CN1717457A - Antifouling water-based coating composition - Google Patents

Antifouling water-based coating composition Download PDF

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CN1717457A
CN1717457A CN 03803289 CN03803289A CN1717457A CN 1717457 A CN1717457 A CN 1717457A CN 03803289 CN03803289 CN 03803289 CN 03803289 A CN03803289 A CN 03803289A CN 1717457 A CN1717457 A CN 1717457A
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parts
water
active agent
silane
emulsion
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CN100357367C (en
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上山靖之
山元淳一
佐佐木惠
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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Abstract

The invention provides an anti-fouling used water paint composite, which comprises (A) an aqueous dispersion, (B) colloid inorganic particles and (C) a surfactant of sulfonic succinic acid species.

Description

Antifouling water-based coating composition
Technical field
The present invention relates to the good water-based paint compositions of a kind of didirtresistance.Be particularly related to a kind of antifouling water-based coating composition of using as coating, building decoration coated material etc., and the coating that it is characterized in that containing this antifouling water-based coating composition, and the coating method that uses this antifouling water-based coating composition.The present invention also further relates to and contains the stain resistance mixture that uses the formed coating of this coating.
Background technology
In recent years, people recognize that the rain line of seeing or the pollution of raindrop occur in the place that rainwater flows down on the wall of buildings, have difference between the stain at the position of itself and the line that do not rain, and therefore diminish the attractive in appearance of buildings.Can prevent that generally this rain line from polluting by the hydrophilic method that improves film coated surface.For example proposed a kind ofly in solvent based coating, made organoalkoxysilane, As time goes on made the technology of film coated surface wetting abilityization by hydrolysis in the film coated surface coordination.The problem of this technology is that it has following shortcoming, according to about 1 month meteorological conditions difference after just formation is filmed, can influence the degree of hydrolysis, particularly continues the exsiccant condition and can postpone hydrolysis, thereby make the pollution of filming.
For aqueous coating, as the method that prevents that this rain line from polluting, in the Te Kaiping 9-52974 communique, proposed by specific solvent is added in the aqueous emulsion, can reduce this water contact angle of filming, to reduce the method for rain line, but its effect is insufficient, and its effect is difficult to continue the long time.
Open in the flat 10-46099 communique the spy, a kind of emulsion polymerization and coating of obtaining of the emulsion polymerization of polymerizability tensio-active agent by specific unsaturated monomer has been proposed, can reduce the method for rain line by this coating, but its effect is difficult to keep the long time.
Open in the flat 10-298489 communique the spy, crosslinked the filming that has proposed a kind of linking agent that is used in combination specific segmented copolymer and dihydrazide compound linking agent, formed by itself and poly-carbonyl compound can be reduced the method for rain line, but its water tolerance is insufficient, its persistence is also relatively poor.
Open in the flat 11-217480 communique the spy, disclose a kind of method of in polymeric emulsifiers, using oxyalkylene group, but its prevent aspect the pollution insufficient.
Open in the clear 54-139938 communique the spy, the outer coating paint that has proposed a kind of mixture with acrylic resin and silica gel is coated in the method on the filming of the silica gel water dispersion inorganic paint that contains inorganic filler, borrows above-mentioned outer coating paint can not obtain sufficient surface hardness and didirtresistance but only rely on.
Open in the flat 7-26165 communique the spy, having proposed a kind of is purpose to improve heat-resisting anti-caking with the storage stability that applies liquid, the method of in the emulsion that uses the reactive surfactant emulsion polymerization to obtain, mixing silica gel, but the addition of its silica gel is more, and the water tolerance of the coating that obtains is also relatively poor.
Open in the clear 56-57860 communique the spy, with the adaptation of improving the undercoat that inorganic building material uses is purpose, in addition, open in the flat 11-116885 communique the spy, to have stain resistance be purpose so that coating is filmed, the two all proposed a kind of will be by the organoalkoxysilane with vinyl group copolymerization generates when the emulsion polymerization emulsion and silica gel blended method, but storage stability for coating liquid, mix coating liquid and when preserving, can cause cohesion and make coating become and to carry out, then can make the water tolerance of filming become very poor if add a large amount of emulsifying agents in order to make its stabilization.
Open in the flat 3-47669 communique the spy, more with respect to the addition of the silica gel of emulsion, the water tolerance of filming that obtains is relatively poor, in addition as the storage stability of coating liquid, mixes coating liquid and can cause cohesion and make coating become and can not carry out when preserving.
Opening in the flat 7-118573 communique the spy, is purpose with the anti-skid, has proposed a kind of method that applies the mixing prod of siliceous latex agent and silica gel, and it can not obtain sufficient gloss when being used for coating.
Open in the clear 59-217702 communique the spy, proposed a kind of silica gel and have emulsifying capacity polymerizable monomer in the presence of, the water dispersion resin combination that obtains by emulsion polymerization, but its polymerization stability and water tolerance are relatively poor, silica gel content is less in addition, can not bring into play low contaminative.
Open in the flat 11-1893 communique the spy, proposed a kind of in the presence of silica gel, activator and water, by vinyl unsaturated compound emulsion polymerization obtain water-based paint compositions, the content of its silica gel is more, polymerization stability and water tolerance are all relatively poor.
Open in the flat 9-165554 communique the spy, a kind of composition that is formed by the latex that contains a large amount of dimethyl siloxane units and ketone group, hydrazide compound and silica gel is disclosed, must be increased in the silica gel that applies in the liquid in order to make it show stain resistance, the storage stability that therefore applies liquid is insufficient.
Open in the flat 10-168393 communique the spy, disclose a kind of emulsion, hydrazide compound and water-disintegrable silane and carried out the composition that surface-treated silica gel forms with ketone group containing and silanol group, but must be increased in the surface treatment silica gel that applies in the liquid in order to make it show stain resistance, the storage stability that therefore applies liquid is insufficient.
Open in the 2001-335721 communique the spy, disclose a kind of silica gel that has coated nonionic surface active agent and vinyl polymer by the surface and mixed the composition that forms with emulsion, but in order to keep stability that more tensio-active agent must be arranged, its water tolerance variation as a result.And stability is also insufficient.
Open in the clear 55-40717 communique the spy, proposed the mixture that a kind of silica gel, specific tensio-active agent and emulsion are formed, its addition with respect to the silica gel of emulsifying agent is more, and the water tolerance of filming, the weathering resistance that obtain are relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of for filming that aqueous coating forms, it exposes to the open air when outdoor to compare with existing product and can reduce that rain line shape pollutes or the pollution of raindrop, particularly can prevent the pollution after just formation is filmed, prevent that rain line shape from polluting or the persistence of the effect of the pollution of raindrop is outstanding, and the good antifouling water-based coating composition of storage stability of coating liquid.
Inventors of the present invention have carried out positive research in order to solve the above problems, found that, for filming of forming by the composition that contains aqueous dispersion, colloidal inorganic particle and specific tensio-active agent, make its to the contact angle of water below 75 °, present and to make the rain line of the filming unconspicuous effect that becomes, finished the present invention thus.
That is to say that the 1st aspect of the present invention is about a kind of containing (A) aqueous dispersion, (B) colloidal inorganic particle and (C) antifouling water-based coating composition of sulfosuccinic acids tensio-active agent.
The 2nd aspect of the present invention is the water-based paint compositions about above-mentioned the 1st aspect, and it further comprises the tensio-active agent that (D) contains oxyalkylene group.
The 3rd aspect of the present invention is the water-based paint compositions about the above-mentioned the 1st or the 2nd aspect record, wherein (A) aqueous dispersion be a kind of (C) sulfosuccinic acids tensio-active agent and/or (D) contain oxyalkylene group tensio-active agent in the presence of, the acrylic acid or the like emulsion that obtains by emulsion polymerization.
The 4th aspect of the present invention is that the water contact angle of filming after its film forming is below 75 ° about the water-based paint compositions of each record in the above-mentioned the 1st～3.
The 5th aspect of the present invention is the water-based paint compositions about each record in the above-mentioned the 2nd～4, wherein with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (B) amount of colloidal inorganic particle is 0.1～95 weight part, (C) amount of sulfosuccinic acids tensio-active agent is 0.1～20 weight part, and the amount that (D) contains the tensio-active agent of oxyalkylene group is 0.1～5 weight part.
The 6th aspect of the present invention is that wherein (A) aqueous dispersion is polysiloxane-modified acrylic acid or the like emulsion about the water-based paint compositions of each record in the above-mentioned the 1st～5.
The 7th aspect of the present invention is that wherein (A) aqueous dispersion is the acrylic acid or the like emulsion that is formed by (E) vinyl unsaturated monomer emulsion polymerization in the presence of (F) water-disintegrable silane about the water-based paint compositions of each record in the above-mentioned the 1st～6.
The 8th aspect of the present invention is the water-based paint compositions about above-mentioned the 7th aspect, and wherein (F) water-disintegrable silane comprises the following general formula (a) of stating
(R 1) n-Si-(R 2) 4-n (a)
(n is 0～3 integer in the formula, R 1Be that to be selected from hydrogen atom, carbonatoms be that 1～16 aliphatic alkyl, carbonatoms are that 5～10 aryl, carbonatoms are that 5～6 cycloalkyl, vinyl, carbonatoms are that 1～10 acrylic acid alkyl and carbonatoms are 1～10 methacrylic dialkylaminobenzoic acid; N R 1Can be the same or different; R 2Be selected from carbonatoms and be 1～8 alkoxyl group, acetoxyl group or hydroxyl; 4-n R 2Can be the same or different.) shown in silane.
The 9th aspect of the present invention is the water-based paint compositions about the record of the above-mentioned the 7th or the 8th aspect, at least a in the silane (II) when wherein (F) water-disintegrable silane comprises silane (I) when being selected from n=0 in the aforementioned formula (a) and n=1 with 100/1～1/100 mol ratio and, silane (IV), the cyclic silane the when silane when being selected from n=2 (III), n=3 and have at least a in the chain siloxanes of hydrolization group.
The 10th aspect of the present invention is that wherein (B) colloidal inorganic particle comprises the colloidal inorganic particle that is coated by organic polymer about the water-based paint compositions of each record in the above-mentioned the 1st～9.
The 11st aspect of the present invention is that wherein (B) colloidal inorganic particle is a silica gel about the water-based paint compositions of each record in the above-mentioned the 1st～10.
The 12nd aspect of the present invention is the water-based paint compositions about each record in the above-mentioned the 1st～11, and wherein (C) sulfosuccinic acids tensio-active agent is not for containing the sulfosuccinic acids tensio-active agent of free-radical polymerised pair of key.
The 13rd aspect of the present invention is the water-based paint compositions about each record in the above-mentioned the 1st～12, wherein (D) to contain the tensio-active agent of oxyalkylene group be the tensio-active agent with the free-radical polymerised pair of key that contains oxyalkylene group.
The 14th aspect of the present invention is the water-based paint compositions about each record in the above-mentioned the 1st～13, wherein (A) aqueous dispersion is the acrylic acid or the like emulsion that is formed by (E) vinyl unsaturated monomer emulsion polymerization, and wherein (E) vinyl unsaturated monomer contains above (methyl) acrylate that contains cycloalkyl of 5 weight %.
The 15th aspect of the present invention is the water-based paint compositions about each record in the above-mentioned the 1st～14, it is characterized in that using it for the purposes of coating.
The 16th aspect of the present invention is about containing the coating of the water-based paint compositions of record in the above-mentioned the 15th.
The 17th aspect of the present invention is about using the coated article of the applying coating in the above-mentioned the 16th.
The 18th aspect of the present invention is about using the outer wall materials of the applying coating in the above-mentioned the 16th.
The 19th aspect of the present invention is about using the buildings of the applying coating in the above-mentioned the 16th.
The 20th aspect of the present invention is the stain resistance mixture about the coating that contains the coating formation of using in the above-mentioned the 16th.
The 21st aspect of the present invention is about it is characterized in that using the coating method of the coating in the above-mentioned the 16th.
Description of drawings
Fig. 1 puts the synoptic diagram of the shape of plate for used outdoor dew in embodiment and the comparative example.
Embodiment
Below, the present invention is described in detail.
Preparation method about (A) water dispersion has no particular limits in the present invention.What can enumerate for example is, the method that makes by emulsion polymerization will obtain the method that polymer dispersed makes in the water by solution polymerization, and polymkeric substance mechanically is distributed in the water and the method that makes etc.Angle from the simplicity of the stability of water dispersion, manufacturing process preferably makes by emulsion polymerization.
(A) water dispersion in the present invention can be enumerated polyurethanes emulsion, fluorine class emulsion, acrylic acid or the like emulsion etc., and the price of polyurethanes emulsion is higher, owing to have caoutchouc elasticity if Individual existence can make environmental degradation.In addition, the price of fluorine class emulsion is higher, because it is relatively poor aspect screening characteristics, contaminative again, the therefore preferred acrylic acid or the like emulsion that uses more preferably uses with the polysiloxane-modified acrylic acid or the like emulsion that forms of weathering resistance more outstanding (SA).
In the present invention, acrylic acid or the like emulsion is meant the emulsion of the polymkeric substance of the paradigmatic structure that contains acrylate or methacrylic ester.
As (E) vinyl unsaturated monomer used when making this acrylic acid or the like emulsion, what at first can enumerate is acrylate, methacrylic ester, (in this application acrylate or methacrylic ester being expressed as in the lump (methyl) acrylate).Can and the monomer of this (methyl) acrylic ester copolymer have no particular limits, as its concrete example, what can enumerate is the rare amides monomer of monomer, methyl-prop with carboxylic acid group, vinyl cyanide base class etc.
As the monomer with carboxylic acid group, what can enumerate is methylene-succinic acid, fumaric acid, toxilic acid, maleic anhydride, toxilic acid and monoesters thereof, vinylformic acid, methacrylic acid, butenoic acid etc.
As the example of (methyl) acrylate, what can enumerate is that the carbonatoms of moieties is that (methyl) alkyl acrylate of 1～18, the carbonatoms of moieties are that (methyl) acrylic acid hydroxy alkyl ester of 1～18, the number of oxyethylene group are that (gathering) ethylene oxide (methyl) acrylate of 1～100, the number of propylene oxide base are that (gathering) propylene oxide (methyl) acrylate of 1～100, the number of oxyethylene group are (gathering) ethylene oxide two (methyl) acrylate of 1～100 etc.
As the concrete example of (methyl) alkyl acrylate, what can enumerate is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid methyl cyclohexane ester, (methyl) dodecylacrylate etc.
As the concrete example of (methyl) acrylic acid hydroxy alkyl ester, what can enumerate is (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl cyclohexyl, (methyl) dodecylacrylate etc.
As the concrete example of (gathering) ethylene oxide (methyl) acrylate, what can enumerate is (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.
As the concrete example of (gathering) propylene oxide (methyl) acrylate, what can enumerate is (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 three four propylene glycol esters, methoxyl group (methyl) vinylformic acid three four propylene glycol esters etc. that contract that contract.
As the concrete example of (gathering) ethylene oxide two (methyl) acrylate, what can enumerate is 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.
With respect to the gross weight of (E) vinyl unsaturated monomer, (methyl) acrylate preferably uses its 80 weight %～100 weight %, more preferably uses its 90 weight %～100 weight %.
In the present invention, as (E) vinyl unsaturated monomer, particularly from helping the weather resistance angle, preferably contain having (methyl) acrylate of cycloalkyl.(methyl) acrylate or its mixture with cycloalkyl are preferably more than the 5 weight % of (E) vinyl unsaturated monomer, more preferably below the above 99 weight % of 5 weight %, more preferably below the above 80 weight % of 5 weight %.(methyl) acrylate with cycloalkyl is in that then weather resistance is good more than 5%, and is good with next film-forming properties 80%.
As (methyl) third rare amides monomer class, what can enumerate is for example (methyl) third rare acid amides, N-methylol (methyl) third rare acid amides, N-hydroxyl butyl (methyl) third rare acid amides etc., and as the vinyl cyanide base class, what can enumerate is (methyl) vinyl cyanide etc.
As the vinyl unsaturated monomer that contains aldehyde radical or ketone group; what can enumerate is propenal, diacetone third rare acid amides, the rare acid amides of diacetone methyl-prop, ethenyl methyl ketone, vinyl ethyl ketone, methacrylic acid acetoacetoxy ethyl ester, vinylformic acid acetoacetoxy ethyl ester, formyl radical vinylbenzene etc., or its combination.
In addition, concrete example as (E) vinyl unsaturated monomer beyond above-mentioned, what can enumerate for example is, ethene, third is rare, olefines such as iso-butylene, the alkadiene of divinyl etc., vinylchlorid, haloalkene hydro carbons such as Ethylene Dichloride, vinyl acetate, propionate, vinyl propionate, the M-nitro benzoic acid vinyl acetate, right-tertiary butyl M-nitro benzoic acid vinyl acetate, the trimethylacetic acid vinyl acetate, the 2 ethyl hexanoic acid vinyl acetate, the tertiary monocarboxylic acid vinyl acetate, vinyl carboxylates classes such as vinyl laurate, isopropenyl acetate, the different propylene ester of the carboxylic acid class of the different propylene ester of propionic acid etc., ethyl vinyl ether, IVE, vinyl ethers such as cyclohexyl vinyl ether, vinylbenzene, aromatic ethenyl compounds such as Vinyl toluene, allyl acetate, allyl ester classes such as M-nitro benzoic acid allyl ester, allyl ethyl ether, allyl glycidyl ether, allyl ether series such as allyl phenyl ether, and then, 4-(methyl) third rare acyloxy-2,2,6, the 6-tetramethyl piperidine, 4-(methyl) third rare acyloxy-1,2,2,6,6-pentamethyl-piperidines, (methyl) vinylformic acid perfluor methyl esters, (methyl) vinylformic acid perfluor propyl ester, (methyl) vinylformic acid perfluoro-methyl propyl ester, vinyl pyrrolidone, trimethylolpropane tris (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2, the 3-cyclohexane oxide, (methyl) allyl acrylate etc., or its combination.
As of the present invention by (SA) the polysiloxane-modified acrylic acid or the like emulsion that forms, so long as in emulsion grain, get final product with the emulsion of the compound coexistence that contains at least a group in siloxanes, polysiloxane, silanol groups or the alkoxysilane group.
For example,
Disclosed in the public clear 51-25369 communique of spy, in the siloxanes emulsion that the dehydrating condensation emulsion polymerization by organoalkoxysilane obtains, add polymerizing catalyst and acrylate monomer, make siloxanes and the acrylate water-based emulsion that copolymerization obtains under acidic conditions;
Open in the flat 3-45628 communique the spy disclosed, make organoalkoxysilane be absorbed in the organic polymer particle after, make it that condensation reaction take place, make the polysiloxane composite polymer particle of compoundization of polysiloxane thus;
Open in the flat 3-227312 communique disclosed the spy, use redox catalyst in the temperature below 60 ℃, under the condition of pH5～8, by (methyl) alkyl acrylate with have the cold cross-linking type emulsion that the polymerizable monomer emulsion polymerization of alkoxysilane group forms;
Open in the flat 4-202515 communique the spy disclosed, but the emulsified copolymer that obtains by the emulsification copolymerization by other vinyl monomer of specific organo-siloxane and copolymerization;
Open in the flat 5-194911 communique disclosed the spy, monomer composition with polysiloxane-based macromonomer, (methyl) acrylate and co-polymerized monomer form mixes the aqueous surface Liniment that obtains with acrylate copolymer emulsion that contains polysiloxane that obtains by emulsion polymerization and vinylformic acid emulsion.
Open in the flat 6-122734 communique disclosed the spy, use redox catalyst in the temperature below 60 ℃, under the condition of pH5～8, will contain polymerizable monomer, (methyl) alkyl acrylate of cycloalkyl and have the durable coating synthetic resins aqueous emulsion that the polymerizable monomer emulsion polymerization of alkoxysilane group forms;
Open in the flat 6-157758 communique disclosed the spy, by organoalkoxysilane, annular siloxane and have poly organic silicon alkanes polymkeric substance emulsion that the polymerizable monomer copolymerization of alkoxysilane group obtains in the presence of, with alkyl (methyl) acrylate and vinyl polymerization of unsaturated monomers, and then in the presence of the poly organic silicon alkanes polymkeric substance emulsion that obtains by this polyreaction, make organoalkoxysilane and annular siloxane carry out the polysilane composition polymer emulsion that condensation reaction obtains;
Open in the flat 6-306123 communique disclosed the spy, the monomer component of the core of emulsion grain is to be formed by the vinyl monomer with silyl, cycloalkyl acrylate and non-hydrophilic other vinyl monomer, the monomer component of the outermost layer of emulsion part is to be formed by the vinyl monomer with silyl, cycloalkyl acrylate and non-hydrophilic other vinyl monomer and hydrophilic ethylene class monomer, the emulsion that these monomer components are obtained by multistage emulsion polymerization;
As of the present invention by (SA) the polysiloxane-modified acrylic acid or the like emulsion that forms, preferably in the presence of (A) aqueous dispersion, (F) water-disintegrable silane, the acrylic acid or the like emulsion that obtains by (E) vinyl unsaturated monomer emulsion polymerization.By carry out emulsion polymerization in the presence of (F) water-disintegrable silane, can make films has higher weather resistance.
As (F) the water-disintegrable silane that uses by (SA) polysiloxane-modified acrylic acid or the like emulsion that forms that is used for the present application, preferably contain and be selected from least a in the silane shown in following general formula (a), that have siloxane structure.
(R 1) n-Si-(R 2) 4-n (a)
(n is 0～3 integer in the formula, R 1Be that to be selected from hydrogen atom, carbonatoms be that 1～16 aliphatic alkyl, carbonatoms are that 5～10 aryl, carbonatoms are that 5～6 cycloalkyl, vinyl, carbonatoms are that 1～10 acrylic acid alkyl and carbonatoms are 1～10 methacrylic dialkylaminobenzoic acid; N R 1Can be the same or different; R 2Be selected from carbonatoms and be 1～8 alkoxyl group, acetoxyl group or hydroxyl; 4-n R 2Can be the same or different.)
Especially, at least a in the silane (II) when (F) water-disintegrable silane preferably contains silane (I) when being selected from formula (a) n=0 and/or n=1, for polymerization stability and the anti-fouling effect that obtains good water dispersion, be more preferably the silane (II) when n=1.
The R of silane (I) 2Be preferably methoxyl group, oxyethyl group, propoxy-, butoxy, methoxy ethoxy, hydroxyl independently of one another.As the preferred concrete example of silane (I), can be tetramethoxy-silicane, tetraethoxysilane etc.
The R of silane (II) 1Be preferably methyl, phenyl, vinyl, γ-(methyl) third rare acyloxy propyl group independently of one another, R 2Be preferably methoxyl group, oxyethyl group, propoxy-, butoxy, methoxy ethoxy, hydroxyl independently of one another.As the preferred concrete example of silane (II), can be methyltrimethoxy silane, phenyltrimethoxysila,e, sec.-propyl Trimethoxy silane etc.As the water-disintegrable silane with free-radical polymerised pair of key of silane (II), can be the rare acyloxy propyl trimethoxy silicane of vinyl Ethoxysilane, γ-third, the rare acyloxy propyl-triethoxysilicane of γ-third, the rare acyloxy propyl trimethoxy silicane of γ-methyl-prop, the rare acyloxy propyl-triethoxysilicane of γ-methyl-prop etc. in addition.These can contain individually, perhaps contain two or morely, preferably the water-disintegrable silane that has the water-disintegrable silane of free-radical polymerised pair of key and do not contain free-radical polymerised pair of key can be used in combination.
In addition, have at needs under the situation of flexibility, (F) water-disintegrable silane preferably uses at least a in the silane (III) that is selected from cyclic silane and obtains when n=2.To be selected from least a and silane (II) in cyclic silane and the silane (III) when using simultaneously, (F) cross-linking density of the polysiloxane polymer of water-disintegrable silane formation reduces, the structure that can prevent polymkeric substance becomes complicated, can make thus from filming of obtaining of aqueous emulsion or acrylic acid or the like emulsion to have flexibility, therefore more preferably.Special preferably combination is used silane (II) and silane (III).
As the concrete example of cyclic silane, what can enumerate is octamethylcyclotetrasiloxane, octaphenyl cyclosiloxane, hexamethyl cyclotrisiloxane, decamethylcyclopentaandoxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane etc.
As the concrete example of silane (III), what can enumerate is dimethyldimethoxysil,ne, dimethoxydiphenylsilane, dimethyldiethoxysilane, phenylbenzene diethoxy silane, aminomethyl phenyl silane, the rare acyloxy propyl group of γ-third methyl methoxy base silane.In order to realize making water contact angle below 60 °, preferred especially dimethoxydiphenylsilane, phenylbenzene diethoxy silane.
When in (F) water-disintegrable silane, contain silane (I) and/or silane (II) and be selected from cyclic silane and silane (III) at least a the time, containing under the two the situation, from obtaining the angle of good anti-fouling effect, silane (I) and/or silane (II) are preferably more than 10/100 with respect to the above-mentioned at least a mol ratio that is selected from cyclic silane and the silane (III), more preferably more than 35/100, more preferably more than 100/100.In addition, when the needs flexibility, can use with the ratio below 100/1.
And then, in (F) water-disintegrable silane, can also contain: the silane (IV) that has the chain polysiloxane, alkoxysilane oligomer of hydrolysising group and in formula (a), obtain during as n=3.
As the concrete example of silane (IV), what can enumerate is triphenyl Ethoxysilane, trimethylammonium methoxy silane etc.
As the example of the chain polysiloxane with hydrolysising group, what can enumerate is by the compound shown in following general formula (15), (16) and (17).
Figure A0380328900181
Figure A0380328900182
Figure A0380328900183
In the formula, R 1Be that to be selected from hydrogen atom, carbonatoms be that 1～16 aliphatic alkyl, carbonatoms are that 5～10 aryl, carbonatoms are that 5～6 cycloalkyl, vinyl, carbonatoms are that 1～10 acrylic acid alkyl and carbonatoms are the group of 1～10 methacrylic dialkylaminobenzoic acid.Each R 2Be selected from carbonatoms independently of one another and be 1～8 alkoxyl group, acetoxyl group, hydroxyl, epoxy group(ing), oxyalkylene group or polyoxyalkylenes; M represents 1～999 positive integer.
As above-mentioned (15), (16) and the chain polysiloxane shown in (17) and the compound of alkoxysilane oligomer, what can enumerate is, the KC-89S that makes of SHIN-ETSU HANTOTAI's chemical industry (strain) for example, KR-500, X-40-9225, KR-217, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-41-1805, X-41-1810, X-40-2308, X-22-164A, X-22-164B, X-22-164C, X-22-174DX, X-24-8201, X-22-2426, サ イ ラ プ レ-Application FM-2231 that intelligence rope (チ Star ソ) (strain) is made, FM-4411, FM-4421, FM-4425, FM-5511, FM-5521, FM-5525, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-0511, FM-0521, FM-0525, FM-0711, FM-0721, FM-0725, the MAC-2101 that Japan's ユ ニ カ-(strain) made, MAC-2301, FZ-3704, AZ-6200, the SF8427 that the beautiful DOW CORNING silicone resin in east (strain) is made, SF8428, the SILRES MSE100 that the triumphant silicone resin of Asahi Chemical Industry's prestige (strain) is made etc.
When in (F) water-disintegrable silane, contain silane (I) and/or silane (II) and be selected from chain polysiloxane with hydrolysising group and silane (IV) at least a kind above-mentioned the two the time, from obtaining the angle of good anti-fouling effect, silane (I) and/or silane (II) are preferably 10/100 or more with respect to being selected from chain polysiloxane with hydrolysising group and a kind mol ratio in the silane (IV) at least, more preferably more than 35/100, more preferably more than 100/100.In addition, when the needs flexibility, can use with the ratio below 100/1.
For silane (III) or silane (IV), as R 1Be preferably methyl, phenyl especially, as R 2Be preferably methoxyl group, oxyethyl group, propoxy-, butoxy, methoxy ethoxy, hydroxyl especially.
(F) water-disintegrable silane is selected from a kind of in silane (II), cyclic silane, silane (III), chain polysiloxane, alkoxysilane oligomer and the silane (IV) except containing, can also contain chlorosilane, for example methyl chlorosilane, dimethyl dichlorosilane (DMCS), dimethyldichlorosilane(DMCS), trimethylchlorosilane, phenyl-trichloro-silicane, diphenyl chlorosilane, vinyl chlorosilane, γ-(methyl) third rare acyloxy propyltrichlorosilan, γ-(methyl) third rare acyloxy propyl group dichlorosilane.
Can pass through 29SiNMR ( 29The Si nuclear magnetic resonance spectrum) or 1HNMR (proton NMR spectrum) predicts the existence of above-mentioned silane condensation thing.For example pass through 29The chemical shift of SiNMR-40～-condenses of silane (II) can be assert in the peak that the 80PPM place shows.In addition.By 29The chemical shift of SiNMR-16～-condenses of silane (IV) or cyclic silane can be assert in the peak that the 26PPM place shows.
With respect to the gross weight of (E) unsaturated monomer, (F) the water-disintegrable silane among the present invention can use with the amount of its 0.01 weight %～300 weight %.
From easy acquisition, cheap angle, as the silica gel preferably of (B) colloidal inorganic particle among the present invention.Can use silica gel by sol-gel method preparation, also can be with commercially available product.By sol-gel method preparation silica gel the time, can be with reference to WernerStober et al; J.Colloid and Interface Sci., 26,62-69 (1968), RickeyD.Badley et al; Lang muir 6,792-801 (1990), look material Xie Hui Chi, 61[9] 488-493 (1998) etc.Silica gel be a kind of be the dispersion of silica in water or water-soluble solvent of elementary cell with silicon-dioxide, the preferred 5～120nm of its median size, more preferably 10～80nm.It is if particle diameter then applies the storage stability of liquid more than 5nm better, if better with next resistance to water-whitening at 120nm.The silica gel of the particle diameter of above-mentioned scope can be any in acid, the alkalescence under the state of aqueous liquid dispersion, can select aptly according to the stabilized zone of blended (A) aqueous dispersion.As being the acidic silica gel of dispersion medium with water, can use ス ノ-テ Star Network ス (trade mark)-O, ス ノ-テ Star Network ス-OL, ア デ ラ イ ト (trade mark) AT-20Q that rising sun electrochemical industry (strain) is made, (trade mark) 20H12, the Network レ ボ ゾ-Le 30CAL25 etc. that Clariant Japan (strain) makes that for example produce chemical industry (strain) daily and make as commercially available product.
Silica gel as alkalescence, what can enumerate is to pass through alkalimetal ion, ammonium ion, the interpolation of amine and the silica of stabilization, what can enumerate is, for example produce ス ノ-テ Star Network ス-20 that chemical industry (strain) is made daily, ス ノ-テ Star Network ス-30, ス ノ-テ Star Network ス-C, ス ノ-テ Star Network ス-C30, ス ノ-テ Star Network ス-CM40, ス ノ-テ Star Network ス-N, ス ノ-テ Star Network ス-N30, ス ノ-テ Star Network ス-K, ス ノ-テ Star Network ス-XL, ス ノ-テ Star Network ス-YL, ス ノ-テ Star Network ス-ZL, ス ノ-テ Star Network ス-PS-M, ス ノ-テ Star Network ス-PS-L etc., the ア デ ラ イ ト AT-20 that rising sun electrochemical industry (strain) is made, ア デ ラ イ ト AT-30, ア デ ラ イ ト AT-20N, ア デ ラ イ ト AT-30N, ア デ ラ イ ト AT-20A, ア デ ラ イ ト AT-30A, ア デ ラ イ ト AT-40, ア デ ラ イ ト AT-50 etc., Network レ ボ ゾ-Le 30R9 that Clariant Japan (strain) makes, Network レ ボ ゾ-Le 30R50, Network レ ボ ゾ-Le 50R50 etc., Le De Star Network ス (trade mark) HS-40 that E.I.Du Pont Company makes, Le De Star Network ス HS-30, Le De Star Network ス LS, Le De Star Network ス SM-30 etc.
In addition, as being the silica gel of dispersion medium with the water-soluble solvent, what can enumerate is for example to produce MA-ST-M (particle diameter is the methyl alcohol decentralized of 20～25nm), IPA-ST (particle diameter is the Virahol decentralized of 10～15nm), EG-ST (particle diameter is the ethylene glycol decentralized of 10～15nm), EG-ST-ZL (particle diameter is the ethylene glycol decentralized of 70～100nm), NPC-ST (particle diameter is the glycol monomethyl propyl ether decentralized of 10～15nm) etc. that chemical industry (strain) is made daily.
In addition, can be with one or more silica gel combination, can also contain aluminum oxide as minor constituent, sodium aluminate etc.In addition, can also contain mineral alkali (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor etc.) or organic bases (tetramethyl-ammonium etc.) in the silica gel as stablizer.
In addition, as (B) colloidal inorganic particle, can also use the mineral compound that silica colloid particle in addition can be provided, as the concrete example of this compound, that can enumerate is TiO 2, TiO 3, SrTiO 3, FeTiO 3, WO 3, SnO 2, Bi 2O 3, In 2O 3, ZnO, Fe 2O 3, RuO 2, CdO, CdS, CdSe, GaP, GaAs, CdFeO 3, MoS 2, LaRhO 3, GaN, CdP, ZnS, ZnSe, ZnTe, Nb 2O 5, ZrO 2, InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb etc. have the semi-conductor of photocatalysis performance, in addition, also have Al 2O 3, AlGa, As, Al (OH) 3, Sb 2O 5, Si 3N 4, Sn-In 2O 3, Sb-In 2O 3, MgF, CeF 3, CeO 2, 3Al 2O 32SiO 2, BeO, SiC, AlN, Fe, Co, Co-FeOx, CrO 2, Fe 4N, BaTiO 3, BaO-Al 2O 3-SiO 2, barium iron ore, SmCO 5, YCO 5, CeCO 5PrCO 5, Sm 2CO 17, Nd 2Fe 14B, Al 4O 3, α-Si, SiN 4, CoO, Sb-SnO 2, Sb 2O 5, MnO 2, MnB, Co 3O 4, Co 3B, LiTaO 3, MgO, MgAl 2O 4, BeAl 2O 4, ZrSiO 4, ZnSb, PbTe, GeSi, FeSi 2, CrSi 2, CoSi 2, MnSi 1.73, Mg 2Si, β-B, BaC, BP, BaC, BP, TiB 2, ZrB 2, HfB 2, Ru 2Si 3, TiO 2(rutile-type), TiO 3, PbTiO 3, Al 2TiO 5, Zn 2SiO 4, Zr 2SiO 4, 2MgO 2-Al 2O 2-5SiO 2, Nb 2O 5, Li 2O-Al 2O 3-4SiO 2, Mg iron ore, Ni iron ore, Ni-Zn iron ore, Li iron ore, Sr iron ore etc.These colloidal inorganic particles may be used singly or as a mixture of two or more.
Colloidal inorganic particle as the organic polymer coating, have no particular limits, preferably for example be with vinyl unsaturated monomer and water-disintegrable silane with free-radical polymerised pair of key in the presence of silica gel, the particle (for example the spy opens shown in the clear 59-71316 communique) that the method by emulsion polymerization obtains; With vinyl unsaturated monomer and anionoid polymerization monomer in the presence of silica gel, the particle (for example the spy opens shown in the clear 59-217702 communique) that the method by emulsion polymerization obtains; By water-soluble high-molecular compound is adsorbed in the inorganic particle, the particle (for example the spy opens shown in the clear 60-58237 communique) that obtains with the method for the polymer overmold of free radical polymerization monomer then; With vinyl unsaturated monomer and vinyl unsaturated monomer with hydroxyl in the presence of silica gel, the particle (for example the spy opens shown in the flat 6-199917 communique) that the method by emulsion polymerization obtains; Has the core/shell structure, in core, do not exist between configuration organic polymer and the organic polymer covalent linkage silica and/or silica gel, in shell, dispose organic polymer, by between core organic polymer/shell organic polymer, forming three-dimensional cross-linked eyed structure and/or IPN structure, make that silica and/or the silica gel in the core does not remain on intragranular particle (for example the spy opens shown in the flat 8-290912 communique) by covalent linkage in physicochemical mode; In the presence of silica gel, activator and water, the particle (for example the spy opens shown in the 11-1893 communique) that the method for vinyl unsaturated compound by emulsion polymerization obtained; By cationic residue, ethene polymers is combined in the particle (for example the spy opens shown in the flat 11-209622 communique) of glue-like silica particle surface; Directly or by nonionogenic tenside ethene polymers is combined in particle (for example the spy opens shown in the 2000-290464 communique) inorganic or that organic granular is surperficial; By nonionogenic tenside at inorganic or the surperficial assembly of organic granular or cohesion and sedimentary colloidal particulate (for example the spy opens shown in the 2001-335721 communique) etc.
In the present invention, with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (B) amount of colloidal inorganic particle is preferably 0.1～95 weight part, more preferably 0.1～50 weight part, more preferably 0.5～20 weight part.
In the present invention, as (C) sulfosuccinic acids tensio-active agent, what can enumerate is sulfosuccinic acid compounds shown in following formula (1).
Figure A0380328900231
R in the formula 3And R bCan be identical or different, expression hydrogen, carbonatoms is 1～20 alkyl, carbonatoms is 1～20 thiazolinyl, carbonatoms is 5～12 cycloalkyl, carbonatoms is 5～10 aryl, carbonatoms is 6～19 alkyl such as aralkyl, or its part is by hydroxyl, these groups that the carboxylic acid group replaces, or the polyoxyalkylenes alkylether radicals (carbonatoms of moieties is 2～4, (carbonatoms of moieties is 0～20 to polyoxyalkylenes alkyl phenyl ether, the carbonatoms of alkylene moiety is 2～4) etc. the organic radical that contains the oxyalkylene group compound, or basic metal, ammonium, organic amine alkali or organic quaternary amine alkali, M represents basic metal, ammonium, organic amine alkali or organic quaternary ammonium hydroxide.
In more detail, in the compound shown in the above-mentioned formula (1), that can enumerate is wherein R aAnd/or R bBe the compound shown in following formula (2), (3) or (4).
-(AO)n-R 21 (2)
Figure A0380328900232
Figure A0380328900241
For in formula (2), (3) or (4) any one, R 21The expression carbonatoms is 1～20 alkyl, carbonatoms is 1～20 thiazolinyl, carbonatoms is 5～12 cycloalkyl, carbonatoms is 5～10 aryl, carbonatoms is 6～19 alkyl such as aralkyl, or its part is by hydroxyl, these groups that the carboxylic acid group replaces, or the polyoxyalkylenes alkylether radicals (carbonatoms of moieties is 2～4, (carbonatoms of moieties is 0～20 to polyoxyalkylenes alkyl phenyl ether, the carbonatoms of alkylene moiety is 2～4) etc. the organic radical that contains the oxyalkylene group compound, A is that carbonatoms is 2～4 the alkylidene group or the alkylidene group of replacement, n is 0～200 integer, R 22Be hydrogen or methyl.)。
In the present invention, as the compound shown in the general formula (I), for example, as the sulfosuccinic acids tensio-active agent that does not contain free-radical polymerised pair of key, the sulfo-succinic acid dioctyl sodium that has that can enumerate (is spent ペ レ Star Network ス (trade mark) OT-P of king's (strain) manufacturing, perhaps エ ア ロ ゾ Le (trade mark) OT-75 that makes of Mitsui サ イ テ Star Network (strain) etc.), sulfo-succinic acid dihexyl sodium (エ ア ロ ゾ Le (trade mark) MA-80 that Mitsui サ イ テ Star Network (strain) is made etc.), エ ア ロ ゾ Le (trade mark) TR-70 that Mitsui サ イ テ Star Network (strain) is made, A-196-85, AY-100, IB-45, A-102, A-103,501 etc.As the sulfosuccinic acids tensio-active agent that contains free-radical polymerised pair of key, the Sanyo that has that can enumerate changes into エ レ ミ ノ-Le (trade mark) JS-2, the JS-5 of (strain) manufacturing, ラ テ system Le (trade mark) S-120, S-180, the S-180A etc. that flower king (strain) makes.Wherein, the aspect of the water contact angle of filming from reduction does not preferably contain the sulfosuccinic acids tensio-active agent of free-radical polymerised pair of key.
In the present invention, with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (C) sulfosuccinic acids tensio-active agent preferably with 0.1～20 weight part, more preferably 0.5～10 weight part, more preferably 1.0～5 weight parts amount and use.If in this scope, use, can form the good coating of water tolerance.
In the present invention, (D) tensio-active agent that contains oxyalkylene group does not contain (C) in its structure, it comprises the aniorfic surfactant that contains oxyalkylene group and contain free-radical polymerised pair of key, contain oxyalkylene group and do not contain free-radical polymerised pair of key aniorfic surfactant, contain oxyalkylene group and contain the nonionic surface active agent of free-radical polymerised pair of key, the nonionic surface active agent that contains oxyalkylene group and do not contain free-radical polymerised pair of key.
In the present invention, the aniorfic surfactant that (D) contains oxyalkylene group can be listed below the compound shown in formula of stating (5) and the formula (6).
R 51-O-(AO)n-SO 3M (5)
In above-mentioned formula (5) and formula (6), R 51The expression carbonatoms is that 1～20 alkyl, carbonatoms are that 1～20 thiazolinyl, carbonatoms are that 5～12 cycloalkyl, carbonatoms are these groups that alkyl such as 6～19 aralkyl or its part are replaced by hydroxyl, carboxylic acid group, or the organic radical that contains the oxyalkylene group compound of polyoxyalkylenes alkylether radicals (carbonatoms of moieties is 0～20, the carbonatoms of alkylene moiety be 2～4), polyoxyalkylenes alkyl phenyl ether (carbonatoms of moieties is 0～20, the carbonatoms of alkylene moiety be 2～4) etc.A is that carbonatoms is that 2～4 alkylidene group or the substituted alkylidene group of part, n are 0～200 integer, and M is ammonium, sodium, potassium.
In the present invention, the aniorfic surfactant that (D) contains oxyalkylene group and contain free-radical polymerised pair of key can be listed below the compound shown in the formula of stating (7), (8) and the formula (9).
Figure A0380328900261
(in the formula, R 71Be that carbonatoms is 6～18 alkyl, thiazolinyl or aralkyl, R 72Be that hydrogen, carbonatoms are 6～18 alkyl, thiazolinyl or aralkyl, R 73Be hydrogen or propenyl, A is that carbonatoms is that 2～4 alkylidene group or the substituted alkylidene group of part, n are 1～200 integer, and M is ammonium, sodium, potassium.)
(in the formula, R 81Be hydrogen or methyl, R 82Be that carbonatoms is 8～24 alkyl or acyl group, A is that carbonatoms is 2～4 alkylidene group, and n is 0～50 integer, and m is 0～20 integer, and M is ammonium, sodium, potassium.)
Figure A0380328900263
(in the formula, R 91Be that carbonatoms is 8～30 alkyl, R 92Be hydrogen or methyl, A is that carbonatoms is that alkylidene group, the n of 2～4 alkylidene group or replacement is 0 or 1～200 integer, and M is ammonium, sodium, potassium or alkanolamine residue.)
As the alkylphenol ether compound shown in the above-mentioned formula (7), ア Network ア ロ Application (trade mark) HS-10 that for example first industrial pharmacy (strain) manufacturing is arranged that can enumerate etc., as the compound shown in the above-mentioned formula (8), having of can enumerating ア デ カ リ ア ソ-プ (trade mark) SE-1025A that for example rising sun electrochemical industry (strain) makes, SR-1025A, SR-10N, SR-20N etc., as the compound shown in the above-mentioned formula (9), ア Network ア ロ Application (trade mark) KH-5, the KH-10 etc. that have for example first industrial pharmacy (strain) to make that can enumerate.As other aniorfic surfactant that contains oxyalkylene group and contain free-radical polymerised pair of key, ラ テ system Le PD-101, PD-104 etc., the Sanyo that Antox (the trade mark)-MS-60 that for example Japanese emulsifying agent (strain) manufacturing is arranged that can enumerate etc., flower king (strain) make changes into エ レ ミ ノ-Le (trade mark) RS-30 of (strain) manufacturing etc.
In the present invention, the nonionic surface active agent that contains oxyalkylene group as (D) can be listed below the compound shown in formula of stating (10) and the formula (11).
R 101-O-(AO)n-R 102 (10)
R 101-(AO)n-R 102 (11)
In above-mentioned formula (10) and formula (11), R 101The expression carbonatoms is that 1～20 alkyl, carbonatoms are that 1～20 thiazolinyl, carbonatoms are that 5～12 cycloalkyl, carbonatoms are these groups that alkyl such as 6～19 aralkyl or its part are replaced by hydroxyl, carboxylic acid group, or the organic radical that contains the oxyalkylene group compound of polyoxyalkylenes alkylether radicals (carbonatoms of moieties is 0～20, the carbonatoms of alkylene moiety be 2～4), polyoxyalkylenes alkyl phenyl ether (carbonatoms of moieties is 0～20, the carbonatoms of alkylene moiety be 2～4) etc.A is that carbonatoms is that 2～4 alkylidene group or the substituted alkylidene group of part, n are 0～200 integer, R 102Be hydrogen or methyl.
In the present invention, the nonionic surface active agent that contains oxyalkylene group as (D) and have a free-radical polymerised pair of key can be listed below the compound shown in the formula of stating (12), (13) and the formula (14).
(in the formula, R 121Be that carbonatoms is 6～18 alkyl, thiazolinyl or aralkyl, R 122Be that hydrogen, carbonatoms are 6～18 alkyl, thiazolinyl or aralkyl, R 123Be hydrogen or propenyl, A is that carbonatoms is that 2～4 alkylidene group or the substituted alkylidene group of part, n are 1～200 integer.)
Figure A0380328900282
(in the formula, R 131Be hydrogen or methyl, R 132Be that carbonatoms is 8～24 alkyl or acyl group, A is that carbonatoms is 2～4 alkylidene group, and n is 0～100 integer, and m is 0～50 integer.)
Figure A0380328900283
(in the formula, R 141Be that carbonatoms is 8～30 alkyl, R 142Be hydrogen or methyl, A is that carbonatoms is that alkylidene group, the n of 2～4 alkylidene group or replacement is 0 or 1～200 integer.)
As the compound shown in the above-mentioned formula (12), that can enumerate is ア Network ア ロ Application (trade mark) RN-10 that makes of for example first industrial pharmacy (strain), RN-20, RN-30, RN-50 etc., as the compound shown in the above-mentioned formula (13), that can enumerate is ア デ カ リ ア ソ-プ (trade mark) NE-20, NE-30, NE-40, ER-10, ER-20, ER-30, the ER-40 etc. that for example rising sun electrochemical industry (strain) is made.
In the present invention, the tensio-active agent that contains oxyalkylene group as (D), polymerization stability is good in order to obtain, the water tolerance good film, preferably contain oxyalkylene group and have the tensio-active agent of free-radical polymerised pair of key, more preferably contain oxyalkylene group and have the aniorfic surfactant of free-radical polymerised pair of key.
In the present invention, (D) tensio-active agent that contains oxyalkylene group has no particular limits, and in order to obtain the water tolerance good film, preferably uses with less amount, with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, can use with the amount of 0.1～5 weight %.
As the tensio-active agent that is used for emulsion polymerization among the present invention, except (C) sulfosuccinic acids tensio-active agent, (D) contain beyond the tensio-active agent of oxyalkylene group, that can also enumerate has a sodium p styrene sulfonate, p styrene sulfonic acid potassium, vinylformic acid-(2-sulfo group second) ester sodium, vinylformic acid-(2-sulfo group second) ester sodium potassium, methacrylic acid-(2-sulfo group second) ester sodium, vinylformic acid-(3-sulfo group third) ester potassium, methacrylic acid-(3-sulfo group third) ester sodium, fatty acid soaps, alkylsulfonate, alkyl sulfo succinate, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene oxygen third rare segmented copolymer etc.
In the present invention, (A) aqueous dispersion, (B) colloidal inorganic particle and/or the colloidal inorganic particle that coated by organic polymer, (C) sulfosuccinic acids tensio-active agent and the mixed order that (D) contains the tensio-active agent of oxyalkylene group have no particular limits, as (A), (B), (C) and concrete blending means (D), among oriented (A) that can enumerate according to (B), (C), (D) order is carried out the blended method, in (A) according to (B), (D), (C) order is carried out the blended method, in (A) according to (C), (B), (D) order is carried out the blended method, in (A) according to (C), (D), (B) order is carried out the blended method, in (A) according to (D), (B), (C) order is carried out the blended method, in (A) according to (D), (C), (B) order is carried out the blended method, in A, mix (B) and mixture (C), the method of remix (D), in A, mix (D), the method of remix (B) and mixture (C), in A, mix (B) and mixture (D), the method of remix (C), in A, mix (C), the method of remix (B) and mixture (D), in A, mix (C) and mixture (D), the method of remix (B), in A, mix (B), the method of remix (C) and mixture (D), to mix (A) earlier, (B), remix (C), the method of mixture (D) is mixed in (A) (B), (C), the method of mixture (D).
As when making (A), using (C) and/or concrete example (D), what can enumerate is to use (C) and/or (D) when making (A), the method of mixing (B) then, when making (A), use (C) and/or (D), mix then (B), (C) ((C) at this moment can be identical to method, also can be different), when making (A), use (C) and/or (D), mix then (B), (D) ((D) at this moment can be identical to method, also can be different), when making (A), use (C) and/or (D), mix then (B), (C), (D) method ((C) at this moment, (D) can be identical, also can be different).When mixing, can at room temperature mix, can be that the ceiling temperature heating mixes also with 90 ℃.
In the present invention, with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (B) solid state component of colloidal inorganic particle is preferably 0.1～95 weight part, more preferably 0.1～50 weight part, more preferably 0.5～20 weight part.If (B) the colloidal inorganic particle is in this scope, the water tolerance of filming that obtains is good, and the rain line of filming is not obvious.
In the present invention, with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (C) sulfosuccinic acids tensio-active agent is preferably 0.1～20 weight part, more preferably 0.5～10 weight part, 1.0～5 weight parts more preferably.If (C) sulfosuccinic acids tensio-active agent is in this scope, the water tolerance of filming that obtains is good, and the rain line of filming is not obvious.And the storage stability of coating liquid is good.
In the present invention, when mixing or during the preceding dispersion of coating pigment, other tensio-active agent that can add when containing the tensio-active agent of oxyalkylene group and polymerization, can use following tensio-active agent as required simultaneously except (C) sulfosuccinic acids tensio-active agent, (D).That specifically can enumerate has, the sodium salt of hexa metaphosphoric acid for example, sylvite or ammonium salt, the sodium salt of tripolyphosphate, sylvite or ammonium salt, sodium salt with polymkeric substance of carboxylic acid groups such as polyacrylic acid, sylvite or ammonium salt, other is higher fatty acid for example, resinous acid, acid higher alcohols, sulfuric ester, senior alkyl sulfonic acid, the sulfonic alkyl allyl ester, the aniorfic surfactant of the salt representative of sulfonated castor oil etc., perhaps ethylene oxide and long chain aliphatic alcohol, the known reaction product representative nonionic surface active agent of phenols or phosphoric acid class, and the cationic surfactant that contains quaternary ammonium salt etc.
In the present invention, preferably with (E) vinyl unsaturated monomer and (C) sulfosuccinic acids tensio-active agent and/or the tensio-active agent that (D) contains oxyalkylene group as pre-emulsion, this pre-emulsion and (F) after the water-disintegrable silane mixture, in aqueous medium, it is added to just in the polymeric reaction system continuously or off and on one by one.
In the present invention, preferably with (E) vinyl unsaturated monomer and (C) sulfosuccinic acids tensio-active agent and/or (D) contain pre-emulsion that the tensio-active agent of oxyalkylene group forms by homogenizer etc. in addition the stirrer of high shear force carry out pre-emulsification.Can also contain water, polymerization starter arbitrarily in addition in the pre-emulsion.
In the present invention, after by (E) vinyl unsaturated monomer and (C) sulfosuccinic acids tensio-active agent and/or the tensio-active agent that (D) contains oxyalkylene group form pre-emulsion, make this pre-emulsion and (F) water-disintegrable silane can be continuously or mix off and on, and in aqueous medium, carry out emulsion polymerization, it must be added to just in the polymeric reaction system continuously or off and on one by one in the polymerization.
In the present invention, this pre-emulsion and (F) water-disintegrable silane is continuously so-called or mix off and on and be meant, in back 1 minute of mixing, preferably in 30 seconds, more preferably in 10 seconds, the two is added to produce in the polymeric reaction system continuously go, most preferably before being about to add reaction system to, after both mixing, this mixture is added to just in the polymeric reaction system continuously or off and on one by one.
Mixing this pre-emulsion and (F) during water-disintegrable silane, carrying out emulsification if the high shear force that uses homogenizer etc. to produce by high speed rotating stirs, (F) water-disintegrable silane hydrolyzate then is because the alcohol that produces etc. can destroy the emulsified state of emulsion.Thereby this pre-emulsion and (F) blending means of water-disintegrable silane must be gentle stirring, specifically, making (F) water-disintegrable silane remain on median size is the above emulsified states of 10 μ m, and preferably making (F) water-disintegrable silane remain on median size in mixed solution is can be by the emulsified state more than the 100 μ m that are visually observed.
As the concrete blending means among the present invention, what can enumerate is, method of static mixer N10 series, N16 series, N60 series (ProductName, ノ リ ケ (strain) makes), the terminal filler metal net of other outlet, Raschig ring or zeolite etc. for example at the Y font.When the 125L, the 275L (ProductName that use as line mixer, Silverson Machines, Inc. manufacturing), T.K. パ イ プ ラ イ Application ホ モ ミ キ サ-(ProductName, special machine chemical industry (strain) manufacturing), T.K. ホ モ ミ Star Network ラ イ Application ミ キ サ-(ProductName, special machine chemical industry (strain) is made) during the stirrer that waits, it also can use if suppress the stirring revolution as much as possible.Temperature during as mixing is below 60 ℃, preferably below 50 ℃, more preferably below 40 ℃.If when not satisfying aforementioned condition, because acid or alkaline, a large amount of water-disintegrable silane generation hydrolysis of free radical polymerization monomer emulsion destroys pre-emulsion, pre-emulsion is separated into monomer layer part and water layer part.Produce a large amount of condensation products in the reaction system of result in polymerization.
Emulsion among the present invention is to obtain by carry out following emulsion polymerization simultaneously in aqueous medium, described emulsion polymerization is promptly based on the emulsion polymerization of the radical polymerization of free radical polymerization monomer, and based on the emulsion polymerization of the hydrolysis-condensation reaction of water-disintegrable silane.As aqueous medium described here, main what use is water, comprises that also it is water-soluble solvent such as 1～3 lower alcohol or ketone and the medium of property one-tenth that Xiang Shuizhong adds carbonatoms.At this moment the quantity of solvent beyond the water of Tian Jiaing is preferably below 20% in emulsion.
When carrying out the emulsion polymerization of (E) vinyl unsaturated monomer in the presence of (F) water-disintegrable silane, the hydrogen ion concentration (pH) of the emulsion polymerization system in the emulsion polymerization is preferably pH below 4.0, and more preferably pH is more than 1.5 below 3.5.Carry out the emulsion polymerization reaction under the pH condition below the above-mentioned upper limit, can promote the condensation reaction of water-disintegrable silane, owing to do not carry out condensation reaction behind the emulsion polymerization, the storage stability of product improves.
In emulsion polymerization, as catalysts for radical polymerization, it is because heat or reducing substances decompose free radical, thereby can make vinyl unsaturated monomer addition polymerization, can advantageously use water-soluble or oil-soluble persulphate, superoxide, tetrazo based compound etc.As example, that can enumerate has Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, tert-butyl hydroperoxide, a TBPB tertiary butyl perbenzoate, 2,2-Diisopropyl azodicarboxylate, 2,2-azo two (2-diaminopropanes) hydrochloride, 2,2-azo two (2, the 4-methyl pentane nitrile) etc., preferred use also is effective Potassium Persulphate, Sodium Persulfate, ammonium persulphate as the hydrolysis reaction that promotes water-disintegrable silane and the catalyzer of condensation reaction.With respect to (E) vinyl unsaturated monomer, the amount of catalysts for radical polymerization is generally 0.05 weight %～1 weight %.
General polymerization reaction is preferred under normal pressure, carry out under 65～90 ℃ polymerization temperature, considers the characteristic of the vapour pressure relevant with monomeric polymerization temperature etc., also can under high pressure carry out.As polymerization time, arranged, boiling (cooking) time after importing the importing time.Under situation about various raw materials being directed into simultaneously in the reaction system, the importing time generally is several minutes, under situation about various raw materials being directed into one by one in the reaction system, because it is can remove owing to be directed into it in reaction system one by one in the scope of the reaction heat that polyreaction produces, therefore make the importing asynchronism(-nization) owing to the polymer concentration in the emulsion that finally obtains is different, generally more than 10 minutes.As the cooking time after importing, preferably at least more than 10 minutes.If below the polymerization time, each raw material may be residual at this, water-disintegrable silane does not then carry out condensation, and is residual with the form of hydrolyzate.
In addition, promote polymerization velocity in hope, and carrying out under the low temperature below 70 ℃ under the polymeric situation that it is favourable for example reductive agent such as sodium bisulfite, iron protochloride, ascorbate salt, rongalite and catalysts for radical polymerization being used in combination.And then, in order to adjust molecular weight, can at random add chain-transfer agents such as lauryl mercaptan.
In addition, when using water-disintegrable silane to carry out emulsion polymerization, after emulsion polymerization finishes, hardening catalyst during as film forming, can in emulsion of the present invention, add for example organic acid metal-salt, n-hexyl amine, 1 such as dibutyl tin dilaurate, two lauric acid, two hot tin, oxalic acid two fourth tin, stannous octoate, tin laurate, iron octoate, lead octoate 36, tetrabutyl titanate, 8-diazabicyclo [5,4,0]-amine compound such as 7-ten-carbene.In addition, when these sclerosis are not under the water miscible situation with catalyzer, when using it, wish to carry out emulsification with tensio-active agent and water.
In the emulsion among the present invention, the median size of preferred dispersate is 10～1000nm.
As the non-volatile component in the emulsion of the present invention, be preferably 20～70 weight %, more preferably 30～65 weight %.
For the antifouling coating composition of using of water-based of the present invention, in order to keep the secular dispersion stabilization of emulsion, the preferred alkaline matter that uses, be the representative alkaline organic compound for example with amines such as ammoniacal liquor, dimethylaminoethanols, be the alkaline inorganic compound etc. of representative with an alkali metal salt of sodium hydroxide, potassium hydroxide etc., adjust pH in 5～10 scope.
In addition, antifouling in water-based of the present invention with in the coating composition, can at random admix and add the blended composition in the aqueous coating usually, for example thickening material, film coalescence aid, softening agent, antifreezing agent, defoamer, dyestuff, sanitas, UV light absorber, photostabilizer etc.
As thickening material, that specifically can enumerate has polyvinyl alcohol (comprising partly-hydrolysed polyvinyl alcohol), methylcyclohexane, hydroxyethyl cellosolve, the contour molecular dispersion stablizer of polyvinylpyrrolidone etc., other polyethers, a polycarboxylic acid thickening material etc.
As film coalescence aid, that specifically can enumerate has butylcarbitol, ethylene glycol monobutyl ether, diethyl carbitol, diethylene glycol dibutyl ether, ethylene glycol one a 2-ethyl hexyl ether, 2,2,4-trimethylammonium-1,3 butylene glycol isopropyl acid ester, pentanedioic acid diisopropyl ester, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether etc.These film coalescence aid can mix arbitrarily individually or in combination.
As softening agent, that specifically can enumerate has dibutyl phthalate, a dioctyl phthalate (DOP) etc.
As antifreezing agent, that specifically can enumerate has propylene glycol, an ethylene glycol etc.
As UV light absorber; benzophenone is arranged; benzotriazole category; triazines; as the benzophenone UV light absorber; that specifically can enumerate has 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid; Octabenzone; 2-hydroxyl-4-positive 12-alkoxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane; 2; 2 '-dihydroxyl-4-methoxy benzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; 2; 2 '; 4,4 '-tetrahydroxybenzophenone; 4-n-dodecane oxygen base-2-dihydroxy benaophenonel; 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone; 2-hydroxyl-4-stearoyl-oxy benzophenone etc.
As the UV light absorber of free-radical polymerised benzophenone, that specifically can enumerate has 2-hydroxyl-4-third rare acyloxy benzophenone, 2-hydroxy-4-methyl third rare acyloxy benzophenone, 2-hydroxyl-5-third rare acyloxy benzophenone, 2-hydroxy-5-methyl base third rare acyloxy benzophenone, 2-hydroxyl-4-(third rare acyloxy-oxyethyl group) benzophenone, 2-hydroxyl-4-(the rare acyloxy-oxyethyl group of methyl-prop) benzophenone, 2-hydroxyl-4-(the rare acyloxy-diethoxy of methyl-prop) benzophenone, 2-hydroxyl-4-(third rare acyloxy-triethoxy) benzophenone etc.
UV light absorber as benzotriazole category, that specifically can enumerate has 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3,5-two uncle's octyl phenyls) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two (α, α ' dimethyl benzyl) benzotriazole phenyl), the condenses of methyl-3-(the 3-tertiary butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl) propionic ester and polyvinyl alcohol (molecular weight 300) (make by Japanese チ バ ガ イ ギ-(strain), ProductName: TINUVIN1130), iso-octyl-3-(3-(2H-benzotriazole-2-the yl)-5-tertiary butyl-4-hydroxyphenyl) propionic ester (make by Japanese チ バ ガ イ ギ-(strain), ProductName: TINUVIN384), 2-(3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (make by Japanese チ バ ガ イ ギ-(strain), ProductName: TINUVIN571), 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-(and 3 "; 4 "; 5 "; 6 "-tetrahydric phthalimide methyl) benzotriazole-5 '-aminomethyl phenyl), 2, (4-(1 for the 2-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol), 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-(make, ProductName: TINUVIN900) etc. by Japanese チ バ ガ イ ギ-(strain).
UV light absorber as radical polymerization class benzotriazole category, the 2-(the rare acyloxy ethylphenyl of 2 '-hydroxyl-5 '-methyl-prop)-2H-benzotriazole (Da mound chemistry (strain) of having that specifically can enumerate makes, ProductName: RUVA-93), 2-(the rare acyloxy ethyl of 2 '-hydroxyl-5 '-methyl-prop-3-tert-butyl-phenyl)-2H-benzotriazole, 2-(the rare acyloxy propyl group of 2 '-hydroxyl-5 '-methyl-prop-3-tert-butyl-phenyl)-5-chloro-2H-benzotriazole, 3-third rare acyloxy-2-hydroxypropyl-3-(3 '-(2 "-benzotriazole)-4-hydroxyl-5-tertiary butyl) the phenylpropionic acid ester (make, ProductName: CGL-104) etc. by Japanese チ バ ガ イ ギ-(strain).
As the triazines UV light absorber, that specifically can enumerate has a TINUVIN400 (ProductName, Japanese チ バ ガ イ ギ-(strain) make).
As photostabilizer, preferred hindered amine light stabilizer, wherein more preferably alkaline junior, preferred especially alkaline constant (pKb) is more than 8.That specifically can enumerate has two (2,2,6,6-tetramethyl--4-piperidyl) succinate, two (2,2,6, the 6-tetramethyl-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) 2-(3,5-di-t-butyl-butyl-4 hydroxybenzyl)-2-butyl malonic acid ester, 1-(2-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) third alkynyloxy group) ethyl)-4-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) third alkynyloxy group)-2,2,6, the 6-tetramethyl piperidine, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate and methyl isophthalic acid, 2,2,6, the mixture of 6-pentamethyl--4-piperidyl-sebate (make, ProductName: TINUVIN292) by Japanese チ バ ガ イ ギ-(strain), two (1-octyl groups-2,2,6,6-tetramethyl--4-piperidyl) sebate, TINUVIN123 (ProductName, Japanese チ バ ガ イ ギ-(strain) made).
As free-radical polymerised hindered amine light stabilizer, that specifically can enumerate has 1,2,2,6,6-pentamethyl--4-piperidino methyl acrylate, 1,2,2,6,6-pentamethyl--4-piperidyl acrylate, 2,2,6,6-tetramethyl--4-piperidino methyl acrylate, 2,2,6,6-tetramethyl--4-piperidyl acrylate, 1,2,2,6,6-pentamethyl--4-imino-piperidino methyl acrylate, 2,2,6,6-tetramethyl--4-imino-piperidino methyl acrylate, 4-cyano group-2,2,6,6-tetramethyl--4-piperidino methyl acrylate, 4-cyano group-1,2,2,6,6-pentamethyl--4-piperidino methyl acrylate etc.
In the present invention, UV light absorber and/or photostabilizer can add in (A) aqueous dispersion by following method: be directed in (A) aqueous dispersion by it is existed during emulsion polymerization in making (A) aqueous dispersion; To add to after the mixing such as UV light absorber and/or photostabilizer and film coalescence aid in (A) aqueous dispersion and import; With mixing such as UV light absorber and/or photostabilizer and film coalescence aid, add tensio-active agent, water and add to after making its emulsification in (A) aqueous dispersion and import.In addition, if use UV light absorber and photostabilizer simultaneously, because synergy can demonstrate remarkable weather resistance.
1 kind of optimal way of the present invention is, (E) the vinyl unsaturated monomer is by (E that can be identical or different 1) and (E 2) form, (C) sulfosuccinic acids tensio-active agent and/or the tensio-active agent that (D) contains oxyalkylene group are by (C that can be identical or different between mutually 1) and/or (D 1), (C 2) and/or (D 2) form, above-mentioned emulsion polymerization carries out in turn according to step (1), step (2).In step (1), (E 1) the vinyl unsaturated monomer is at (C 1) sulfosuccinic acids tensio-active agent and/or (D 1) contain under the existence of tensio-active agent of oxyalkylene group, in aqueous medium, carry out emulsion polymerization, obtain the emulsion of step (1).In step (2), (E 2) the vinyl unsaturated monomer is at (C 2) sulfosuccinic acids tensio-active agent and/or (D 2) contain under the existence of tensio-active agent of oxyalkylene group, can add in the emulsion of step (1) with aqueous medium as required, carry out emulsion polymerization, it is silicone-modified to use (F) water-disintegrable silane to carry out, and obtains (A) aqueous dispersion.By in (A) aqueous dispersion that obtains, mixing the colloidal inorganic particle that (B) colloidal inorganic particle and/or organic polymer coat, and mix the tensio-active agent that (C) sulfosuccinic acids tensio-active agent, (D) contain oxyalkylene group as required, obtain the antifouling coating composition of using of water-based.
In addition, in addition a kind of optimal way of the present invention is, (E) the vinyl unsaturated monomer is by (E that can be identical or different 1), (E 2) and (E 3) form, (C) sulfosuccinic acids tensio-active agent and/or the tensio-active agent that (D) contains oxyalkylene group are by (C that can be identical or different between mutually 1) and/or (D 1), (C 2) and/or (D 2) and (C 3) and/or (D 3) form, above-mentioned emulsion polymerization carries out in turn according to step (1), step (2), step (3).In step (1), (E 1) the vinyl unsaturated monomer is at (C 1) sulfosuccinic acids tensio-active agent and/or (D 1) contain under the existence of tensio-active agent of oxyalkylene group, in aqueous medium, carry out emulsion polymerization, it is silicone-modified to use (F) water-disintegrable silane to carry out, and obtains the emulsion of step (1).In step (2), (E 2) the vinyl unsaturated monomer is at (C 2) sulfosuccinic acids tensio-active agent and/or (D 2) contain under the existence of tensio-active agent of oxyalkylene group, can add in the emulsion of step (1) with aqueous medium as required, carry out emulsion polymerization, it is silicone-modified to use (F) water-disintegrable silane to carry out, and obtains the emulsion of step (2).In step (3), (E 3) the vinyl unsaturated monomer is at (C 3) sulfosuccinic acids tensio-active agent and/or (D 3) contain under the existence of tensio-active agent of oxyalkylene group, can add in the emulsion of step (2) with aqueous medium as required, carry out emulsion polymerization, it is silicone-modified to use (F) water-disintegrable silane to carry out, and obtains (A) aqueous dispersion.By in (A) aqueous dispersion that obtains, mixing the colloidal inorganic particle that (B) colloidal inorganic particle and/or organic polymer coat, and mix the tensio-active agent that (C) sulfosuccinic acids tensio-active agent, (D) contain oxyalkylene group as required, obtain the antifouling coating composition of using of water-based.
Water-based paint compositions of the present invention can be applied to coating, building building decoration coated material etc.
About the coated article that can use the coating that contains water-based paint compositions of the present invention to apply.Article as these coatings, the inorganic substrate that concrete sheet-pile, reinforced cement-mortar board, slabstone, flexible board, printed circuit board (PCB), ALC plate, silicon plate, plasterboard, extrusion molding plate, concrete blocks etc. are arranged that specifically can enumerate, weaving cotton cloth or tNonwovens is the building material, metal sheet, metal parts class, timber, plastics, stone material etc. of material, and these coated article had passes in time and the old applicator surface of deterioration etc.Preferably undertaken adjusting under the surface by priming paint, sealing coating, cement filling or priming paint coating, by with on water-based paint compositions of the present invention article, can obtain demonstrating the coated article of good didirtresistance as application of paints adjustment under these processes are surperficial.As the aggregation of these coated articles, that can enumerate has buildings, automobile, ship, a bridge etc.
Contain the outer wall materials that the coating of water-based paint compositions of the present invention applies as use, ceramic industry wooden partition, extrusion molding cement plate outer wall materials, ALC outer wall materials, extraneous adornment ceramic tile, metal wooden partition etc. are for example arranged.
Contain the buildings that the coating of water-based paint compositions of the present invention applies, communal facilitys such as a guy's dwelling house that can enumerate, condominium, high building, bridge, gymnasium, court as use.
Contain the coating method of the coating of water-based paint compositions of the present invention as use, that can enumerate has spread coating, rolling method, spraying method, the coating of curtain membrane type, a roller painting etc.
By the following examples and comparative example the present invention will be described in detail.In addition, umber in embodiment and comparative example and % represent weight part and weight % respectively.In addition, in the physical property test of the water-based paint compositions that obtains, use this water-based paint compositions to form preparation coating, test according to test method shown below according to the mixing shown in following.
＜coating mixes to be formed 〉
The manufacturing of varnish colour (except the comparative example 3 and 4)
500.00 parts of each didirtresistance water-based paint compositions (being scaled solid state component)
100.00 parts of the mixed solutions of 50 parts of ethylene glycol monobutyl ethers and 50 parts of water
100.00 parts of CS-12 (ProductName, intelligence rope (strain) is made)
(in comparative example 3 and 4, do not mix ethylene glycol monobutyl ether, CS-12.)
The manufacturing of pigment dispersion
Dispersion agent: Pig.Disperser MD20 (ProductName, BASF ヅ ヤ パ Application (strain) is made)
5.35 part
0.50 part of ammoniacal liquor
23.50 parts of propylene glycol
147.50 parts in water
333.50 parts of イ ペ-Network CR-97 (trade(brand)name, the former industry of stone (strain) is made)
Defoamer: BYK-028 (trade(brand)name, PVC Star Network ケ ミ-ヅ ヤ パ Application (strain) is made)
2.85 part
Said mixture was disperseed 20 minutes in desk-top sand mill, obtain pigment dispersion.
The manufacturing of enamel paint (except the comparative example 3 and 4)
500.00 parts of each didirtresistance water-based paint compositions (being scaled solid state component)
100.00 parts of the mixed solutions of 50 parts of ethylene glycol monobutyl ethers and 50 parts of water
100.00 parts of CS-12 (ProductName, intelligence rope (strain) is made)
513.20 parts of above-mentioned pigment dispersions
Thickening material: 10% aqueous solution of ア デ カ ノ-Le UH-438 (rising sun electrochemical industry (strain) manufacturing) is an amount of
(in comparative example 3 and 4, do not mix ethylene glycol monobutyl ether, CS-12.)
＜test method 〉
The solid state component of water dispersion etc.
With the dry mass of solid state component determination object things such as water dispersion after under 105 ℃ dry 3 hours.
The resin solid state component of water dispersion
At 105 ℃ down the dry weight after dry 3 hours, deduct the weight behind the dry weight of tensio-active agent, polymerization starter etc. from water dispersion.
The solid state component Determination on content of water dispersion etc.
In the aluminum dish that passes through weighing in advance, the solid state component assay objects such as water dispersion of the accurate about 1g of weighing, drying is after 3 hours down at 105 ℃ in the freeze-day with constant temperature machine, and at the moisture eliminator of having put into silica gel, the radiation cooling is accurate weighing after 30 minutes.With the dry back weight of this material divided by weight before dry, with this as solid state component content.
The storage stability of coating liquid
Above-mentioned enamel paint mixture is put into encloses container, in 50 ℃ thermostatic bath, placed for 4 weeks, the state after 4 weeks is judged by visual.Determinating reference is as follows.
◎: viscosity does not rise, and has flowability.
△: viscosity rises, and has flowability.
*: be gelation.
The water contact angle of transparent film
With the insulated wire coating machine above-mentioned varnish colour is coated on the sheet glass, makes dry film thickness become 100g/m 2, obtain test film after at room temperature dry 4 weeks.The water contact angle of the CA-X150 type contact angle determination device determination test sheet of making by consonance interface science (strain).
Water tolerance
Above-mentioned enamel paint mixture is coated on the sulfuric acid corrosion protection aluminium sheet at room temperature dry 2 days with insulated wire coating machine No.50.And then at 50 ℃ times dry 2 days, dipping was 30 days in 20 ℃ water, by its state of visual judgement.Determinating reference is as follows.
◎: do not have expansion, loss of gloss fully.
Zero: expand slightly, do not find loss of gloss.
△: have and expand and loss of gloss.
*: whole superficial expansion, loss of gloss is obvious.
Rainwater pollution
With the insulated wire coating machine with the mixture of each embodiment, comparative example as applying coating on corrosion protection aluminium sheet shown in Figure 1, make dry film thickness become 100g/m 2, obtain test film after at room temperature dry 4 weeks.This test film is placed outdoor, make ground vertical, and fix, exposing beginning to the open air after back 3 months, by visual judgement rainwater pollution towards the north with coated side.Determinating reference is as follows.
◎: line does not fully rain.
Zero: pollution is arranged on the whole, do not find the rain line.
△: whole contaminated, some rain lines are arranged.
*: see tangible rain line.
Weathering resistance
Above-mentioned enamel paint mixture is coated on the sulfuric acid corrosion protection aluminium sheet at room temperature dry 30 days with insulated wire coating machine No.50.Then carry out exposure test (rainfall cycle with daylight type weather meter (ス ガ trier (strain) manufacturing, WEL-SUN-DC); 18 minutes/2 hours, 60～66 ℃ of blackboard temperatures).Observe exposing to the open air through the appearance change after 2000 hours, determinating reference is as follows.
◎: do not change.
Zero: find loss of gloss.
△: the crackle of finding loss of gloss and part.
*: the crackle of finding loss of gloss and whole surface.
[preparation example 1 of water dispersion]
To stirrer is housed, reflux cooler, drop into 296 parts of water in the reactor of dropping bath and thermometer, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of methacrylic acids, 2 parts of ラ テ system Le S-180A, 4 parts of anionic reactive surfactant (ProductNames: ア Network ア ロ Application KH-10 that contain oxyalkylene group, the first industrial pharmacy (strain) manufacturing) 25% aqueous solution, 5 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: エ マ Le ゲ Application 120, flower king (strain) manufacturing) of oxyalkylene group, 2% the aqueous solution of 15 parts of ammonium persulphates, the emulsification mixed solution of 51 parts of water formation flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, the emulsification mixed solution that is formed by 2% the aqueous solution of 109 parts of methyl methacrylates, 160 parts of cyclohexyl methacrylates, 123 parts of n-butyl acrylates, 8 parts of methacrylic acids, 8 parts of ラ テ system Le S-180A, 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10,20% aqueous solution of 20 parts of エ マ Le ゲ Application 120,60 parts of ammonium persulphates, 204 parts of water flowed into 160 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.7%, the single 98nm that is distributed in of particle diameter.
[preparation example 2 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.Drop into 296 parts of water, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes) temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of methacrylic acids, 4 parts of ラ テ system Le S-180A, 4 parts of anionic reactive surfactant (ProductNames: ア Network ア ロ Application KH-10 that contain oxyalkylene group, the first industrial pharmacy (strain) manufacturing) 25% aqueous solution, 5 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: エ マ Le ゲ Application 120, flower king (strain) manufacturing) of oxyalkylene group, 2% the aqueous solution of 15 parts of ammonium persulphates, the emulsification mixed solution of 54 parts of water formation flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, emulsification mixed solution of being made up of 2% the aqueous solution of 109 parts of methyl methacrylates, 160 parts of cyclohexyl methacrylates, 123 parts of n-butyl acrylates, 8 parts of methacrylic acids, 16 parts of ラ テ system Le S-180A, 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10,20% aqueous solution of 20 parts of エ マ Le ゲ Application 120,60 parts of ammonium persulphates, 216 parts of water and the mixed solution be made up of 1 part of rare acyloxy propyl trimethoxy silicane of γ-third, 5 parts of dimethyldimethoxysil,ne, 35 parts of methyltrimethoxy silanes flowed into 160 minutes from each dropping bath respectively.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.12%.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.9%, the single 100nm that is distributed in of particle diameter.
[preparation example 3 of water dispersion]
To stirrer is housed, reflux cooler, drop into 296 parts of water in the reactor of dropping bath and thermometer, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of methacrylic acids, 0.5 part rare acyloxy propyl trimethoxy silicane of γ-third, 2 parts of ラ テ system Le S-180A, 4 parts of anionic reactive surfactant (ProductNames: ア デ カ リ ア ソ-プ SR-1025 that contain oxyalkylene group, rising sun electrochemical industry (strain) is made), 5 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: ア デ カ リ ア ソ-プ NE-20, rising sun electrochemical industry (strain) manufacturing) of oxyalkylene group, 2% the aqueous solution of 15 parts of ammonium persulphates, the emulsification mixed solution of 51 parts of water formation flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, the emulsification mixed solution that is formed by 2% the aqueous solution of 109 parts of methyl methacrylates, 160 parts of cyclohexyl methacrylates, 123 parts of n-butyl acrylates, 8 parts of methacrylic acids, 2 parts of rare acyloxy propyl trimethoxy silicanes of γ-third, 8 parts of ラ テ system Le S-180A, 16 parts of ア デ カ リ ア ソ-プ SR-1025,20 parts of ア デ カ リ ア ソ-20% aqueous solution of プ NE-20,60 parts of ammonium persulphates, 204 parts of water flowed into 160 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.08%.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.8%, the single 97nm that is distributed in of particle diameter.
[preparation example 4 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.In reactor, drop into 296 parts of water, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes) temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of methacrylic acids, 5 parts of anionic reactive surfactant (ProductNames: ラ テ system Le PD-104 that contain oxyalkylene group, flower king (strain) makes), 5 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: エ マ Le ゲ Application 920, flower king (strain) manufacturing) of oxyalkylene group, 2% the aqueous solution of 15 parts of ammonium persulphates, the emulsification mixed solution of 47 parts of water formation flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, emulsification mixed solution that is formed by 2% the aqueous solution of 109 parts of methyl methacrylates, 160 parts of cyclohexyl methacrylates, 123 parts of n-butyl acrylates, 8 parts of methacrylic acids, 20 parts of ラ テ system Le PD-104,20% aqueous solution of 20 parts of エ マ Le ゲ Application 920,60 parts of ammonium persulphates, 188 parts of water and the mixed solution that formed by 1 part of rare acyloxy propyl trimethoxy silicane of γ-third, 5 parts of dimethyldimethoxysil,ne, 35 parts of methyltrimethoxy silanes flowed into 160 minutes from each dropping bath respectively.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.10%.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.7%, the single 98nm that is distributed in of particle diameter.
[preparation example 5 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.In reactor, drop into 296 parts of water, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 32 parts of methyl methacrylates, 60 parts of cyclohexyl methacrylates, 30 parts of n-BMAs, 74 parts of n-butyl acrylates, 4 parts of methacrylic acids, 1 part of benzotriazole category UV light absorber (ProductName: TINUVIN384, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes), the mixture of 1 part of hindered amine light stabilizer (ProductName: TINUVIN123, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes); 8 parts of ラ テ system Le S-180A; 8 parts of 25% aqueous solution that contain the anionic reactive surfactant (ProductName: ア Network ア ロ Application KH-10, the first industrial pharmacy (strain) manufacturing) of oxyalkylene group; 10 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: エ マ Le ゲ Application 120, flower king (strain) manufacturing) of oxyalkylene group; 2% the aqueous solution of 30 parts of ammonium persulphates; The emulsification mixed solution of forming with 86 parts of water, and the mixed solution of forming by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 20 parts of methyltrimethoxy silanes respectively from dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixed solution of 16 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-BMAs, 9 parts of n-butyl acrylates, 10 parts of methacrylic acids, 0.5 part of TINUVIN384,0.5 part of TINUVIN123; 25% aqueous solution of 4 parts of ラ テ system Le S-180A, 4 parts of ア Network ア ロ Application KH-10; 20% aqueous solution of 5 parts of エ マ Le ゲ Application 120; 2% the aqueous solution of 15 parts of ammonium persulphates; The emulsification mixed solution of forming with 42 parts of water flows into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixture of 42 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 30 parts of n-BMAs, 24 parts of n-butyl acrylates, 4 parts of methacrylic acids, 1 part of TINUVIN384,1 part of TINUVIN123; 8 parts of ラ テ system Le S-180A; 25% aqueous solution of 8 parts of ア Network ア ロ Application KH-10; 20% aqueous solution of 10 parts of エ マ Le ゲ Application 120; 2% the aqueous solution of 30 parts of ammonium persulphates; Emulsification mixed solution that forms with 86 parts of water and the mixed solution formed by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 20 parts of methyltrimethoxy silanes respectively from each dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.05%.The solid state component content of the acrylic acid or the like emulsion that obtains is 45.5%, the single 98nm that is distributed in of particle diameter.
[preparation example 6 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.In reactor, drop into 296 parts of water, 4 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 35 parts of methyl methacrylates, 60 parts of cyclohexyl methacrylates, 101 parts of n-BMAs, 4 parts of methacrylic acids, 8 parts of ラ テ system Le S-180A, 16 parts of anionic reactive surfactant (ProductNames: ア Network ア ロ Application KH-10 that contain oxyalkylene group, the first industrial pharmacy (strain) manufacturing) 25% aqueous solution, 10 parts of nonionic surface active agent (ProductNames: エ マ Le ゲ Application 120 that contain oxyalkylene group, flower king (strain) manufacturing) 20% aqueous solution, 2% the aqueous solution of 30 parts of ammonium persulphates, 80 portions of emulsification mixed solutions that water forms, and by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, the mixed solution of 60 parts of methyltrimethoxy silane formation flowed into 80 minutes by above-mentioned Y-piece from each dropping bath.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, the emulsification mixed solution that is formed by 2% the aqueous solution of 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of n-BMAs, 10 parts of methacrylic acids, 4 parts of ラ テ system Le S-180A, 25% aqueous solution of 8 parts of ア Network ア ロ Application KH-10,20% aqueous solution of 5 parts of エ マ Le ゲ Application 120,15 parts of ammonium persulphates, 40 parts of water flowed into 40 minutes from each dropping bath respectively.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, emulsification mixed solution that forms by 2% the aqueous solution of 49 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 47 parts of n-BMAs, 4 parts of methacrylic acids, 8 parts of ラ テ system Le S-180A, 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10,20% aqueous solution of 10 parts of エ マ Le ゲ Application 120,30 parts of ammonium persulphates, 80 parts of water and the mixed solution that forms by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 60 parts of methyltrimethoxy silanes respectively from each dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.12%.The solid state component content of the acrylic acid or the like emulsion that obtains is 45.5%, the single 102nm that is distributed in of particle diameter.
[preparation example 7 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.In reactor, drop into 292 parts of water, 8 parts of sulfosuccinic acids reactive surfactant (ProductNames: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 18 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 78 parts of n-BMAs, 4 parts of methacrylic acids, 1 part of benzotriazole category UV light absorber (ProductName: TINUVIN384, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes), the mixture of 1 part of hindered amine light stabilizer (ProductName: TINUVIN123, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes); 5.3 the non-response type surfactant active of part sulfosuccinic acids (ProductName, エ ア ロ ゾ Le OT-75 (effective constituent: about 75%), Mitsui サ イ テ イ Network (strain) makes); 16 parts of 25% aqueous solution that contain the anionic reactive surfactant (ProductName: ア Network ア ロ Application KH-10, the first industrial pharmacy (strain) manufacturing) of oxyalkylene group; 2% the aqueous solution of 30 parts of ammonium persulphates; The emulsification mixed solution of forming with 90.7 parts of water, and the mixed solution of forming by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 25 parts of methyltrimethoxy silanes, 1.5 parts of dimethyldimethoxysil,ne from dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixed solution of 27 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 13 parts of n-BMAs, 10 parts of methacrylic acids, 0.5 part of TINUVIN384,0.5 part of TINUVIN123; 2.7 part エ ア ロ ゾ Le OT-75; 25% aqueous solution of 8 parts of ア Network ア ロ Application KH-10; 2% the aqueous solution of 15 parts of ammonium persulphates; The emulsification mixed solution of forming with 45.3 parts of water flowed into 40 minutes from each dropping bath respectively.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixture of 18 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 78 parts of n-BMAs, 4 parts of methacrylic acids, 1 part of TINUVIN384,1 part of TINUVIN123; 5.3 part エ ア ロ ゾ Le OT-75; 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10; 2% the aqueous solution of 30 parts of ammonium persulphates; Emulsification mixed solution of forming with 90.7 parts of water and the mixed solution formed by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 25 parts of methyltrimethoxy silanes, 1.5 parts of dimethyldimethoxysil,ne respectively from each dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.2.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.13%.The solid state component content of the acrylic acid or the like emulsion that obtains is 45.2%, the single 108nm that is distributed in of particle diameter.
[preparation example 8 of water dispersion]
Be ready to be equipped with the reactor of stirrer, reflux cooler, 2 dropping baths and thermometer, assemble 2 dropping baths and make that reaction raw materials can (exit of Y-piece embeds 100 purpose wire cloths by Y-piece, fill モ レ キ ユ ラ シ-Block ス 3A (ProductName: and the pure medicine of light (strain) is made) up to the place that the liquid mixing of 2 dropping baths is compiled, adjust then so that contain the pre-emulsion and the water-disintegrable silane of free radical polymerization monomer and can leniently mix.) flow in the reaction system.In reactor, drop into 292 parts of water, 8 parts of anionic reactive surfactant (ProductNames: ア Network ア ロ Application KH-10 that contain oxyalkylene group, the first industrial pharmacy (strain) manufacturing) 25% aqueous solution, temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 18 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 78 parts of n-BMAs, 4 parts of methacrylic acids, 1 part of benzotriazole category UV light absorber (ProductName: TINUVIN384, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes), the mixture of 1 part of hindered amine light stabilizer (ProductName: TINUVIN123, チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes); 16 parts of 25% aqueous solution that contain the anionic reactive surfactant (ProductName: ア Network ア ロ Application KH-10, the first industrial pharmacy (strain) manufacturing) of oxyalkylene group; 2% the aqueous solution of 30 parts of ammonium persulphates; The emulsification mixed solution of forming with 119 parts of water, and the mixed solution of forming by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 25 parts of methyltrimethoxy silanes, 1.5 parts of dimethyldimethoxysil,ne from dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixed solution of 27 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 13 parts of n-BMAs, 10 parts of methacrylic acids, 0.5 part of TINUVIN384,0.5 part of TINUVIN123; 25% aqueous solution of 8 parts of ア Network ア ロ Application KH-10; 2% the aqueous solution of 15 parts of ammonium persulphates; The emulsification mixed solution of forming with 46 parts of water flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, by the mixture of 18 parts of methyl methacrylates, 100 parts of cyclohexyl methacrylates, 78 parts of n-BMAs, 4 parts of methacrylic acids, 1 part of TINUVIN384,1 part of TINUVIN123; 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10; 2% the aqueous solution of 30 parts of ammonium persulphates; Emulsification mixed solution of forming with 119 parts of water and the mixed solution formed by 0.5 part of rare acyloxy propyl trimethoxy silicane of γ-third, 25 parts of methyltrimethoxy silanes, 1.5 parts of dimethyldimethoxysil,ne respectively from each dropping bath by above-mentioned Y-piece with inflow in 80 minutes.In silicone-modified reaction, keep pH below 4.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.1.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.11%.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.7%, the single 107nm that is distributed in of particle diameter.
[preparation example 9 of water dispersion]
To stirrer is housed, reflux cooler, drop into 290 parts of water in the reactor of dropping bath and thermometer, 10 parts of aniorfic surfactant (ProductNames: ア Network ア ロ Application KH-10 that contain oxyalkylene group, the first industrial pharmacy (strain) manufacturing) 25% aqueous solution, temperature from reactor rises to 80 ℃ and begins to calculate, at 2% aqueous solution that adds 10 parts of ammonium persulphates after 5 minutes, by 25 parts of methyl methacrylates, 50 parts of cyclohexyl methacrylates, 15 parts of butyl acrylates, 10 parts of methacrylic acids, 25% aqueous solution of 4 parts of ア Network ア ロ Application KH-10,5 parts of 20% aqueous solution that contain the nonionic surface active agent (ProductName: エ マ Le ゲ Application 120, flower king (strain) manufacturing) of oxyalkylene group, 2% the aqueous solution of 15 parts of ammonium persulphates, the emulsification mixed solution of 48 parts of water formation flowed into 40 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 30 minutes at 80 ℃.
Then, the emulsification mixed solution that is formed by 2% the aqueous solution of 109 parts of methyl methacrylates, 160 parts of cyclohexyl methacrylates, 123 parts of butyl acrylates, 8 parts of methacrylic acids, 25% aqueous solution of 16 parts of ア Network ア ロ Application KH-10,20% aqueous solution of 20 parts of エ マ Le ゲ Application 120,60 parts of ammonium persulphates, 192 parts of water flowed into 160 minutes from dropping bath.The temperature of reactor remains on 80 ℃ in inflow.Begin to calculate when flow into finishing, the temperature of reactor was kept 120 minutes at 80 ℃.
After being cooled to room temperature, measure hydrogen ion concentration, pH is 2.0.Add 25% ammonia soln adjustment pH to 8, filter with 100 purpose wire cloths.With respect to whole monomers, the dry mass of filtering condensation product is small 0.07%.The solid state component content of the acrylic acid or the like emulsion that obtains is 44.5%, the single 98nm that is distributed in of particle diameter.
[embodiment 1]
In 223.7 parts of water dispersions that in water dispersion preparation example 1, obtain, according to 4 parts of sulfosuccinic acids tensio-active agents (ProductName: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), 2 parts of aniorfic surfactant (ProductNames: レ ベ ノ-Le WZ (effective constituent: about 26%) that contain oxyalkylene group, flower king (strain) makes), 2.5 part is contained the nonionic surface active agent (ProductName: エ マ Le ゲ Application 920 of oxyalkylene group, flower king (strain) manufacturing) 20% aqueous solution, 33.3 part silica gel (ProductName: ス ノ-テ Star Network ス-30, daily output chemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 42.6% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 2]
In 222.7 parts of water dispersions that in water dispersion preparation example 2, obtain, according to 2 parts of sulfosuccinic acids tensio-active agents (ProductName: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), 2 parts of aniorfic surfactant (ProductNames: エ マ-Le 20C (effective constituent: about 25%) that contain oxyalkylene group, flower king (strain) makes), 2.5 part is contained the nonionic surface active agent (ProductName: エ マ Le ゲ Application 130K of oxyalkylene group, flower king (strain) manufacturing) 20% aqueous solution, 33.3 part silica gel (ProductName: ア デ ラ イ ト AT-30, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 42.7% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 3]
In 222.7 parts of water dispersions that obtain in water dispersion preparation example 2,33.3 parts of silica gel of uniform mixing (ProductName: ア デ ラ イ ト AT-30, rising sun electrochemical industry (strain) is made) obtain solid state component content and are 43.1% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 4]
In 223.2 parts of water dispersions that in water dispersion preparation example 3, obtain, according to 4 parts of sulfosuccinic acids tensio-active agents (ProductName: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), 2 parts of aniorfic surfactant (ProductNames: エ マ-Le 20C (effective constituent: about 25%) that contain oxyalkylene group, flower king (strain) makes), 2.5 part is contained the nonionic surface active agent (ProductName: エ マ Le ゲ Application 120 of oxyalkylene group, flower king (strain) manufacturing) 20% aqueous solution, 33.3 part silica gel (ProductName: ス ノ-テ Star Network ス-30, daily output chemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 44.0% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 5]
In 223.7 parts of water dispersions that in water dispersion preparation example 4, obtain, according to 4 parts of sulfosuccinic acids tensio-active agent (ProductNames, エ ア ロ ゾ Le OT-75 (effective constituent: about 75%), Mitsui サ イ テ イ Network (strain) is made), 2 parts of aniorfic surfactant (ProductNames: レ ベ ノ-Le WZ (effective constituent: about 26%) that contain oxyalkylene group, flower king (strain) makes), 2.5 part is contained the nonionic surface active agent (ProductName: ニ ユ-コ-Le 506 of oxyalkylene group, Japan's emulsifying agent (strain) manufacturing) 20% aqueous solution, 25 parts of silica gel (ProductNames: ア デ ラ イ ト AT-40, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 44.2% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 6]
In 223.7 parts of water dispersions that in water dispersion preparation example 4, obtain, according to 6 parts of sulfosuccinic acids tensio-active agents (ProductName: ラ テ system Le S-180A (effective constituent: about 50%), flower king (strain) makes), 2.5 part is contained the nonionic surface active agent (ProductName: ニ ユ-コ-Le 506 of oxyalkylene group, Japan's emulsifying agent (strain) manufacturing) 20% aqueous solution, 50 parts of silica gel (ProductNames: ス ノ-テ Star Network ス-C, daily output chemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 40.1% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 7]
In 223.7 parts of water dispersions that in water dispersion preparation example 4, obtain, according to 8 parts of sulfosuccinic acids tensio-active agents (ProductName: エ レ ミ ノ-Le JS-2 (effective constituent: about 38%), Sanyo changes into industry (strain) and make), 50 parts of silica gel (ProductNames: ア デ ラ イ ト AT-20A, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 40.0% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 8]
In 219.8 parts of water dispersions that in water dispersion preparation example 5, obtain, according to 1.5 parts of sulfosuccinic acids tensio-active agent (ProductNames, エ ア ロ ゾ Le OT-75 (effective constituent: about 75%), Mitsui サ イ テ イ Network (strain) makes), 33.3 parts of silica gel (ProductNames: ア デ ラ イ ト AT-30A, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 43.6% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 9]
In 219.8 parts of water dispersions that in water dispersion preparation example 6, obtain, according to 1.5 parts of sulfosuccinic acids tensio-active agents (ProductName: ペ レ Star Network ス OT-P (effective constituent: about 70%), flower king (strain) makes), 33.3 parts of silica gel (ProductNames: ア デ ラ イ ト AT-30, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 43.6% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 10]
In 219.8 parts of water dispersions that obtain in water dispersion preparation example 7,33.3 parts of silica gel of uniform mixing (ProductName: ア デ ラ イ ト AT-30A, rising sun electrochemical industry (strain) is made) obtain solid state component content and are 43.2% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[embodiment 11]
In 223.7 parts of water dispersions that in water dispersion preparation example 8, obtain, according to 2.7 parts of sulfosuccinic acids tensio-active agent (ProductNames, エ ア ロ ゾ Le OT-75 (effective constituent: about 75%), Mitsui サ イ テ イ Network (strain) makes), 33.3 parts of silica gel (ProductNames: ア デ ラ イ ト AT-30A, rising sun electrochemical industry (strain) is made) the order uniform mixing, obtain solid state component content and be 43.1% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[comparative example 1]
Water dispersion that will obtain in water dispersion preparation example 7 and aforementioned coating mix, and carry out each test.The result is as shown in table 1.
[comparative example 2]
In 224.7 parts of water dispersions that in water dispersion preparation example 7, obtain, the order uniform mixing of 33.3 parts of silica gel of uniform mixing (ProductName: ス ノ-テ Star Network ス-30, daily output chemical industry (strain) are made) obtains solid state component content and is 42.6% the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid coating in the coating composition, carry out each test.The result is as shown in table 1.
[comparative example 3]
The composition that 90 parts of dimethyl annular compounds (ring-type dimethyl siloxane oligopolymer 3～7 polymers mixtures), the 10 parts of rare acyloxy propyl group of γ-third dimethoxy-methyl silane (graft crosslinking agent), 300 parts of deionized waters and 0.5 part of Sodium dodecylbenzene sulfonate (tensio-active agent) are formed in homogenizer after the pre-mixing, 200kg/cm in addition in homogenizer 2Press-cutting, carry out forced emulsification and obtain polysiloxane raw material emulsion.
Then, 100 parts of deionized waters and 10 parts of Witco 1298 Soft Acids (acid emulsifying agent) are fed in the flask that stirrer, condenser, temperature-control device and dropping liquid pump are housed, keep the interior temperature of flask at 85 ℃, in 3 hours, drip above-mentioned polysiloxane raw material emulsion simultaneously.After the dropping, further heated 1 hour, after continuing to stir, the emulsion that obtains is cooled to room temperature, use in the sodium hydroxide and Witco 1298 Soft Acid, obtain silicone emulsions (hereinafter referred to as SEm1).The number-average molecular weight of the polysiloxane that obtains (GPC measured value) is about 100,000.
With 500 parts of SEm1,164 parts of deionized waters and 2.4 parts of Potassium Persulphates are fed into stirrer are housed, condenser, temperature-control device, in the flask of dropping liquid pump and nitrogen ingress pipe, be warming up to after 70 ℃, under nitrogen atmosphere, stir, in 4 hours, drip 168 parts of methacrylic acids (hereinafter referred to as MMA) simultaneously, 168 parts of n-BMAs (hereinafter referred to as n-BMA), 44 parts of methacrylic acid 2-ethyl cyclohexyls (hereinafter referred to as 2-EHA) and 8 parts of methacrylic acids (hereinafter referred to as MMA), the mixture of 12 parts of diacetone third rare acid amides (hereinafter referred to as DAAm).After drip finishing, kept 1 hour, further be warming up to 80 ℃ and kept 1 hour at 70 ℃.Reaction solution is cooled to room temperature, obtains graft block copolymer emulsion with the ammoniacal liquor neutralization.Carry out to polymerization-stable, do not find the generation of condensation product.
Then, under agitation (dioxide-containing silica is 30 weight %, and daily output chemical industry (strain) is made, trade(brand)name: ス ノ-テ Star Network ス-30), at room temperature kept 1 hour to silica gel aqueous dispersions that wherein to add 500 parts of median sizes be 10～20nm.Under agitation add 7.6 parts of ethylene acid hydrazides (hereinafter referred to as ADH), 100 parts of ethylene glycol monobutyl ethers then, further stirred 30 minutes, obtain the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid enamel paint in the coating composition, carry out each test.The result is as shown in table 1.
[comparative example 4]
The composition that 90 parts of dimethyl annular compounds (ring-type dimethyl siloxane oligopolymer 3～7 polymers mixtures), the 10 parts of rare acyloxy propyl group of γ-third dimethoxy-methyl silane (graft crosslinking agent), 300 parts of deionized waters and 0.5 part of Sodium dodecylbenzene sulfonate (tensio-active agent) are formed in homogenizer after the pre-mixing, 200kg/cm in addition in homogenizer 2Press-cutting, carry out forced emulsification and obtain polysiloxane raw material emulsion.
Then, 100 parts of deionized waters and 10 parts of Witco 1298 Soft Acids (acid emulsifying agent) are fed in the flask that stirrer, condenser, temperature-control device and dropping liquid pump are housed, keep the interior temperature of flask at 85 ℃, in 3 hours, drip above-mentioned polysiloxane raw material emulsion simultaneously.After the dropping, further heated 1 hour, after continuing to stir, the emulsion that obtains is cooled to room temperature, use in the sodium hydroxide and Witco 1298 Soft Acid, obtain silicone emulsions (hereinafter referred to as SEm1).The number-average molecular weight of the polysiloxane that obtains (GPC measured value) is about 100,000.
With 500 parts of SEm1,164 parts of deionized waters and 2.4 parts of Potassium Persulphates are fed into stirrer are housed, condenser, temperature-control device, in the flask of dropping liquid pump and nitrogen ingress pipe, be warming up to after 70 ℃, under nitrogen atmosphere, stir, in 4 hours, drip 168 parts of methacrylic acids (hereinafter referred to as MMA) simultaneously, 168 parts of n-BMAs (hereinafter referred to as n-BMA), 44 parts of methacrylic acid 2-ethyl cyclohexyls (hereinafter referred to as 2-EHA) and 8 parts of methacrylic acids (hereinafter referred to as MMA), the mixture of 12 parts of diacetone third rare acid amides (hereinafter referred to as DAAm).After drip finishing, kept 1 hour, further be warming up to 80 ℃ and kept 1 hour at 70 ℃.Reaction solution is cooled to room temperature, obtains graft block copolymer emulsion with the ammoniacal liquor neutralization.Carry out to polymerization-stable, do not find the generation of condensation product.
Then, under agitation (dioxide-containing silica is 30 weight %, and daily output chemical industry (strain) is made, trade(brand)name: ス ノ-テ Star Network ス-30), kept 1 hour at 60 ℃ to silica gel aqueous dispersions that wherein to add 200 parts of median sizes be 10～20nm.
Under agitation add 7.6 parts of ethylene acid hydrazides (hereinafter referred to as ADH), 100 parts of ethylene glycol monobutyl ethers then, further stirred 30 minutes, obtain the antifouling coating composition of using of water-based.Antifouling to this water-based with mixing aforesaid enamel paint in the coating composition, carry out each test.The result is as shown in table 1.
Table 1
Paint stability Water contact angle (degree) Water tolerance Rainwater pollution Weathering resistance
Embodiment 1 ○ 50 △ ◎ △
Embodiment 2 ○ 72 △ ◎ △
Embodiment 3 ○ 74 ○ ○ ○
Embodiment 4 ○ 70 △ ◎ △
Embodiment 5 ○ 70 △ ◎ △
Embodiment 6 ○ 72 △ ○ △
Embodiment 7 ○ 70 ○ ○ △
Embodiment 8 ○ 65 ◎ ◎ ◎
Embodiment 9 ○ 68 ◎ ○ ◎
Embodiment 10 ○ 65 ◎ ◎ ◎
Embodiment 11 ○ 65 ◎ ◎ ◎
Comparative example 1 ○ 82 ◎ × ◎
Comparative example 2 × 78 ○ × ○
Comparative example 3 × 87 △ ○ △
Comparative example 4 × 85 △ ◎ △
Industrial applicibility
Antifouling water-based coating composition of the present invention is applied to aqueous coating, when outdoor, can reduce its rain line shape by filming of forming of said composition exposing to the open air, particularly can prevent the pollution after just formation is filmed, can also long term maintenance reduce the effect that rain line shape pollutes. And the storage stability of this coating liquid is good.

Claims (21)

1. antifouling water-based coating composition wherein comprises (A) aqueous dispersion, (B) colloidal inorganic particle and (C) sulfosuccinic acids tensio-active agent.
2. water-based paint compositions as claimed in claim 1 wherein further comprises the tensio-active agent that (D) contains oxyalkylene group.
3. water-based paint compositions as claimed in claim 1 or 2, wherein (A) aqueous dispersion be a kind of (C) sulfosuccinic acids tensio-active agent and/or (D) contain oxyalkylene group tensio-active agent in the presence of, the acrylic acid or the like emulsion that obtains by emulsion polymerization.
4. as each described water-based paint compositions in the claim 1 to 3, the water contact angle of filming after its film forming is below 75 °.
5. as each described water-based paint compositions in the claim 2 to 4, wherein with respect to the resin solid state component of (A) aqueous dispersion of 100 weight parts, (B) amount of colloidal inorganic particle is 0.1～95 weight part, (C) amount of sulfosuccinic acids tensio-active agent is 0.1～20 weight part, and the amount that (D) contains the tensio-active agent of oxyalkylene group is 0.1～5 weight part.
6. as each described water-based paint compositions in the claim 1 to 5, wherein (A) aqueous dispersion is polysiloxane-modified acrylic acid or the like emulsion.
7. as each described water-based paint compositions in the claim 1 to 6, wherein (A) aqueous dispersion is the acrylic acid or the like emulsion that is formed by (E) vinyl unsaturated monomer emulsion polymerization in the presence of (F) water-disintegrable silane.
8. water-based paint compositions as claimed in claim 7, wherein (F) water-disintegrable silane comprises the following general formula (a) of stating
(R 1) n-Si-(R 2) 4-n (a)
(n is 0～3 integer in the formula, R 1Be that to be selected from hydrogen atom, carbonatoms be that 1～16 aliphatic alkyl, carbonatoms are that 5～10 aryl, carbonatoms are that 5～6 cycloalkyl, vinyl, carbonatoms are that 1～10 acrylic acid alkyl and carbonatoms are 1～10 methacrylic dialkylaminobenzoic acid; N R 1Can be the same or different; R 2Be selected from carbonatoms and be 1～8 alkoxyl group, acetoxyl group or hydroxyl; 4-n R 2Can be the same or different.) shown in silane.
9. as claim 7 or 8 described water-based paint compositions, wherein (F) water-disintegrable silane comprises with 100/1～1/100 mol ratio: at least a in the silane (II) when silane (I) when being selected from n=0 in the aforementioned formula (a) and n=1 and, silane (IV), the cyclic silane the when silane when being selected from n=2 (III), n=3 and have at least a in the chain siloxanes of hydrolization group.
10. as each described water-based paint compositions in the claim 1 to 9, wherein (B) colloidal inorganic particle comprises the colloidal inorganic particle that is coated by organic polymer.
11. as each described water-based paint compositions in the claim 1 to 10, wherein (B) colloidal inorganic particle is a silica gel.
12. as each described water-based paint compositions in the claim 1 to 11, wherein (C) sulfosuccinic acids tensio-active agent is not for containing the sulfosuccinic acids tensio-active agent of free-radical polymerised pair of key.
13. as each described water-based paint compositions in the claim 2 to 12, wherein (D) to contain the tensio-active agent of oxyalkylene group be the tensio-active agent with the free-radical polymerised pair of key that contains oxyalkylene group.
14. as each described water-based paint compositions in the claim 1 to 13, wherein (A) aqueous dispersion is the acrylic acid or the like emulsion that is formed by (E) vinyl unsaturated monomer emulsion polymerization, should contain above (methyl) acrylate that contains cycloalkyl of 5 weight % by (E) vinyl unsaturated monomer.
15., it is characterized in that using it for the purposes of coating as each described water-based paint compositions in the claim 1 to 14.
16. contain the coating of the water-based paint compositions of claim 15 record.
17. use the coated article of the applying coating of claim 16.
18. use claim 16 applying coating outer wall materials.
19. use the buildings of the applying coating of claim 16.
20. contain the stain resistance mixture of the coating that the coating of useful claim the 16 forms.
21. a coating method is characterized in that using the coating of claim 16.
CNB038032899A 2002-02-04 2003-02-03 Antifouling water-based coating composition Expired - Fee Related CN100357367C (en)

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CN101851413B (en) * 2009-03-31 2012-07-18 3M创新有限公司 Paint composition, anti-foul easy-cleaning product and preparation method thereof
CN110627949A (en) * 2013-03-14 2019-12-31 阿克佐诺贝尔国际涂料股份有限公司 Hybrid latex emulsions and coating compositions formed from hybrid latex emulsions
CN113004605A (en) * 2021-03-02 2021-06-22 苏州市金泽利塑料有限公司 Preparation method of friction-resistant polyethylene sandbag
CN114044857A (en) * 2021-12-02 2022-02-15 万华化学集团股份有限公司 Preparation method of polyacrylate aqueous dispersion with rich carboxyl groups on surface, dispersion and application thereof
CN116694217A (en) * 2023-07-03 2023-09-05 天津市职业大学 Solar catalysis self-cleaning paint and preparation and application methods thereof

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JPH08231887A (en) * 1995-02-22 1996-09-10 Nisshin Chem Ind Co Ltd Anti-fogging agent composition
JPH11116885A (en) * 1997-10-21 1999-04-27 Nippon Paint Co Ltd Low-fouling water-based coating material composition
JPH11263936A (en) * 1998-03-18 1999-09-28 Toagosei Co Ltd Coating composition
JP4531922B2 (en) * 2000-04-12 2010-08-25 株式会社カネカ Water-based paint composition

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Publication number Priority date Publication date Assignee Title
CN101851413B (en) * 2009-03-31 2012-07-18 3M创新有限公司 Paint composition, anti-foul easy-cleaning product and preparation method thereof
CN110627949A (en) * 2013-03-14 2019-12-31 阿克佐诺贝尔国际涂料股份有限公司 Hybrid latex emulsions and coating compositions formed from hybrid latex emulsions
CN113004605A (en) * 2021-03-02 2021-06-22 苏州市金泽利塑料有限公司 Preparation method of friction-resistant polyethylene sandbag
CN114044857A (en) * 2021-12-02 2022-02-15 万华化学集团股份有限公司 Preparation method of polyacrylate aqueous dispersion with rich carboxyl groups on surface, dispersion and application thereof
CN114044857B (en) * 2021-12-02 2024-04-09 万华化学集团股份有限公司 Preparation method of polyacrylate aqueous dispersion with carboxyl-rich surface, dispersion and application of polyacrylate aqueous dispersion
CN116694217A (en) * 2023-07-03 2023-09-05 天津市职业大学 Solar catalysis self-cleaning paint and preparation and application methods thereof

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