-34) is 28mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of the 7cm × 15cm or 5cm × 5cm base material X that are coated with enamel-cover coating in advance utilize spraying carry out the above-mentioned aqueous coating agent composition (K-34) of application to make glue spread for 50g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-34) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-34), film and test board (L-34) and evaluation result are listed in table 4.
[comparative example 1]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (C ' D-11) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C '-11), obtain the aqueous coating agent composition (K-35) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-35) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-35) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-35) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-35), film and test board (L-35) and evaluation result are listed in table 4.
[comparative example 2]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (C ' D-12) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C '-12), obtain the aqueous coating agent composition (K-36) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-36) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-36) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-36) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-36), film and test board (L-36) and evaluation result are listed in table 4.
[comparative example 3]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (C ' D-13) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C '-13), obtain the aqueous coating agent composition (K-37) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-37) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-37) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-37) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-37), film and test board (L-37) and evaluation result are listed in table 4.
[comparative example 4]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (C ' D-14) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C '-14), obtain the aqueous coating agent composition (K-38) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-38) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-38) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-38) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-38), film and test board (L-38) and evaluation result are listed in table 4.
[comparative example 5]
Do not use water dispersion (CD-1) 180.0g of polymkeric substance (C-1), and use water dispersion (C ' D-15) 180.0g (solid component content 10.0 quality %) of polymkeric substance (C '-15), obtain the aqueous coating agent composition (K-39) that solid component content is 6.0 quality % in addition similarly to Example 1.The viscosity of this aqueous coating agent composition (K-39) is 2mPas.
Then, the one side (being coated with the face of enamel-cover coating in advance) of 7cm × 15cm base material X being coated with enamel-cover coating in advance utilize spraying to carry out application aqueous coating agent composition (K-39) to make glue spread for 17g/m 2.Base material through application is kept level, leaves standstill 48 hours 50% time in temperature 23 DEG C, relative humidity, obtain the test board (L-39) being formed with film on base material.The various physical property of this aqueous coating agent composition (K-39), film and test board (L-39) and evaluation result are listed in table 4.
Can be confirmed by above-mentioned, the aqueous coating agent composition of the present embodiment all can form the film that can maintain outward appearance and stain resistance with high level.
Industrial applicibility
Aqueous coating agent composition of the present invention, film and coated articles can be used as the various parts etc. such as optics such as construction exterior purposes, exterior display purposes, automotive part, display screen or lens and utilize.

Claims (12)

1. an aqueous coating agent composition, it contains:
The dispersion (CD) of multipolymer (C), this multipolymer (C) comprises structural unit (A) and structural unit (B), described structural unit (A) derives from by the silane (a) shown in following general formula (1), and described structural unit (B) derives from by the silane (b) shown in following general formula (2); With
Inorganic oxide (D);
The content of the described structural unit (A) in described multipolymer (C) is scaled 32 quality % ~ 70 quality % with hydrolytic condensate,
The content of the described structural unit (B) in described multipolymer (C) is scaled 23 quality % ~ 45 quality % with hydrolytic condensate,
(R 1) 2-Si-(R 2) 2···(1)
In formula (1), R 1represent independently of one another hydrogen atom, carbonatoms be 1 ~ 16 aliphatic alkyl, the carbonatoms aryl that is 6 ~ 10, the carbonatoms cycloalkyl that is 5 ~ 6, phenyl, carbonatoms be 1 ~ 10 acrylic acid alkyl ester group or carbonatoms be 1 ~ 10 alkyl methacrylate base, R 2represent that carbonatoms is alkoxyl group, acetoxyl group or the hydroxyl of 1 ~ 8 independently of one another,
R 3-Si-(R 4) 3···(2)
In formula (2), R 3represent hydrogen atom, carbonatoms be 1 ~ 16 aliphatic alkyl, carbonatoms be 6 ~ 10 aryl, carbonatoms be 5 ~ 6 cycloalkyl, phenyl, carbonatoms be 1 ~ 10 acrylic acid alkyl ester group or carbonatoms be 1 ~ 10 alkyl methacrylate base, R 4represent that carbonatoms is alkoxyl group, acetoxyl group or the hydroxyl of 1 ~ 8 independently of one another.
2. aqueous coating agent composition as claimed in claim 1, wherein, the dispersion (CD) of described multipolymer (C) is by least using described silane (a) with described silane (b) and carrying out letex polymerization and obtain.
3. aqueous coating agent composition as claimed in claim 1 or 2, wherein, described inorganic oxide (D) is silicon-dioxide.
4. the aqueous coating agent composition as described in any one of claims 1 to 3, wherein, described composition is further containing the inorganic oxide (E) with photocatalytic activity.
5. the aqueous coating agent composition as described in any one of Claims 1 to 4, wherein, described composition is further containing fluorocarbon surfactant (F).
6. the aqueous coating agent composition as described in any one of Claims 1 to 5, wherein, described composition is further containing fadedness pigment (G).
7. the aqueous coating agent composition as described in any one of claim 1 ~ 6, wherein, described composition is further containing cellulose-based thickeners (H).
8. the aqueous coating agent composition as described in any one of claim 1 ~ 7, wherein, described composition is further containing the material of more than a kind be selected from the group that is made up of algaecide and mould inhibitor (J).
9. an aqueous coating, it contains the aqueous coating agent composition described in any one of claim 1 ~ 8.
10. a film, it is obtained by aqueous coating according to claim 9.
11. 1 kinds of coated articles, it contains base material and film according to claim 10, and this film is formed at the surface of described base material at least partially.
12. coated articles as claimed in claim 11, wherein, described base material is organic substrate.
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