CN102449083A - Additive for coating material, and coating material containing same - Google Patents
Additive for coating material, and coating material containing same Download PDFInfo
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- CN102449083A CN102449083A CN2010800233266A CN201080023326A CN102449083A CN 102449083 A CN102449083 A CN 102449083A CN 2010800233266 A CN2010800233266 A CN 2010800233266A CN 201080023326 A CN201080023326 A CN 201080023326A CN 102449083 A CN102449083 A CN 102449083A
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- ethylenic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Disclosed is an additive for a coating material, which is an additive for obtaining an aqueous coating material that has an excellent balance among all the properties such as weather resistance and surface tackiness and is capable of forming a coating film that has excellent water resistance and contamination resistance. Also disclosed is an aqueous coating material which contains the additive for a coating material. Specifically, the coating material contains an additive for a coating material which contains (A) an aqueous resin that is obtained by polymerizing (a) a polymerizable unsaturated monomer. The (A) aqueous resin has an acid value of 20-60 mgKOH/g, and the (a) polymerizable unsaturated monomer contains (a1) a monomer that has a hydroxyl group and an ethylenic double bond. Consequently, the coating material has an excellent balance among all the properties such as weather resistance and surface tackiness, and is capable of forming a coating film that has excellent water resistance and contamination resistance. The (a) polymerizable unsaturated monomer preferably contains (a2) a monomer that has an alkoxysilyl group and an ethylenic double bond. The additive for a coating material can be used as a contamination resistance-providing agent.
Description
Technical field
The present invention relates to coating with additive and the coating that contains this additive.
Background technology
As the desired performance of in buildings and application, using of outer coatings, except the weathering resistance of filming that forms by coating, the stain resistance that the rainfall pollution that in most cases will consider to produce for wind and rain, waste gas, dust, sand etc. etc. are polluted.In recent years, in paint field, also consider environmentally friendlyly etc., constantly carry out the displacement to water system from solvent system, but the tendency that aqueous coating has is low by its hardness of filming that forms, stain resistance reduces.
Patent documentation 1 discloses a kind of low pollution agent, and it surpasses 10% polymkeric substance the containing of the repeating unit that has 2 above hydroxyls more than 1 and this repeating unit proportional (weight basis) and constitute by containing.
It is the coating agent that patent documentation 2 discloses a kind of solvent; It comprises: will contain α; The organoalkoxysilane of β-single ethylenic unsaturated group, contain α; The hydroxy alkyl ester of β-single ethylenic unsaturated group, other contain α, but other of the compound of β-single ethylenic unsaturated group and copolymerization contain α, and the weight-average molecular weight that the compound of β-single ethylenic unsaturated group obtains through the solution polymerization of having used organic solvent is 3000～200000 vinyl-based resin.
But among the embodiment of patent documentation 1, because the water tolerance of resin is insufficient, therefore formed water tolerance of filming is insufficient.In addition, low pollutionization agent can be flowed out from resulting resin, and therefore low pollutant performance can reduce.
The coating agent of patent documentation 2 is because stain resistance and resin stable insufficient and be that solvent is, so is difficult in the water system purposes, use.
If the consideration environmental problem then requires increasingly high performance for aqueous coating from now on.In the coating industry, the task of top priority is exploitation a kind of formed water tolerance of filming and stain resistance is good and over-all propertieies such as weathering resistance and surface viscosity balancedly keep good water-borne coatings.
Patent documentation 1:JP2003-055617A
Patent documentation 2:JP2005-232265A
Summary of the invention
Invent technical problem to be solved
The present invention carries out in view of such situation; Its purpose is to provide a kind of coating with additive and contain the water-borne coatings of such coating with additive, and this coating is used to obtain formed water tolerance of filming with additive and stain resistance is good and over-all propertieies such as weathering resistance and surface viscosity balancedly keep good water-borne coatings.
Be used to solve the means of problem
The inventor has carried out deep research repeatedly; The result finds, for containing the coating of following coating with additive, in the time of in the acid number with water-base resin is controlled at specific scope; Water tolerance of filming and stain resistance by coating forms are good; And weathering resistance and surface viscosity etc. in general balancedly keep good, and said coating contains with additive the polymerizability unsaturated monomer that comprises specific monomer is carried out polymerization and the water-base resin that obtains, thereby has accomplished the present invention.
Promptly; First purport of the present invention provides a kind of coating and uses additive; It contains and (a) polymerizability unsaturated monomer is carried out polymerization obtains (A) water-base resin; Wherein, (A) acid number of water-base resin is 20～60mgKOH/g, and (a) the polymerizability unsaturated monomer comprises the monomer that (a1) has hydroxyl and the two keys of ethylenic.
Coating of the present invention through in the coating that adds particularly outer dress usefulness to, can be given good performance with additive to coating.Particularly can be preferably used as the anti-pollution agent.
The present invention provides a kind of coating to use additive in first scheme, and wherein, (a) the polymerizability unsaturated monomer also comprises the monomer that (a2) has alkoxysilyl and the two keys of ethylenic.
The present invention provides a kind of coating to use additive in another program, and wherein, (a) the polymerizability unsaturated monomer also comprises (a4) other monomers.
Another purport of the present invention provides a kind of coating, and it contains above-mentioned coating uses additive.
The invention effect
Coating of the present invention contains with additive and (a) polymerizability unsaturated monomer is carried out polymerization obtains (A) water-base resin; Wherein, (A) acid number of water-base resin is 20～60mgKOH/g, and the polymerizability unsaturated monomer comprises the monomer that (a1) has hydroxyl and the two keys of ethylenic.Therefore; Compare with additive with coating in the past; When using coating of the present invention to use additive, can access formed water tolerance of filming and stain resistance is good and over-all propertieies such as weathering resistance and surface viscosity balancedly keep good water-borne coatings.
Coating of the present invention also comprises under the monomeric situation that (a2) have the two keys of alkoxysilyl and ethylenic at (a) polymerizability unsaturated monomer with additive, can access the water-borne coatings that formed stain resistance of filming further improves.
Coating of the present invention also comprises under (a4) other monomeric situation at (a) polymerizability unsaturated monomer with additive; Can control the second-order transition temperature (Tg) of (A) water-base resin with being more prone to, can make by containing the surface viscosity performance of filming, the anti-fouling performance raising that the water-borne coatings of coating of the present invention with additive forms.
Coating of the present invention can be used as the anti-pollution agent with additive.
Coating of the present invention is owing to contain coating of the present invention and use additive, so formed stain resistance of filming and having excellent water-resistance, and performances such as weathering resistance and surface viscosity performance is harmonious good.Therefore coating of the present invention particularly can suit to use in outdoor buildings because formed stain resistance of filming etc. are good.
Embodiment
Coating of the present invention contains with additive and (a) polymerizability unsaturated monomer is carried out polymerization obtains (A) water-base resin; Wherein, (A) acid number of water-base resin is 20～60mgKOH/g, and (a) the polymerizability unsaturated monomer comprises the monomer that (a1) has hydroxyl and the two keys of ethylenic.
Among the present invention, " (a) polymerizability unsaturated monomer " is meant the free radical polymerization monomer with the two keys of ethylenic.As (a) polymerizability unsaturated monomer, can illustration go out: the monomer of the two keys of hydroxyl and ethylenic " (a1) have ", the monomer of the two keys of alkoxysilyl and ethylenic " (a2) have ", the monomer of the two keys of acidic group and ethylenic " (a3) have " and " (a4) other have the monomer of ethylenic pair keys ".(a) the polymerizability unsaturated monomer comprises (a1) monomer, according to circumstances can comprise (a2)～(a4) monomer.
In this specification sheets, " the two keys of ethylenic " are meant two keys between the carbon atom that can carry out polyreaction (radical polymerization).Functional group as having the two keys of such ethylenic for example can illustration go out: vinyl (CH
2=CH-), (methyl) allyl group (CH
2=CH-CH
2-and CH
2=C (CH
3)-CH
2-), (methyl) acryloxy (CH
2=CH-COO-and CH
2=C (CH
3)-COO-), (methyl) acryloyloxyalkyl (CH
2=CH-COO-R-and CH
2=C (CH
3)-COO-R-) and-COO-CH=CH-COO-etc.
In addition, in this specification sheets, vinylformic acid and methylacrylic acid are generically and collectively referred to as " (methyl) vinylformic acid ", propenoate and methacrylic ester are also referred to as " (methyl) propenoate ".About the appellation of allyl group and acryloxy, also be same.
The monomer of the two keys of hydroxyl and ethylenic " (a1) have " (below; Be also referred to as " (a1) monomer ") be meant the compound that can in (A) water-base resin that obtains through Raolical polymerizable, introduce hydroxyl; So long as can access (A) water-base resin of the present invention and can access with the compound of additive just, have no particular limits as the coating of target.(a1) monomer that has two keys of hydroxyl and ethylenic has hydroxyl and the two keys of ethylenic simultaneously, and hydroxyl and ethylenic pair keys for example can carry out bonding through other functional groups such as ester bond, amido linkage and alkylidene groups.
Have the monomer of the two keys of hydroxyl and ethylenic as (a1), be preferably compound by following formula (I) expression.
(I)：CH
2＝CR
1-X-R
2
[wherein, in the formula (I), R
1Expression H, methyl or ethyl, X represent ester group or carboxamido-group (be preferably-COO-and-CONH-), R
2Expression has the functional group of hydroxyl].
R as formula (I)
2, being preferably hydroxyalkyl, the alkyl of hydroxyalkyl can have substituting group, also can have ring texture.As hydroxyalkyl, for example can illustration go out: hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxyl amyl group, 6-hydroxyl hexyl, 7-hydroxyl heptyl, 4-hydroxy-cyclohexyl, (4-hydroxymethyl cyclohexyl) methyl, 3-chloro-2-hydroxypropyl etc.
Contain hydroxyl and have the monomeric object lesson of the two keys of ethylenic as (a1), can illustration go out: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 5-hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl cyclohexyl, (methyl) vinylformic acid (4-methylol cyclohexyl) methyl esters, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, N-methylol (methyl) acrylic amide, (methyl) vinylformic acid hydroxy methyl, Hydroxyethyl Acrylate etc.If consider the equilibrium of water tolerance and stain resistance, then more preferably (methyl) vinylformic acid 2-hydroxy methacrylate.
The monomer of the two keys of alkoxysilyl and ethylenic " (a2) have " among the present invention (below be also referred to as " (a2) monomer ") is meant the compound that can in (A) water-base resin that obtains through Raolical polymerizable, introduce alkoxysilyl; So long as can access (A) water-base resin of the present invention and can access with the compound of additive just, have no particular limits as the coating of target.(a2) monomer that has two keys of alkoxysilyl and ethylenic has alkoxysilyl and the two keys of ethylenic simultaneously, and alkoxysilyl and ethylenic pair keys for example can carry out bonding through other functional groups such as ester bond, amido linkage and alkylidene groups.
Wherein, " alkoxysilyl " is meant through hydrolysis and introduces the siliceous functional group with the hydroxyl (Si-OH) of silicon bonding.As " alkoxysilyl ", for example can illustration go out: alkoxysilyls such as trimethoxysilyl, triethoxysilyl, dimethoxy silyl, dimethoxy-methyl silyl, diethoxy silyl, monosubstituted ethoxy silyl and mono methoxy silyl.Be preferably trimethoxysilyl and triethoxysilyl especially.About " the two keys of ethylenic " as stated.
Because (a) the polymerizability unsaturated monomer comprises (a2) monomer, therefore (A) water-base resin comprises alkoxysilyl.In the time will carrying out drying by filming of containing that the coating of coating of the present invention with additive forms; Alkoxysilyl generation dehydration condensation; Crosslinked in filming; Inside at (A) water-base resin perhaps can form crosslinking structure between (A) water-base resin, thus the raising of the weathering resistance that can help to film and water tolerance etc.In addition, according to thinking, after the drying of filming, on the surface of filming, can make coating of the present invention use the additive immobilization, therefore can make the stain resistance of filming and surface viscosity etc. long-term lasting.
Have the monomer of the two keys of alkoxysilyl and ethylenic as (a2), can illustration go out: by the compound of following formula (II) expression.
(II)：R
5Si(OR
6)(OR
7)(OR
8)
[wherein, in the formula (II), R
5For having the functional group of the two keys of ethylenic, R
6, R
7And R
8It for carbonatoms 1～5 alkyl.R
6, R
7And R
8Can be the same or different each other].
As R
5The functional group with the two keys of ethylenic, for example can illustration go out: vinyl, (methyl) allyl group, (methyl) acryloxy, 2-(methyl) acrylyl oxy-ethyl, 2-(methyl) acryloyl-oxy propyl group, 3-(methyl) acryloyl-oxy propyl group, 2-(methyl) acryloyl-oxy butyl, 3-(methyl) acryloyl-oxy butyl, 4-(methyl) acryloyl-oxy butyl.
As R
6, R
7, R
8Carbonatoms be 1～5 alkyl, for example can illustration go out: the alkyl of straight chain such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl and n-pentyl or side chain.
Contain alkoxysilyl and have the monomer of the two keys of ethylenic as (a2); Be preferably following compound: (a2-1) vinyl trialkyl oxysilanes such as vinyltrimethoxy silane, vinyltriethoxysilane and vinyl three n-butoxy silane; And by the compound of following formula (III) expression
(III)：CH
2＝CR
3-COO-Z-Si(OR
4)
3
[wherein, in the formula (III), R
3Expression H or CH
3, R
4The expression carbonatoms is that 1～3 alkyl, Z represent that carbonatoms is 1～6 alkylidene group].
Compound as formula (III) expression is preferably 3-(methyl) acryloyl-oxy propyl trimethoxy silicane and 3-(methyl) acryloyl-oxy propyl-triethoxysilicane, is preferably 3-(methyl) acryloyl-oxy propyl trimethoxy silicane especially.
These (a2) contain alkoxysilyl and have the monomer of the two keys of ethylenic, can suit to select according to the character of the coating that contains (A) water-base resin with additive, can use or make up use separately.
Among the present invention,, can use " monomer that (a3) has the two keys of acidic group and ethylenic " (below be also referred to as " (a3) monomer ") according to the acid number of (A) water-base resin.Wherein, The monomer of the two keys of acidic group and ethylenic " (a3) have " is meant the compound that can in (A) water-base resin that obtains through Raolical polymerizable, introduce acidic group; So long as can access (A) water-base resin of the present invention and can access with the compound of additive just, have no particular limits as the coating of target.
In this specification sheets, " acidic group " be meant release hydrogen ions in water and can form the functional group with corresponding negative charge functional group (for example-COOH and-SO
3H etc.), have this corresponding negative charge functional group (for example-COO
-And-SO
3 -Deng) and negative charge through the phase counter cation carry out charge neutrality functional group (for example-COO-Na
+And-SO
3 -K
+Deng).Certainly, these " in water release hydrogen ions and can form the functional group of the functional group with negative charge ", " functional group with negative charge " and " negative charge carries out the functional group of charge neutrality through the phase counter cation " for example change pH etc. according to the state around each functional group and can easily change each other.
Wherein, as " in water release hydrogen ions and can form the functional group of functional group ", for example can illustration go out: carboxyl (COOH), sulfonic group (perhaps sulfo group) (SO with negative charge
3H) and phosphate (PO
4H
2) etc.
In addition, as " negative charge carries out the functional group of charge neutrality through the phase counter cation " and " functional group ", for example can illustration go out: carboxylate group (COO with negative charge
-And-COOM
1), sulphonate-base (SO
3 -And-SO
3M
2) and phosphate base (PO
4H
-,-PO
4 2-And-PO
4M
3M
4) wait [wherein, M
1, M
2, M
3, and M
4Be basic metal, alkaline-earth metal or ammonium (M in addition,
3And M
4Any one all can be hydrogen)].
About " the two keys of ethylenic ", as stated.
As such " (a3) contain acidic group and have the monomer of the two keys of ethylenic ", for example can illustration go out following compound:
The half ester of vinylformic acid, methylacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid, toxilic acid etc. has the compound of carboxyl and the two keys of ethylenic and has carboxylate group and the compound of the two keys of ethylenic;
Styrene sulfonic acids etc. have the compound of sulfonic group and the two keys of ethylenic and have sulphonate-base and the compound of the two keys of ethylenic;
(methyl) vinylformic acid oxygen buserelin phosphoric acid salt etc. has the compound of phosphate and the two keys of ethylenic and has phosphate base and the compound of the two keys of ethylenic.
In addition, the phase counter cation of carboxylate group, sulphonate-base and phosphate base is preferably ammonium ion and alkalimetal ion class etc., is preferably ammonium ion, potassium ion and sodium ion especially.
The monomer that particularly has acidic group and the two keys of ethylenic as (a3) is preferably the compound with carboxyl and the two keys of ethylenic and has carboxylate group and the compound of the two keys of ethylenic, is preferably vinylformic acid and methylacrylic acid especially.
These (a3) monomers can use separately, and perhaps combination is used, can be according to the present invention as the coating of target with the use that suits of the characteristic of additive.
The present invention preferably provides (a) polymerizability unsaturated monomer also to comprise (a4) other monomeric coating and uses additive.
" (a4) other monomers " among the present invention (below be also referred to as " (a4) monomer ") be meant above-mentioned (a1)～(a3) in addition have the two keys of ethylenic and can with the monomer of above-mentioned (a1)～(a3) copolymerization (radical polymerization).Can suit according to character to use as (A) water-base resin of target.About " the two keys of ethylenic ", as stated.
(a4) to state second-order transition temperature (being designated hereinafter simply as " Tg ") very important after for control (A) water-base resin for other monomers.Can think that through further raising Tg, coating improves with the surface viscosity performance of additive, and anti-fouling performance also improves.
As (a4) other monomers, for example can illustration go out: (methyl) alkyl-acrylates, these materials are preferred.
As (methyl) alkyl-acrylates, for example can illustration go out: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) NSC 11786, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) decyl acrylate, (methyl) dodecylacrylate etc.
(methyl) alkyl-acrylates can use or make up use separately.
(A) of the present invention water-base resin can obtain through (a) polymerizability unsaturated monomer is carried out radical polymerization.As long as can access (A) water-base resin as target, the not special system limit of polymerization method can use common free radical polymerisation process to obtain (A) water-base resin.For example can (a) polymerizability unsaturated monomer be carried out polymerization in organic solvent, be replaced as aqueous medium then and obtain, this method is preferred.(A) water-base resin can be according to its characteristic such as water-soluble and is neutralized with alkaline matter where necessary.
(A) the water-base resin preferred preparation becomes the form of microemulsion, brings into play low pollutant performance with less amount.
Second-order transition temperature (Tg) about (A) water-base resin uses with additive if be considered as coating, then is preferably more than 20 ℃, more preferably more than 40 ℃, is preferably especially more than 60 ℃.This be because, be lower than at the Tg of (A) water-base resin under 20 ℃ the situation, if formed filming is exposed in the atmosphere, on then the pollution substance in the atmosphere can be attached to easily and film, stain resistance can reduce.
(A) Tg of water-base resin can set through regulating employed monomeric quality percentage.(A) Tg of the water-base resin monomeric quality percentage that can use following calculating formula (i) from the Tg of the homopolymer (homopolymer) that obtained by each monomer and (A) water-base resin, to use is obtained.Be benchmark preferably, confirm the monomer composition with the Tg that tries to achieve through this calculating.
(i)：1/Tg＝W1/Tg1+W2/Tg2+……+Wn/Tgn
[in the above-mentioned formula (i), Tg representes the second-order transition temperature of (A) water-base resin, W1, W2 ... Wn representes each monomeric quality percentage, Tg1, Tg2 ... Tgn representes the second-order transition temperature of corresponding monomeric homopolymer].In addition, the Tg of homopolymer can adopt " POLYMER HANDBOOK " (the 4th edition; John Wiley & Sons, Inc. distribution) etc. the numerical value of putting down in writing in the publication.
For example the Tg of following monomeric homopolymer is following:
2-hydroxyethyl methacrylate: 55 ℃
Methylacrylic acid: 130 ℃
TEB 3K: 105 ℃
N-butyl acrylate :-54 ℃
In addition, when calculating the Tg of (A) water-base resin, considered (a1) monomer, (a3) monomer and (a4) monomer, because (a2) monomer be a small amount of, therefore not consideration.
The hydroxyl value of (A) water-base resin among the present invention is preferably greater than 80mgKOH/g, more preferably more than the 210mgKOH/g, is preferably more than the 240mgKOH/g especially.
" hydroxyl value " expression mg number with the needed Pottasium Hydroxide of acetate of hydroxyl bonding that is used to during with the acetylize of 1g resin to neutralize in this specification sheets.
Among the present invention, particularly, (ii) calculate with following formula.
(ii): the weight of formula weight * 1000/ (A) water-base resin of the mole number * KOH of the hydroxyl that contains in 1 mole of the monomer of hydroxyl value=((a1) monomeric weight/(a1) monomeric molecular weight) * (a1)
The acid number of (A) of the present invention water-base resin is 20～60mgKOH/g.When (A) acid number of water-base resin was lower than 20mgKOH/g, (A) stain resistance stable and that film of water-base resin reduced, and when (A) acid number of water-base resin was higher than 60mgKOH/g, the water tolerance of filming reduced.Remain in the above-mentioned specific scope through acid number, when giving good water tolerance and stain resistance, can balancedly give performances such as weathering resistance and surface viscosity filming with (A) water-base resin.
In addition, about " acid number " of (A) of the present invention water-base resin, be assumed to all free acid that form of the acidic group that contains in the 1g resin, the calculated value of the mg number through the needed Pottasium Hydroxide of this acid that is used to neutralize is represented.Even therefore the form with alkali exists in the system of reality, also be thought of as free acid.This is corresponding with the acidic group that (a3) monomer comprises." acid number " of the present invention can (iii) try to achieve through following formula.
(iii): the weight of formula weight * 1000/ (A) water-base resin of the mole number * KOH of the acidic group that contains in 1 mole of the monomer of acid number=((a3) monomeric weight/(a3) monomeric molecular weight) * (a3)
For example, use the method for common solution polymerization, in organic solvent, use suitable catalyzer etc., above-mentioned (a) polymerizability unsaturated monomer is carried out radical polymerization, can carry out the polymerization of (a) polymerizability unsaturated monomer thus.Wherein, " organic solvent " do not have special qualification so long as can be used in polymerization (a) polymerizability unsaturated monomer, the coating after the polyreaction is not produced dysgenic organic solvent just in fact with the characteristic of additive.As such solvent, for example can illustration go out: ester and their combination such as lower alcohol such as methyl alcohol, ethanol and propyl alcohol and ETHYLE ACETATE.
(a) condition of polyreactions such as the kind of the kind of the polymeric temperature of reaction of polymerizability unsaturated monomer, reaction times, organic solvent, monomeric kind and concentration, stirring velocity and catalyzer and concentration can wait suitable the selection according to the characteristic as (A) water-base resin of target.
" catalyzer " is meant the polymeric compounds that can just cause (a) polymerizability unsaturated monomer through a small amount of interpolation, those catalyzer that preferably can in organic solvent, use.For example can illustration go out: ammonium persulphate, Sodium Persulfate, Potassium Persulphate, peroxidized t-butyl perbenzoate, 2; 2-Diisopropyl azodicarboxylate (AIBN) and 2; 2-azo two (2-amidine propane) dihydrochloride and 2,2-azo two (2, the 4-methyl pentane nitrile) etc.; Be preferably 2 especially, 2-Diisopropyl azodicarboxylate (AIBN).
Chain-transfer agent can suit to use in the polymerization of the present invention." chain-transfer agent " as being used to regulate molecular weight can use compound well known to those skilled in the art.For example can illustration go out: thio-alcohols such as n-dodecyl mercaptan and undecyl methyl mercaptan.
After the polymerization, preferred use medium displacement organic solvent.Use medium displacement organic solvent can use ordinary method.For example can illustration go out: the method for through distillation the organic solvent distillation being removed behind the method for adding aqueous medium, the adding aqueous medium after through distillation the organic solvent distillation being removed.
In this specification sheets, " aqueous medium " is meant so-called water such as zero(ppm) water, ion exchanged water and pure water, can comprise water miscible organic solvent, for example acetone and lower alcohol etc.Through organic medium is replaced as aqueous medium, can obtain (A) water-base resin.
According to the characteristic of (A) water-base resin, (A) water-base resin can neutralize.Wherein " neutralization " can be used for the neutral alkaline matter through adding usually and carry out.Its result, (A) anionic group of water-base resin, particularly carboxyl are neutralized, and can give water-soluble to (A) water-base resin.But (A) not need be water miscible to water-base resin fully, so long as the water-soluble of degree of the characteristic variation that adds the coating that coating of the present invention obtains with additive got final product.
In this specification sheets; " alkaline matter " is meant through dissolving in water and presents the material greater than 7 pH; Usually the form of alkaline matter can be gas, liquid and solid; Owing in water, can the water miscible form of dissolved handle and control easily neutralization reaction easily, be preferred therefore." alkaline matter " as such for example can illustration go out: earth alkali metal such as basic metal such as ammonia, sodium and potassium, calcium and magnesium etc. are preferably ammoniacal liquor, sodium water solution and aqueous solutions of potassium.
The preferred alkaline matter that adds reaches more than 8.0 the pH of the aqueous medium that contains (A) water-base resin, more preferably adds alkaline matter, makes pH reach 8.0～10.0, especially preferably adds alkaline matter, makes pH reach 8.0～9.5.
Coating of the present invention does not have special qualification so long as contain coating of the present invention with additive just.For example, be that all common coating of principal constituent are containing under the situation of coating of the present invention with additive with xylene resin, Synolac, urethane resin, epoxy resin, vinyl resin etc., include within coating of the present invention.
Coating of the present invention can be used as paint and also can be used as silane coupling agent (paint and so-called sealing agent in comprising) use.Wherein " go up paint " is also referred to as surfacer, and it is meant the coating in the outermost coating, and its raising etc. that is meant raising with outward appearance, glazing, water-proof raising, weathering resistance is the coating that purpose is coated with.And " silane coupling agent " is meant the coating beyond the paint, and it comprises: mainly be the sealing agent (also being sometimes referred to as substrate regulator or priming paint) of purpose and direct coating on base material with water-repellancy, moisture resistance, the adhering raising of base material etc.; And main the connection go up between paint and the sealing agent and be the middle paint that purpose is coated with the raising of water-repellancy, moisture resistance, anti-whipability etc.
Coating of the present invention can be coated on the various base materials.As base material, can on common all base materials such as metal, wood materials, plastics, inanimate matter building materials, be coated with.
Coating of the present invention can contain pigment well-known to those skilled in the art, weighting agent, rust-preventive agent, thickening material, dispersion agent, skimmer, sanitas, film coalescence aid etc. as required.
Pigment does not have special qualification so long as can form the material of pigment usually and get final product.Pigment is categorized as pigment dyestuff and mineral dye usually.
As pigment dyestuff, for example can illustration go out: isoindoline class pigment such as dyeing such as phthalocyanine pigments such as insoluble azo colour, copper phthalocyanine such as fast yellow, two azophosphines, two azo oranges and naphthol red, Fa Naer color lake, Weibull color lake and bordeaux (Katanol) color lake, isoindoline yellow-green colour and isoindoline yellowish red color etc., quinacridine ketone pigment, perylene scarlet with and perylene class pigment such as the brown red-purple of perylene etc.
As mineral dye, for example can illustration go out: carbon black, white lead, red lead, chrome yellow, cinnabar, ultramarine, powder blue, titanium oxide, titan yellow, strontium yellow, molybdenum red, strontium molybdate, iron oxide black, lithopone (Lithopone), emerald green, Guignet's green, cobalt blue etc.
Weighting agent is meant for performance raising, cost reduction etc. the material that adds, so long as usually as the material of weighting agent just, have no particular limits.Particularly, can illustration go out: lime carbonate, magnesiumcarbonate, silicon-dioxide, talcum, clay, aluminum oxide etc.
Rust-preventive agent is meant the material that is used to suppress raw-material corrosion and adds, so long as usually as the material of rust-preventive agent just, have no particular limits.For example can illustration go out: red lead, white lead, zinc impregnation lead, alkaline white lead sulfate, basic lead chromate, calcium plumbite, zinc chromium, plumbic acid urea anhydride, zinc powder, dichromate, baryta yellow, Sodium Nitrite, nitrous acid two hexamethylene ammoniums, cyclohexylamine carbonate, antirust wet goods.
Thickening material is not so long as usually as the material of thickening material just, have special qualification.For example, can illustration go out modified acrylic polymer as the thickening material of alkali-thickening type; As the thickening material of association type, can illustration go out urethane-modified polyethers and polyethers etc.As the thickening material of alkali-thickening type, for example can illustration go out: Natvosol (SP600 (trade(brand)name) Diacel chemical company system), SN Thickener 615 (trade(brand)name) (Sannopco Co., Ltd. system), ASE60 (trade(brand)name) (R&H Co., Ltd. system), KA10K (trade(brand)name) (Henkel Technologies Amada Co., Ltd. system) etc.In addition, as the thickening material of association type, for example can illustration go out: SN812 (trade(brand)name) (Sannopco Co., Ltd. system), RM8W (trade(brand)name) (R&H Co., Ltd. system), UH752 (trade(brand)name) (ADEKA Co., Ltd. system) etc.
Dispersion agent is not so long as usually as the material of dispersion agent just, have special qualification.For example can illustration go out: Potassium tripolyphosphate (peaceful chemical Industry Co., Ltd system), Primer 850 (trade(brand)name) (Rohm & Haas corporate system), Demoru EP (trade(brand)name) (Kao Corp's system), Discoat N-14 (trade(brand)name) (Di-ichi Kogyo Seiyaku Co., Ltd.'s system), Orotan 165A (trade(brand)name) (R&H system), SN Dispersant 5020 (trade(brand)name) (Sannopco Co., Ltd. system).
Skimmer is not so long as usually as the material of skimmer just, have special qualification.For example have: hydrophobic silica, metallic soap class, amides, modified siloxane class, siloxanes title complex class, polyethers, emulsion class, powdery type etc.For example, as hydrophobic silica, can illustration go out: NOPCO SN Deformer 777 (trade(brand)name) (Sannopco Co., Ltd. system), SN Deformer VL (trade(brand)name) (Sannopco Co., Ltd. system); As the metallic soap class, can illustration go out: NOPCO NXZ (trade(brand)name) (Sannopco Co., Ltd. system); As the amides skimmer, can illustration go out: NOPCO 267-A (trade(brand)name) (Sannopco Co., Ltd. system); As the modified siloxane defoamer, can illustration go out: siloxanes KM80 (trade(brand)name) (SHIN-ETSU HANTOTAI's chemistry system); As siloxanes title complex defoamer, can illustration go out: SN Deformer 121N (trade(brand)name) (Sannopco Co., Ltd. system); As the polyethers skimmer, can illustration go out: SN Deformer PC (trade(brand)name) (Sannopco Co., Ltd. system); As the emulsion defoamer, can illustration go out: NOPCO KF-99 (trade(brand)name) (Sannopco Co., Ltd. system); As the powdery type skimmer, can illustration go out: SN Deformer 14-HP (trade(brand)name) (Sannopco Co., Ltd. system) etc.
As sanitas, for example can illustration go out: ACTICIDE LG (trade(brand)name) (Thor Amada Co., Ltd. system), ACTICIDE MBS (trade(brand)name) (Thor Amada Co., Ltd. system) etc.
Film coalescence aid is not so long as usually as the material of film coalescence aid just, have special qualification.For example can illustration go out: the organosilane ester of polyvalent alcohol list alkane ethers such as CS-12 (trade(brand)name) (CHISSO Co., Ltd. system), benzylalcohol, butyleneglycol, 2-Rutgers 612, phenyl Ucar 35, dibutyl Diethylene Glycol, dipropylene glycol mono-n-butyl ether, tripropylene glycol n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, Diethylene Glycol mono-n-butyl ether, 3-ethoxy-c acid esters class, acetate 3-methoxyl group-3-methyl-butyl ester etc.
In addition, coating of the present invention can comprise with additive and coating and has the compound (being also referred to as silicone oil usually) of methyl by following formula (IV) expression at two ends of YSR 3286 structure.
(IV)：[-Si(CH
3)
2-O-]n
[wherein, n is generally 10～100 natural number].
If interpolation silicone oil then can improve formed stain resistance of filming.This is because dimethylsilane imparting water repellency on dried coating can prevent adhering to of dirt.
As such silicone oil, particularly, for example can illustration go out: X-22 173DX, X-22 170BX, X-22 170DX, X-22 176DX, X-22 160F (trade(brand)name) (Shin-Etsu Chemial Co., Ltd's system) etc.
As long as the period that coating adds silicone oil in additive and coating be can access the present invention as the coating of target with additive and coating, not special qualification.For example can silicone oil be added in (a) polymerizability unsaturated monomer, when monomeric polymerization, exist in the stage of making (A) water-base resin; Also can after the manufacturing of (A) water-base resin, silicone oil be added in the water-base resin, also can when making coating, silicone oil be added in the coating.
Comprise " silicone oil " in such silicone oil with the two keys of ethylenic." silicone oil with the two keys of ethylenic " is meant and can in (A) water-base resin that obtains through Raolical polymerizable, introduces the compound by the YSR 3286 structure shown in the following formula (IV); So long as can access (A) water-base resin of the present invention and can access with the compound of additive just, have no particular limits as the coating of target.
(IV)：[-Si(CH
3)
2-O-]n
[wherein, n is 10～100 natural number].
About " the two keys of ethylenic ", as stated.
About in coating, adding the period of " silicone oil ", preferably join in (a) polymerizability unsaturated monomer in the stage of making (A) water-base resin with the two keys of ethylenic.
As such silicone oil with the two keys of ethylenic; Be preferably the silicone oil that has the two keys of ethylenic at the single end side of YSR 3286 structure; For example can illustration go out: X-22 174DX (trade(brand)name), X-22 2426, X-22 2475 (trade(brand)name) (Shin-Etsu Chemial Co., Ltd's system) are preferably X-22 174DX (trade(brand)name).
According to thinking, when use had the silicone oil of the two keys of ethylenic, formed stain resistance of filming can further improve, therefore more preferably.This is because when use has the silicone oil of the two keys of ethylenic, can in (A) water-base resin, introduce the dimethyl silica alkyl structure, so the dimethyl silica alkyl structure can prevent adhering to of dirt to the dried coating imparting water repellency.In addition, because the dimethyl silica alkyl structure is incorporated in (A) water-base resin through chemical bond, therefore can keep performance more chronically.
Silicone oil with the two keys of ethylenic can use or make up use separately.In addition, when the calculating of the Tg of (A) water-base resin, there is not to consider to have the silicone oil of the two keys of ethylenic.
As stated, coating of the present invention contains with additive and (a) polymerizability unsaturated monomer is carried out polymerization obtains (A) water-base resin.
Coating of the present invention compares with additive and additive in the past, and is good by water tolerance of filming and stain resistance that coating forms, and weathering resistance and surface viscosity etc. in general balancedly keep good.This can think to be caused by following reason.
Can think that coating of the present invention plays a role as protective colloid in coating with additive, above-mentioned effect shows when being taken in dried coating film on the surface of filming that is formed by coating.By inference, when rainfall, on the hydrophilic group surface that promptly " hydroxyl that wetting ability is high " filming that coating contains in additive, separate out, thereby produce the effect of washing the dirt that on filming, adheres to effectively, so stain resistance improves.
In addition, because (A) acid number of water-base resin is controlled to the such particular value of 20～60mgKOH/g, therefore water-proof reduction also can further reduce.
In addition, (A) in the water-base resin owing to use (a2) to have the monomer of alkoxysilyl and the two keys of ethylenic, therefore film dry the time coating with additive in generation crosslinked.Its result, anti-fouling performance is more lasting, and weathering resistance and surface viscosity performance also improve.
Can think that because aforesaid reason, coating of the present invention has good character with additive and the coating that contains this additive, but the present invention does not receive any restriction of these reasons.
Embodiment
Below, through embodiment and comparative example to the present invention more specifically and explanation at length, but these embodiment scheme of the present invention only, the present invention does not receive any qualification of these examples.In addition, among the embodiment, part expression weight part.
< containing of the manufacturing of the coating of (A) water-base resin>with additive A 1～A9, A ' 10～A ' 12
Below, the monomer (a) that uses in the manufacturing of (A) water-base resin is shown.
Have the monomer of the two keys of hydroxyl and ethylenic as (a1), use (a1-1) 2-hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.'s system).
Have the monomer of the two keys of alkoxysilyl and ethylenic as (a2), use (a2-1) 3-methyl allyl acyloxypropyl trimethoxysilane (SZ-6030; Dow Corning Toray Co., Ltd. system).
Have the monomer of the two keys of acidic group and ethylenic as (a3), use (a3-1) methylacrylic acid (Wako Pure Chemical Industries, Ltd.'s system).
Other have the monomer of the two keys of ethylenic as (a4), use (a4-1) TEB 3K (Wako Pure Chemical Industries, Ltd.'s system) and (a4-2) n-butyl acrylate (Wako Pure Chemical Industries, Ltd.'s system).
The amount of in the four-hole boiling flask that possesses stirring rake, TM and reflux cooler, being put down in writing with table 1 adds monomer and n-DM (n-dodecyl mercaptan) and according to circumstances can add the silicone oil (X-22 174DX (trade(brand)name), Shin-Etsu Chemial Co., Ltd's system) with the two keys of ethylenic; Add 100 parts 2-propyl alcohol (Wako Pure Chemical Industries, Ltd.'s system) and 1 part 2,2 '-Diisopropyl azodicarboxylate ianthone Otsuka Chemical Co., Ltd system).Under 80 ℃, stir and made the compound copolymerization in 4 hours.After reaction mixture is cooled to room temperature, add 500 parts water, add ammoniacal liquor simultaneously and modulate, make the pH of mixture reach 9.Remove through decompression the 2-propyl alcohol is removed, obtain (A) water-base resin that even and transparent mixture promptly exists in aqueous medium.With resulting (A) water-base resin directly as coating with additive A 1～A9 and A ' 10～A ' 12.Coating is 20 weight % with the concentration of additive A 1～A9 and A ' 10～A ' 12.In addition, this concentration be in 105 ℃ the baking oven after dry 3 hours residual part with respect to the weight percent of the weight before dry.
Table 1
The acid number of water-base resin, hydroxyl value, second-order transition temperature (Tg) use aforementioned calculation formula (i)～(iii) try to achieve.In addition, when asking the Tg that calculates water-base resin, to n-DM, X22 174DX and (a2-1) monomer do not take in.
Below, make and contain the coating of coating with additive A 1～A9 or A ' 10～A ' 12, estimate its character.Below, to the manufacturing of coating with and the evaluation of character describe.
< making of coating >
Mix 7 parts of 0.06 part of Natvosol (SP600 (trade(brand)name), Diacel chemical company system), 3.3 parts of zero(ppm) water, 0.6 part of terepthaloyl moietie (Wako Pure Chemical Industries, Ltd.'s system), 2.33 parts of 4% Potassium tripolyphosphates (peaceful chemical Industry Co., Ltd system), 0.15 part of Primer 850 (trade(brand)name) (Rohm Haas corporate system), 21.3 parts of titaniums (CR97 (trade(brand)name), the former industry corporate system of stone) and CS12 (trade(brand)name) (CHISSO corporate system) in 100 parts of hydrotropisms's resins (YODOZOL AD138 (trade(brand)name), Henkel Technologies Amada Co., Ltd. system), obtain coating and use mixture.In 100 parts in this mixture, add coating with additive A 1～A9 or A ' 10～A ' 12, obtain the coating of embodiment 1～10 and comparative example 1～4.About the addition of coating, be shown in Table 2 with additive A 1～A9 and A ' 10～A ' 12.In addition, the weight part of coating use additive is the weight part that comprises aqueous medium.
To containing the coating of coating, carry out following evaluation test with additive A 1～A9 (embodiment 1～10), A ' 10～A ' 12 (comparative example 1～4).
< stain resistance of filming >
Each coating is applied on the aluminium sheet (Yukata Panel Service company) with the mode that is issued to the thickness of about 500 μ m at wet state, makes it dry fully, filmed.With this aluminium sheet outdoor exposure three months, through the visual dirt of estimating the surface of filming after the exposure.Metewand is following.
◎: do not have dirt fully
Zero: adhere to less debris, but no problem in practical application.
*: clear view is to the rainwater vestige.
This result is shown in Table 2.
< weathering resistance of filming >
Each coating is applied on the aluminium sheet (Yukata Panel Service company) with the mode that is issued to the thickness of about 500 μ m at wet state, makes its thorough drying, filmed.
Then, with Eye Super UV trier W type (SUV-W-13: the rugged electric system of rock) carry out accelerated weathering test.Particularly, in the black panel temperature ultraviolet ray 4 hours of shining 295～450nm wavelength under 60 ℃ the condition, at 2.1kgcm
2Hydraulic pressure under from shower nozzle the water spray 30 seconds.Under humidity 90%, 30 ℃ the outer temperature, guarantee to generate the state 4 hours of dewfall.
Use varied-angle glossmeter to be determined at the gloss of filming (NIPPON DENSHOKU KOUGYOU Co., Ltd.) before and after keeping in the above-mentioned weather resistance test machine, calculate gloss retention.Metewand is following.
Zero: gloss retention is higher than 80%
△: gloss retention is 60%～80%
*: gloss retention is lower than 60%
This result is shown in Table 2.
< water tolerance of filming >
Each coating is applied on the aluminium sheet (Yukata Panel Service company) with the mode that is issued to the thickness of about 500 μ m at wet state, makes its thorough drying, filmed.Be impregnated in 20 ℃ the water 1 day with filming, the state of filming through visual observation.Metewand is following.
Zero: do not change
△: the continuous swelling of filming
*: observe and bubble or stripping
This result is shown in Table 2.
< surface viscosity of filming >
Each coating is applied on the aluminium sheet (Yukata Panel Service company) with the mode that is issued to the thickness of about 500 μ m at wet state, makes its thorough drying, filmed.Observe the viscosity on this surface of filming through finger touch.Metewand is following.
Zero: do not observe viscosity
△: observe viscosity slightly
*: observe viscosity
This result is shown in Table 2.
< comprehensive evaluation of filming >
According to the above evaluation of filming, coating is carried out comprehensive evaluation with additive.Metewand is following.
◎: anti-fouling performance be ◎ and other performances do not comprise * situation.
Zero: anti-fouling performance be zero and other performances be ◎ or zero situation.
△: anti-fouling performance be zero and other performances comprise △ but do not comprise * situation.
*: all properties includes * situation.
This result is shown in Table 2.
Table 2
As shown in table 2, because the coating of embodiment 1～10 contains coating of the present invention with additive A 1～A9, therefore formed water tolerance of filming and stain resistance are good, and over-all propertieies such as weathering resistance and surface viscosity balancedly keep good.Particularly embodiment 2～4 and 6 coating are good, and comprehensive evaluation is ◎.With respect to this, because the coating of comparative example 1～4 does not contain coating of the present invention with additive A 1～A9, therefore formed water tolerance of filming and stain resistance are ungood, and the harmony of over-all properties is poor.Particularly, the stain resistance of the coating of comparative example 1～3 shortcoming, the weathering resistance of the coating of comparative example 4, water tolerance shortcoming.
Can know that by these results coating of the present invention has good effect with additive A 1～A9.
[related application]
In addition, the application advocate with on April 28th, 2009 in the application number 2009-109501 of japanese publication right of priority based on the 4th of Treaty of Paris as the basis application.The content of this basis application is introduced in this specification sheets through carrying out reference.
Claims (4)
1. a coating is used additive; It contains and (a) polymerizability unsaturated monomer is carried out polymerization obtains (A) water-base resin; Wherein, (A) acid number of water-base resin is 20～60mgKOH/g, and (a) the polymerizability unsaturated monomer comprises the monomer that (a1) has hydroxyl and the two keys of ethylenic.
2. coating according to claim 1 is used additive, and wherein, (a) the polymerizability unsaturated monomer also comprises the monomer that (a2) has alkoxysilyl and the two keys of ethylenic.
3. coating according to claim 1 and 2 is used additive, and it is as the anti-pollution agent.
4. coating, it contains in the claim 1～3 each described coating uses additive.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP109501/2009 | 2009-04-28 | ||
| JP2009109501A JP5322762B2 (en) | 2009-04-28 | 2009-04-28 | Paint additive and paint containing the same |
| PCT/JP2010/056830 WO2010125930A1 (en) | 2009-04-28 | 2010-04-16 | Additive for coating material, and coating material containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102449083A true CN102449083A (en) | 2012-05-09 |
Family
ID=43032083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800233266A Pending CN102449083A (en) | 2009-04-28 | 2010-04-16 | Additive for coating material, and coating material containing same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5322762B2 (en) |
| CN (1) | CN102449083A (en) |
| WO (1) | WO2010125930A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928765A (en) * | 2017-03-10 | 2017-07-07 | 青岛海尔空调器有限总公司 | A kind of application method of photocatalyst additive and the hydrophilic coating containing the additive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841355A2 (en) * | 1996-11-07 | 1998-05-13 | Shin-Etsu Chemical Co., Ltd. | Silicone resin-containing emulsion compositions, methods for making them, and cured films thereof |
| JP2003138018A (en) * | 2001-11-08 | 2003-05-14 | Jsr Corp | Aqueous dispersion and coated material |
| JP2005232265A (en) * | 2004-02-18 | 2005-09-02 | Toei Kasei Kk | Vinyl resin and coating agent containing the same |
| JP2006056973A (en) * | 2004-08-19 | 2006-03-02 | Kansai Paint Co Ltd | Method for producing aqueous resin dispersion |
-
2009
- 2009-04-28 JP JP2009109501A patent/JP5322762B2/en active Active
-
2010
- 2010-04-16 WO PCT/JP2010/056830 patent/WO2010125930A1/en active Application Filing
- 2010-04-16 CN CN2010800233266A patent/CN102449083A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841355A2 (en) * | 1996-11-07 | 1998-05-13 | Shin-Etsu Chemical Co., Ltd. | Silicone resin-containing emulsion compositions, methods for making them, and cured films thereof |
| JP2003138018A (en) * | 2001-11-08 | 2003-05-14 | Jsr Corp | Aqueous dispersion and coated material |
| JP2005232265A (en) * | 2004-02-18 | 2005-09-02 | Toei Kasei Kk | Vinyl resin and coating agent containing the same |
| JP2006056973A (en) * | 2004-08-19 | 2006-03-02 | Kansai Paint Co Ltd | Method for producing aqueous resin dispersion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928765A (en) * | 2017-03-10 | 2017-07-07 | 青岛海尔空调器有限总公司 | A kind of application method of photocatalyst additive and the hydrophilic coating containing the additive |
| CN106928765B (en) * | 2017-03-10 | 2020-05-29 | 青岛海尔空调器有限总公司 | Photocatalyst additive and application method of hydrophilic coating containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5322762B2 (en) | 2013-10-23 |
| JP2010254911A (en) | 2010-11-11 |
| WO2010125930A1 (en) | 2010-11-04 |
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Application publication date: 20120509 |