CN1931917A - Aqueous resin dispersion, aqueous resin composition and method for producing aqueous resin composition - Google Patents
Aqueous resin dispersion, aqueous resin composition and method for producing aqueous resin composition Download PDFInfo
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- CN1931917A CN1931917A CNA2006101416255A CN200610141625A CN1931917A CN 1931917 A CN1931917 A CN 1931917A CN A2006101416255 A CNA2006101416255 A CN A2006101416255A CN 200610141625 A CN200610141625 A CN 200610141625A CN 1931917 A CN1931917 A CN 1931917A
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- 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
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- 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
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Abstract
The aqueous resin dispersion comprises resin particles having an average particle diameter of 1-100[mu]m obtained by suspension polymerization of a monomer component mixture comprising (a) a (meth)acrylate, (b) a multifunctional crosslinkable monomer and (c) an unsaturated monomer having a UV absorbing group.
Description
The application be the applying date be on October 17th, 2003, application No. is the 200310102422.1, divisional applications of the application for a patent for invention of entitled " manufacturing method of aqueous resin dispersion, aqueous resin composition and the composition ".
Technical field
The present invention relates to aqueous resin dispersion, aqueous resin composition and its manufacturing methods.In more detail, coating, coating agent, optical component, electronic material, medical inspection medicine etc. be may be used as, as most effective application method, be used as enamel and transparent antiglossing pigment.
Background technique
The delustering agents such as antiglossing pigment composition particle containing inorganic or organic in the composition mostly, based on beautiful purpose, wherein aqueous composition is mostly in the covering with paint of building material surface.
In the past, the particle used in delustering agent composition, inorganic particle, especially silica-based powder be it is main, due to its low cost and be widely used, still, due to water imbibition, therefore in terms of there is water resistance, and it is easy albefaction, the problem of there is also in terms of weatherability, frost.
On the other hand, there is the aqueous resin composition obtained by the way that hydrophilic organic solvent is added in the resin particle aqueous dispersion obtained by suspension polymerization in water as the method for mixing organic resin particle (referring for example to patent document 1).
But the aqueous resin composition obtained in this way is able to suppress the formation bonded firmly, but can be easily separated and settles, since it forms hard bonding, when redisperse must expense, have the shortcomings that so-called industrial insufficient.
1 Japanese Patent Publication 2000-313720 of patent document
Subject to be solved by the invention
Therefore, the purpose of the present invention is to provide a kind of novel aqueous resin dispersions.
Other objects of the present invention are to provide the excellent aqueous resin composition of weatherability and its manufacturing method.
Low it is a further object of the present invention to provide water imbibition and overlay film excellent transparency high weatherability and the excellent aqueous resin composition and its manufacturing method of frost tolerance.
Other objects of the present invention are to provide forms grid by the way that tackifier are added in suspension polymerisation water-borne dispersions between particles, inhibit the mutual contact of particle, inhibit the generation bonded firmly, also, obtained water-borne dispersions are by a few days non-settling economical, excellent aqueous resin composition and its manufacturing method.
Means for solving the problems
Above-mentioned purpose is by following (1)~(7) come what is reached.
(1) aqueous resin dispersion, 1~100 micron of average grain diameter of resin particle (the 1st invention) for generating the monomer component suspension polymerisation of the unsaturated monomer containing (a) (methyl) acrylate, (b) multifunctional cross-linkable monomer and (c) with UV stable base and/or ultraviolet radiation absorption base containing (A).
(2) aqueous resin dispersion that above-mentioned (1) is recorded, wherein (A) (a) (methyl) acrylate is with naphthenic base and/or tert-butyl (methyl) acrylate.
(3) aqueous resin composition constitutes (the 2nd invention) by the aqueous resin dispersion that (A) contains by the aqueous resin dispersion and (B) of 1~100 micron of average grain diameter of the resin particle that the monomer mixture suspension polymerisation for containing the unsaturated monomer of (methyl) acrylate, (b) multifunctional cross-linkable monomer and (c) with UV stable base and/or ultraviolet radiation absorption base of (a) with naphthenic base and/or tert-butyl generates containing average grain diameter for 0.01~1 micron of resin particle.
(4) aqueous resin composition, 50~99 mass % of (methyl) acrylate of naphthenic base and/or tert-butyl will be had containing (a) by being contained by (A), (b) multifunctional 0.1~20 mass % of cross-linkable monomer and 0~49.9 mass % of (d) other monomers be (wherein, (a), (b) and (d) add up to 100 mass %) monomer mixture suspension polymerisation generate 1~100 micron of average grain diameter of resin particle aqueous resin dispersion and (B) containing average grain diameter be 0.01~1 micron resin particle aqueous resin dispersion constitute (the 3rd invention).
(5) manufacturing method of aqueous resin composition, it is characterised in that (C) tackifier are added in the aqueous resin dispersion of 1~100 micron of resin particle of the average grain diameter generated containing suspension polymerisation and mix the aqueous resin dispersion (the 4th invention) for the resin particle that (B) is 0.01~1 micron containing average grain diameter.
(6) manufacturing method of aqueous resin composition, it is characterized in that will have (methyl) acrylate of naphthenic base and/or tert-butyl containing (A) (a) containing, (b) (C) tackifier are added in the aqueous resin dispersion for 1~100 micron of average grain diameter of the resin particle that the monomer mixture suspension polymerisation that multifunctional cross-linkable monomer and (c) contain the unsaturated monomer with UV stable base and/or ultraviolet radiation absorption base generates, and mix the aqueous resin dispersion (the 5th invention) for the resin particle that (B) is 0.01~1 micron containing average grain diameter.
(7) manufacturing method of aqueous resin composition, it is characterized in that will have 50~99 mass % of (methyl) acrylate of naphthenic base and/or tert-butyl containing (a) containing, (b) multifunctional 0.1~20 mass % of cross-linkable monomer and 0~49.9 mass % of (d) other monomers be (wherein, (a), (b) and (d) add up to 100 mass %) monomer mixture suspension polymerisation generate 1~100 micron of average grain diameter of resin particle aqueous resin dispersion in be added (C) tackifier, and mix the aqueous resin dispersion (the 6th invention) for the resin particle that (B) is 0.01~1 micron containing average grain diameter.
Invention effect
The present invention has to be constituted as described above, and therefore, prepared aqueous resin dispersion and aqueous resin composition are capable of forming the excellent overlay film of the transparency, weatherability, frost tolerance.And, by the way that tackifier are added in suspension polymerisation water-borne dispersions, grid can be formed between particles, inhibits the mutual contact of particle, the water-borne dispersions for inhibiting the generation bonded firmly, and obtaining were formed by a few days also non-settling economically excellent aqueous resin composition.
Preferred plan for carrying out an invention
As (A) (a) (methyl) acrylate that monomer of the invention uses, as described below.
(a) it is used as (methyl) acrylate, can specifically enumerate ester i.e. (methyl) acrylate of such as (methyl) acrylic acid such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite and the alcohol of C1~C18 (including aliphatic, alicyclic, aromatic series)；(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid and monoesters of polypropylene glycol etc. have (methyl) esters of acrylic acid of hydroxyl etc..
It is preferred that (methyl) the acrylic acid acids with naphthenic base, (methyl) acrylic compounds with tert-butyl can be enumerated, more preferably with (methyl) acrylic compounds of naphthenic base.
As the naphthenic base construction in the polymerism unsaturated monomer with above-mentioned naphthenic base, cyclobutyl construction, cyclopenta construction, cyclohexyl construction, suberyl construction, cyclooctyl construction, cyclononyl construction, cyclodecyl construction, ring undecyl construction, cyclo-dodecyl construction, ring tridecyl construction, ring myristyl construction, cyclopentadecane base construction, ring cetyl construction, ring heptadecyl construction, ring octadecyl construction etc. are suitable.
As the polymerism unsaturated monomer with above-mentioned naphthenic base, cyclohexyl (methyl) acrylate, methylcyclohexyl (methyl) acrylate, tert-butylcyclohexyl (methyl) acrylate, cyclooctyl (methyl) acrylate, cyclo-dodecyl (methyl) acrylate, isobornyl methacrylate (chemistry society, common prosperity society system, trade name: lightweight ester IB-X), iso-bornyl acrylate (chemical conversion industry society, Hitachi system, trade name: FA-544A；Chemistry society, common prosperity society system, trade name: light acrylate IB-XA), dicyclopentylmethyl acrylate (chemical conversion industry society, Hitachi system, trade name: FA-513M), bicyclopentyl acrylate (chemical conversion industry society, Hitachi system, trade name: FA-513A), 4- hydroxymethylcyclohexyl methacrylate (chemical conversion industry society, Hitachi system, trade name: CHDMMA), 4- methylcyclohexylmethyl (methyl) acrylate, cyclohexyl methyl (methyl) acrylate etc. be it is suitable, they can be used more than one or two kinds of.Wherein, more preferable cyclohexyl (methyl) acrylate, 4- methylcyclohexylmethyl (methyl) acrylate, cyclohexyl methyl (methyl) acrylate.
As (methyl) acrylic compounds with tert-butyl, Tert-butyl Methacrylate, tert-butyl acrylate can be enumerated.
Its dosage is not particularly limited in the invention of the 1st, the 2nd, the 4th and the 5th, preferably 5~99 mass %, more preferably 30~99 mass %.It is 50~99 mass %, preferably 60~95%, more preferably 70~90 mass % in the 3rd and the 6th invention.
As (A) (b) multifunctional cross-linkable monomer, the ester of the polyalcohols such as (methyl) acrylic acid and ethylene glycol, propylene glycol, 1,3-BDO, diethylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol can be enumerated；The polyfunctional groups vinyl compound such as divinylbenzene；(methyl) acrylic acid and allyl ester etc. such as (methyl) allyl acrylate.Its dosage is not particularly limited in the 1st, the 2nd and the 4th, preferably 0.1~20 mass %, more preferably 5~15 mass %.
There is the unsaturated monomer of UV stable base and/or ultraviolet radiation absorption base as (A) (c), such as 2 can be enumerated, 4- dihydric benzophenone or 2, 2 ', 2- hydroxyl -4- [3- (methyl) acryloxy -2- hydroxy propyloxy group] benzophenone that 4- trihydroxy benzophenone and the reaction of (methyl) glycidyl acrylate generate, 2, the benzophenones class monomers such as 2 '-dihydroxy -4- [3- (methyl) acryloxy -2- hydroxy propyloxy group] benzophenone, with 2- [2 '-hydroxyls -5 '-(methacryloxymethyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(methacryloxypropyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(Methacryloxyhexyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyls -3 '-tert-butyl -5 '-(methacryloxyethyl) phenyl] -2 benzotriazole, 2- [2 '-hydroxyls -5 '-tert-butyl -3 '-(methacryloxyethyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] chloro- 2H- benzotriazole of -5-, 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -5- methoxyl group -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -5- cyano -2H- benzotriazole, 2- [2 '-hydroxyls -5 '-(methacryl Oxygroup ethyl) phenyl] -5- tert-butyl -2H- benzotriazole, benzotriazoles monomers such as 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -5- tert-butyl -2H- benzotriazole etc. have the monomer of ultraviolet radiation absorption function, 4- (methyl) acryloxy -2, 2, 6, 6- tetramethyl piperidine, 4- (methyl) Acryloyl amino -2, 2, 6, 6- tetramethyl piperidine, 4- (methyl) acryloyl group Oxy-1, 2, 2, 6, 6- pentamethvl, 4- (methyl) Acryloyl amino -1, 2, 2, 6, 6- pentamethvl, 4- cyano -4- (methyl) acryloyl group oxygroup -2, 2, 6, 6- tetramethyl piperidine, 1- (methyl) acryloyl group -4- (methyl) acrylamido -2, 2, 6 , 6- tetramethyl piperidine, 4- crotons acyloxy -2,2,6; 6- tetramethyl piperidine, 4- crotonocyl amino -2,2,6,6- tetramethyl piperidines, 1- crotonyl -4- crotons acyloxy -2; piperidines polymerizable monomer such as 2,6,6- tetramethyl piperidines etc. has the monomer etc. of ultraviolet stabilization function.
This purple, base is stablized in 4 outside lines and/or the usage amount of ultraviolet radiation absorption base is not particularly limited, preferably 0.1~10 mass %, more preferably 0.5~5 mass %, and the weatherability of the aqueous resin composition thus prepared improves.
The total amount of (a), (b) and (c) in above-mentioned monomer mixture are 100 mass %.
In the invention of the 1st, the 2nd, the 4th and the 5th of the application, (d) other monomers are not required, but can also be added.Its usage amount is not particularly limited, preferably 0~94.8 mass %.
As these (d) other monomers, as long as can be copolymerized with above-mentioned monomer, any one can be used.It can be enumerated as main polymerizable monomer
The ester of the alcohol of (methyl) acrylic acid such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite and C1~C18 (including aliphatic, alicyclic, aromatic series) is (methyl) acrylate；(methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid and monoesters of polypropylene glycol etc. have (methyl) esters of acrylic acid of hydroxyl；
The ethylene unsaturated monocarboxylic such as acrylic acid, methacrylic acid, crotonic acid；The unsaturated polybasic carboxylic acid class of fumaric acid, itaconic acid；The partial esterification of the unsaturated polynary monocarboxylic acid of the ethylene such as ethyl maleate, ethyl itaconate closes the polymerizable monomer with carboxyl of object；
(methyl) glycidyl acrylate, (methyl) acrylic acid -2- methylglycidyl esters, allyl glycidyl ether etc. have the polymerizable monomer of epoxy group；
Methylacryloyl aziridine, (methyl) acrylic acid -2- aziridine ethyl ester etc. have the polymerizable monomer of '-aziridino；
2- isopropenyl -2- oxazoline, 2- vinyl-oxazoline etc. have the polymerizable monomer of oxazoline group；
(methyl) acrylamide, mono- ethyl of N- (methyl) acrylamide, N- monomethyl (methyl) acrylamide, N, (methyl) acrylamide derivative such as N- dimethyl (methyl) acrylamide；
The alkaline polymerizations monomers such as (methyl) acrylate, dimethyl aminoethyl (methyl) acrylamide, vinylpyridine, vinyl imidazole, vinyl pyrrolidone；
Bridging properties (methyl) acrylic amides such as N- methylol (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide；
The styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, 1-chloro-4-methyl-benzene；
(methyl) acrylonitrile etc. has the polymerizable monomer of cyano；
(methyl) acrylic acid -2- sulfonic acid and its salt, vinyl sulfonic acid and its salt etc. have sulfonic polymerizable monomer；
Vinyltrimethoxysilane, γ-(methyl) propenyloxy group propyl trimethoxy silicane, allyltriethoxysilane, trimethoxy-silylpropyl allyl amine etc. have the vinyl esters such as unsaturated monomer, vinyl acetate base ester, the vinyl propionate base ester of organic silicon substrate；
The halogenated monomers classes such as difluoroethylene, vinylidene difluoride, dichloroethylene, dichloro Asia ethylene
Butadiene, isoprene equiconjugate dienes；
Ethylene, propylene, butylene class olefines etc..These polymerizable monomers enumerated can only use one kind, can also be simultaneously using two or more.
The polymerization initiator used when as suspension polymerisation; oil-soluble initiator can be used; such as lauroyl peroxide, benzoyl peroxide, t-butyl peroxy -2- ethyl ケ キ サ ノ エ-ト, 1 can be enumerated; the peroxide type initiators such as 1- di-t-butyl-peroxide -2- hexahydrotoluene; 2; 2 '-azodiisobutyronitriles, 2,2 '-azos two -2, azo-initiators such as 4- methyl pentane nitrile etc..The usage amount of these initiators is 0.01~5 mass parts preferably with respect to above-mentioned 100 mass parts of monomer mixture.
The dispersion stabilizer used when as suspension polymerisation, the cellulose families such as polyvinyl alcohol, polyvinylpyrrolidone, poly- (methyl) acrylic acid or its salt, carboxycellulose, methylcellulose, methyl hydroxy cellulose, the water-soluble polymers such as gelatin can be used；The inorganic powders such as barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, calcium phosphate；With the reactive surfactant of more than one polymerizable carbon-to-carbon unsaturated bond in all activating agents and molecule such as anionic based surfactants, nonionic class surfactant, cationic based surfactants, amphoteric surfactant, high molecular surfactant.They can be more than one or two kinds of, and the usage amount of these dispersion stabilizers is 0.01~10 mass parts, more preferable 0.1~5 mass parts preferably with respect to above-mentioned 100 mass parts of monomer mixture.
Aqueous resin dispersion (A) containing 1~100 micron of resin particle of average grain diameter is that the monomer mixture being made up of the monomer mixture or monomer (a), (b) and (d) as needed for constituting above-mentioned monomer (a), (b), (c) and (d) as needed carries out suspension polymerisation preparation in the presence of dispersion stabilizer or polymerization initiator in an aqueous solvent by conventional method.Reaction temperature is usually 50~100 DEG C, and preferably 60~90 DEG C.Reaction temperature can be certain, can also change in the reaction.There is no particular limitation for polymerization time, can suitably be selected according to the carry out situation of reaction, is usually 1~10 hour from polymerization start and ending, preferably 2~5 hours.
Average grain diameter in above-mentioned aqueous resin dispersion (A) is 1~100 micron, preferably 5~60 microns, further preferably 10~50 microns.That is, extinction effect is insufficient when less than 1 micron, and 100 microns if more than, the storage stability for the aqueous resin dispersion that suspension polymerisation obtains is substantially reduced.Solid fraction concentration in the aqueous resin dispersion (A) is 5~50 mass %, preferably 10~30 mass %.
There is no particular limitation for the use form of aqueous resin dispersion (A) containing 1~100 micron of resin particle of average grain diameter, aqueous dispersion can directly be used, it is mixed after can also being obtained in the form of particle powder, but, from the viewpoint of economic, operability, the method for aqueous dispersion is preferably directly used.
Aqueous resin dispersion (B) containing 0.01~1 micron of resin particle of average grain diameter can be prepared by the way that the monomer or monomer mixture that are made of any one or the two or more mixtures in above-mentioned monomer (d) and monomer (a) as needed, (b), (c) are carried out emulsion polymerization in an aqueous solvent by conventional method in the presence of emulsifier and polymerization initiator.Reaction temperature is usually 50~90 DEG C, and preferably 60~85 DEG C.Reaction temperature can be certain, can also change during the reaction.Polymerization time is not particularly limited, and can suitably be selected according to the carry out situation of reaction, is usually 1~10 hour from polymerization start and ending, preferably 1~5 hour.
Average grain diameter in above-mentioned aqueous resin dispersion (B) is 0.01~1 micron, preferably 0.04~0.5 micron, further preferably 0.08~0.2 micron.Solid fraction concentration in the aqueous resin dispersion (B) is 5~70 mass %, preferably 30~60 mass %.
Monomer used in the manufacture of aqueous resin dispersion (B) is if it is polymerizable monomer, any one can be used, there is unsaturated monomer 0.1~10 the mass %, further preferred a) 30~70 mass % of unsaturated monomer with naphthenic base of UV stable base and/or ultraviolet radiation absorption base, (c) to have 0.5~5 mass % of unsaturated monomer of UV stable base and/or ultraviolet radiation absorption base by preferably a) 5~99 mass % of unsaturated monomer with naphthenic base, (c).The calculating Tg of preferred emulsion is -20 DEG C~90 DEG C, more preferable 0~60 DEG C.Here, Tg (K) is given by:
The glass transition point temperature for the homopolymer for constituting each monomer of the polymer formed by n kind monomer is set as TgI (K), the distribution of weight of each monomer is WI.Wherein
It is usually water as used water class solvent in the manufacturing method of any one of the above aqueous resin dispersion, it as needed can be simultaneously using hydrophilic solvents such as lower alcohol and ketone.The usage amount of aqueous solvent, can make the use total amount relative to above-mentioned polymerizable monomer ingredient, and the solid portion content of obtained aqueous resin dispersion uses in above-mentioned certain range.
As emulsifier, there is no particular limitation, and all surfactants such as anionic based surfactants, nonionic class surfactant, cationic based surfactants, amphoteric surfactant, high molecular surfactant can be used for example.The reactive surfactant in molecule with more than one polymerizable carbon-to-carbon unsaturated bond can be used.
As anionic based surfactants, specifically it can be cited for example that the alkali metal alkyl sulfates such as lauryl sodium sulfate, dodecyl sulphate potassium；The alkylsurfuric acids ammonium salt such as ammonium lauryl sulfate；Brij-35 sodium sulphate；Sodium sulfonate；The alkylsulfonates such as ammonium salt of the alkali metal salts of sulfonation alkane esters, sulfonation alkane esters；The fatty acid salts such as sodium laurate, Emulphor FM, triethanolamine abietate；The alkylaryl sulfonates such as alkali metal sulfates of neopelex, alkali metal phenolic hydroxyl group ethylene；High alkylnaphthalene sulfonate；Naphthalene sulfonic acid-formaldehyde condensation product；Dialkyl sulfosuccinates；Polyethylene glycol oxide alkyl sulfate；Polyethylene glycol oxide alkyl aryl sulfate etc..
As nonionic class surfactant, such as polyethylene oxide alkyl ethers specifically can be used；Polyethylene glycol oxide alkyl aryl ether；Sorbitan fatty acid ester；Polyoxyethylene sorbitan aliphatic ester；The glycerine monofatty esters such as one laurate of glycerol；Polyethylene glycol oxide propylene oxide copolymer；Ethylene oxide and the condensation product of aliphatic amine, amide or acid etc..
As high molecular surfactant, specifically it can be cited for example that polyvinyl alcohol；Poly- (methyl) sodium acrylate, poly- (methyl) potassium acrylate, poly- (methyl) ammonium acrylate, poly- hydroxyethyl (methyl) acrylate；The two or more copolymer of the component unit polymerizable monomer of poly- hydroxypropyl (methyl) acrylate or these polymer or with the copolymer of other monomers etc..The related moving catalyst of coronal ethers etc. has surface-active, therefore can be used as surfactant use.
As reactive surfactant, specifically it can be cited for example that having acrylic -2- ethylhexyl phenyl esters of sulfosuccinic acids sodium, the sulfuric ester of (methyl) acrylic acid polyethylene glycol oxide, polyethylene glycol oxide alkyl base ether ammonium sulfate salt, the phosphate of (methyl) acrylic acid polyoxyethylene enester, two (the polycyclic phenyl ether of polyethylene glycol oxide) methacrylated sulfate ammonium salts, the construction of polyethylene glycol oxide alkyl aryl sulfate, and there is acrylic, isopropenyl, allyl, it is acrylate-based, methacrylate etc. has the anionic property reactive surfactant of polymerism etc.；With polyethylene glycol oxide alkyl phenyl ether (methyl) acrylate, polyethylene oxide alkyl ethers (methyl) acrylate, polyethylene glycol oxide alkyl aryl ether construction, and nonionics reactive surfactant such as polymerism with isopropenyl, aryl etc. etc..These emulsifier, that is, surfactant uses can only use one kind, two or more can also use simultaneously, still, if it is considered that the water resistance of the dry coating of aqueous resin dispersion, then preferred reactive surfactant.
There is no particular limitation for the usage amount of emulsifier, relative to the total amount of polymerizable monomer ingredient, preferably 0.3~5 mass %, more preferable 0.5~3 mass %.If the usage amount of emulsifier is excessive, the water resistance of film is reduced, and if very few, the polymerization stability of resin particle is substantially reduced.The partial size of resin is because the type of emulsifier is greatly affected, and therefore, dosage must make selection appropriate according to used emulsifier within the above range.
There is no particular limitation for polymerization initiator, can specifically enumerate such as 2,2 '-azodiisobutyronitriles, 2,2 '-azo two (2- amidine propane) dicarboxylates, 4, the water-soluble azo compounds such as 4 '-azos two (4- cyanopentanoic acid)；The persulfuric acid salt of potassium peroxydisulfate；Peroxide such as hydrogen peroxide, peracetic acid, benzoyl peroxide, di-tert-butyl peroxide etc..
There is no particular limitation for the usage amount of polymerization initiator, relative to the use total amount of polymerizable monomer ingredient, preferably 0.1~3 weight %, more preferably 0.5~2 weight %.When the usage amount of polymerization initiator is excessive, the water resistance of film is reduced, and it is very few when, polymerization speed slows down, and is easy the monomer of remained unreacted, therefore, not preferably.One kind can be used in polymerization initiator, also can be used two or more.In order to accelerate polymerization speed, as needed, the metal salts such as the reducing agents such as sodium hydrogensulfite and ferrous sulfate and above-mentioned polymerization initiator can be used simultaneously.
The Adding Way of polymerization initiator is not particularly limited, and can be any one method such as being added, be separately added into together, be continuously added dropwise.In order to accelerate the completion of polymerization, before and after all monomer components are added dropwise, a part of polymerization initiator can be specifically added.
When polymerization other than polymerization initiator, as needed, chain-transferring agent can be added, compound and α-methylstyrenedimer with mercapto such as tert-dodecylmercaotan etc. can be added.
There is no particular limitation for the neutralizer used in and when acidic-group, and currently known various neutralizers can be used.The alkali metal compound such as sodium hydroxide, potassium hydroxide can specifically be enumerated；The alkali earth metallic compounds such as calcium hydroxide, calcium carbonate；Ammonia；Water-soluble organic amines classes such as monomethyl amine, dimethyl amine, Trimethylamine, an ethylamine, diethylamide, triethylamine, a propyl amine, dimethyl propyl amine, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine, diethylenetriamines etc..Wherein, the low boiling points such as ammonia, monomethyl amine, dimethyl amine, Trimethylamine amine heats readily volatilized at normal temperature, therefore, can prevent the water resistance of the cured coating film in the coating containing aqueous resin dispersion from reducing, therefore preferably, more preferable ammonia.The above-mentioned neutralizer enumerated can only use one kind, two or more can also use simultaneously.
In the 4th and the 5th invention, it is that tackifier (C) is added in the aqueous resin dispersion (A) containing 1~100 micron of average grain diameter of resin particle, then, the manufacturing method of the aqueous resin composition of the aqueous resin dispersion of the resin particle containing 0.01~1 micron of average grain diameter is mixed.
As above-mentioned tackifier (C), there is no particular limitation, if enumerating an example, such as described below.
(1) water soluble polymer
As the concrete example for the water soluble polymer that tackifier use, such as methylcellulose, cellulose ethers (such as HYDROXY PROPYL METHYLCELLULOSE etc.), polyethylene oxide, polypropylene oxide, polyethylene glycol, polyacrylamide, polyvinyl alcohol can be enumerated etc..
(2) associativity tackifier
The associativity tackifier used as tackifier usually connect the hydrophobicitys side groups such as senior alkyl in the end of hydrophilic macromolecule main chain and on the way.The discovery mechanism of the tackifying effect of associativity tackifier is known as generating due to the associativity that the secondary binding force (for example, hydrophobic binding power) of hydrophobicity side group generates.The concrete example of the associativity tackifier used as tackifier can for example enumerate polyvinyl alcohol associativity tackifier and acrylic compounds associativity tackifier.One scheme of polyvinyl alcohol associativity tackifier is to combine hydrophobicity side group at the both ends of polyvinyl alcohol.
(3) acrylic compounds associativity tackifier
Acrylic compounds associativity tackifier are in the hydrophobicitys side group such as the end of hydrophilic acrylic's high polymer main chain or intermediate connection senior alkyl.The concrete examples of acrylic compounds associativity tackifier it can be cited for example that acrylic monomer and the associative monomer (for example, with the hydrophobicitys side groups such as alkyl, aralkyl and ethylene unsaturated monomer i.e. reactive surfactant etc. for being copolymerized with acrylic monomer) with the hydrophobicitys side group such as senior alkyl copolymer.Specifically tackifier shown in preferred special open 2001-240633 bulletin.
The additional amount of tackifier (C) is that the aqueous resin dispersion (B) for the resin particle that every 100 mass parts contain 0.01~1 micron of above-mentioned average grain diameter is 0.05~2 mass parts, preferably 0.1~1.5 mass parts, more preferable 0.1~0.7 mass parts.This is because Efficient Adhesive Promotion is not presented when the amount of tackifier (C) is less than 0.05 mass parts, on the other hand, if it exceeds 2 mass parts, water resistance is reduced.
In whole inventions, the additional amount of aqueous resin dispersion (A) containing 1~100 micron of resin particle of average grain diameter is that the solid portion of the aqueous resin dispersion (B) for the resin particle that every 100 mass parts contain 0.01~1 micron of above-mentioned average grain diameter is 1~30 mass parts, preferably 5~25 mass parts.That is, extinction effect is insufficient when the amount of aqueous resin dispersion (A) is less than 1 mass parts, on the other hand, if it exceeds 30 mass parts, storage stability are also insufficient.
Aqueous resin composition of the invention can directly only use above-mentioned aqueous resin dispersion, also can according to need containing various additives.As additive, can be added such as pigment, film forming host agent, filler (filler), toning coating material, wetting agent, antistatic agent, pigment dispersing agent, plasticizer, antioxidant, flow control agent, viscosity modifier.Other water-soluble resins or water-dispersed resin are used in mixed way furthermore, it is possible to be added.These resins are it can be cited for example that styrene-acrylate, acrylic acid, urethane, silicone, acrylic acid silicone, acrylic acid urethane, fluorine, acrylic acid fluorine etc..
In above-mentioned additive, inorganic pigment as the colored pigment such as the white pigments such as titanium oxide, calcium oxide, antimony trioxide, the flowers of zinc, lithopone, white lead and carbon black, yellow lead, molybdate orange, colcother, titanellow, Huang Hua can be enumerated especially as pigment；The organic pigment of the phthalocyanines such as the azo-compounds such as benzidine, hansa yellow or copper phthalocyanine indigo plant.These dyestuffs can only use one kind, two or more can also use simultaneously.In these examples enumerated, in order not to the film reduced weatherability, it is preferable to use the good pigment of weatherability.For example, when using white pigment titanium oxide, it is preferable to use the titanium oxide of rutile-type construction compared with the titanium oxide of anatase construction.In the titanium oxide constructed using rutile-type, in order to which long-term weatherability is presented, compared with sulfuric acid process titanium oxide, chlorine method titanium oxide is more preferably used.
Embodiment
Enumerating embodiment below, the present invention will be described in more detail.Expression " mass parts " and " quality % " is not particularly limited in " part " and " % " recorded below.
In the reaction vessel, by polyvinyl alcohol (Ku Lalei Co. Ltd. system, trade name: PVA-CST) 0.5 part of 25% aqueous solution of 0.5 part and polyethylene glycol oxide oil ether sulfuric ester ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd., trade name: 18E is revealed in Ha Yidi promise) is dissolved in 154.5 parts of deionized water.Wherein, 88 parts of cyclohexyl methacrylate, 4- methacryloxy -2,2,6,6- tetramethyl piperidines (sub- Supreme Being's card Co. Ltd. system, trade name: sub- Supreme Being Ka Sitapu LA-87 is added；Hereinafter referred to as piperidines A) 2 parts, 10 parts and 1 part of lauroyl peroxide of trimethylol-propane trimethacrylate (TMPTMA: Nippon Shokubai Co., Ltd's system), the monomer mixture solution of mixing is added, is stirred with blender.With the observation of optics microscopic visual measurement as a result, having obtained about 10 microns of partial size of monomer dispersion liquid.The dispersion liquid is added in 2 liters of separation flask, adds 254 parts of deionized waters, stir in a nitrogen atmosphere, while being warming up to 75 DEG C.After polymerization starts, then fever cures 3 hours at 85 DEG C, obtains aqueous resin dispersion up to 85 DEG C.The average grain diameter of obtained aqueous resin dispersion is about 9 microns with the result that Kou Erde counter (Coulter counter) measures.
Suspension polymerisation Production Example 2
In addition to make unsaturated monomer group become 60 parts of cyclohexyl methacrylate, TMPTMA10 part, other than 2 parts of piperidines (A) and 28 parts of methyl methacrylate (MMA), with the same progress of suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is about 10 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 3
In addition to make unsaturated monomer group become 40 parts of cyclohexyl methacrylate, TMPTMA10 part, 2 parts of piperidines (A), other than 1 part of 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -2H- benzotriazole (hereinafter referred to as benzotriazole (B)) and 47 parts of methyl methacrylate (MMA), with the same progress of suspension polymerisation Production Example 1.
The average grain diameter of obtained aqueous resin dispersion is about 9 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 4
In addition to make unsaturated monomer group become 93 parts of cyclohexyl methacrylate, TMPTMA5 part, other than 2 parts of piperidines (A), with the same progress of suspension polymerisation Production Example 1.
The average grain diameter of obtained aqueous resin dispersion is about 10 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 5
In addition to make unsaturated monomer group become 83 parts of cyclohexyl methacrylate, TMPTMA15 part, other than 2 parts of piperidines (A), with the same progress of suspension polymerisation Production Example 1.
The average grain diameter of obtained aqueous resin dispersion is about 10 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 6
Other than making unsaturated monomer group become 70 parts, TMPTMA10 parts, MMA20 parts of cyclohexyl methacrylate, equally carried out with suspension polymerisation Production Example 1.
The average grain diameter of obtained aqueous resin dispersion is about 11 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 7
Other than making unsaturated monomer group become 90 parts, TMPTMA10 parts of cyclohexyl methacrylate, equally carried out with suspension polymerisation Production Example 1.
The average grain diameter of obtained aqueous resin dispersion is about 9 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 8
Other than making unsaturated monomer group become TMPTMA10 parts, MMA90 parts, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is about 12 microns with the result that Kou Erde counter measures.
Suspension polymerisation Production Example 9
In addition to making 80 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA18 and emulsifier be polyoxyalkylene alkylamine phenyl ether sulfate ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd., trade name: " Ha Yidi promise reveal N-08 ") except 1 part, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 10 microns.
Suspension polymerisation Production Example 10
In addition to making 80 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA18 and emulsifier be polyethylene glycol oxide alkyl base phenyl ether sulfate ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd., trade name: " sub-library Asia Lip river BC-10 ") except 1 part, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 11 microns.
Suspension polymerisation Production Example 11
In addition to making 80 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA18 and emulsifier be two (the polycyclic phenyl ether of polyethylene glycol oxide) methacrylated sulfate ammonium salt (Japanese emulsifier Co. Ltd. systems, trade name: " Ya Duzikusi MS-60 ") except 1 part, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 11 microns.
Suspension polymerisation Production Example 12
Other than making 83 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA15 and emulsifier be to breathe out her 0.3 part of 18E of dike promise dew, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 12 microns.
Suspension polymerisation Production Example 13
Other than making 83 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA15 and emulsifier be to breathe out her 0.5 part of 18E of dike promise dew, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 12 microns.
Suspension polymerisation Production Example 14
In addition to making 83 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA15 and emulsifier be PVA-CST1.5 parts, other than 1.5 parts of 18E of Ha Yidi promise dew, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 9 microns.
Suspension polymerisation Production Example 15
Other than making 83 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA15 and emulsifier be LP0.5 parts, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 10 microns.
Suspension polymerisation Production Example 16
Other than making 83 parts of unsaturated monomer composition cyclohexyl methacrylate, TMPTMA15 and initiator be 2 parts of LPO, equally carried out with suspension polymerisation Production Example 1.The average grain diameter of obtained aqueous resin dispersion is measured with Kou Erde counter, is about 10 microns.
Suspension polymerisation Production Example 1~16 more than conclusion is indicated in table 1.
Table 1
| Production Example 1 | Production Example 2 | Production Example 3 | Production Example 4 | Production Example 5 | Production Example 6 | Production Example 7 | Production Example 8 | Production Example 9 | Production Example 10 | Production Example 11 | Production Example 12 | Production Example 13 | Production Example 14 | Production Example 15 | Production Example 16 | |
| (polymer) | ||||||||||||||||
| CHMA | 88 | 60 | 40 | 93 | 83 | 70 | 90 | 0 | 80 | 80 | 80 | 83 | 83 | 83 | 83 | 83 |
| TMPTMA | 10 | 10 | 10 | 5 | 15 | 10 | 10 | 10 | 18 | 18 | 18 | 15 | 15 | 15 | 15 | 15 |
| MMA | - | 28 | 27 | - | - | 20 | - | 90 | - | - | - | - | - | - | - | - |
| t-BMA | 20 | |||||||||||||||
| Piperidines (A) | 2 | 2 | 2 | 2 | 1 | - | - | - | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Benzotriazole (B) | - | - | 1 | - | - | - | - | - | ||||||||
| (initiator) | ||||||||||||||||
| LPO | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 0.5 | 2 |
| (emulsifier) | ||||||||||||||||
| PVA-CST | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1.5 | 0.5 | 0.5 |
| Breathe out her dike promise dew 18E | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.3 | 0.5 | 1.5 | 0.5 | 0.5 | |||
| Breathe out her dike promise dew N-08 | 1 | |||||||||||||||
| Sub-library Asia Lip river BC-10 | 1 | |||||||||||||||
| Ya Duzikusi MS-60 | 1 | |||||||||||||||
| Polymerism stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ◎ | ◎ | △ | ○ | ◎ | ○ | ○ |
Polymerization stability piperidines (A): 4- methacryloxy -2,2,6,6- tetramethyl piperidines (rising sun electrification Co. Ltd. system, trade name: sub- Supreme Being Ka Sitapu LA-87)
Benzotriazole (B): 2- [2 '-hydroxyls -5 '-(methacryloxyethyl) phenyl] -2H- benzotriazole (Otsuka Kagaku K.K. RUVA-93)
Acrylic emulsion Production Example 1
963.0 mass parts of pure water are added into the flask for having dropper, blender, nitrogen inlet, thermometer and the cooling tube that flows back, are slowly blown into nitrogen, while being warming up to 75 DEG C under stiring.On the other hand, to by 529.0 mass parts of methyl methacrylate (MMA), 25% aqueous solution, 80 mass parts of sub-library Asia Lip river BC-10 are added in the monomer mixture solution that 361.0 mass parts of 2- ethylhexyl acrylate (hereinafter referred to as 2EHA) and 100.0 mass parts of styrene (hereinafter referred to as St) and acrylic acid (hereinafter referred to as AA) are constituted, 230 mass parts of 25% aqueous solution, 40 mass parts and pure water of polyethylene glycol oxide alkyl phenyl ether (Di-ichi Kogyo Seiyaku Co., Ltd. nonionic reactive emulsifier sub-library Asia Lip river RN-20) (Di-ichi Kogyo Seiyaku Co., Ltd.'s nonionic reactive emulsifier), pre-emulsion mix is made.10 mass % of the pre-emulsion mix are added in above-mentioned flask, are maintained at after 75 DEG C, 5% 60.0 mass parts of ammonium persulfate aqueous solution are added, start to polymerize.It will be kept at 80 DEG C in reaction system after ten minutes, by the uniform dropwise addition in 180 minutes of remaining pre-emulsion mix.After completion of dropwise addition, with 20 mass parts pure water dropwise adding tanks, cleaning solution is added in above-mentioned flask.During dropwise addition, it will be maintained at 80 DEG C, after completion of dropwise addition in reaction system, stir 60 minutes at 80 DEG C, cure simultaneously, terminates polymerization.Then, it is cooled down, the ammonium hydroxide 9.3g of reaction system addition 25% at 50 DEG C or less is cooled to room temperature after stirring 10 minutes or more, is filtered with the wire mesh of 100 mesh, obtains polymeric dispersion.The average grain diameter of obtained acrylic emulsion uses up the measurement of scattering formula particle size determination device, about 150nm.
Acrylic emulsion Production Example 2
943.0 mass parts of pure water are added into the flask for having dropper, blender, nitrogen inlet, thermometer and the cooling tube that flows back, are slowly blown into nitrogen, while being warming up to 75 DEG C under stiring.On the other hand, 25% aqueous solution, 40 mass parts, 115 mass parts of 25% aqueous solution, 20 mass parts and pure water of sub-library Asia Lip river RN-20 (Di-ichi Kogyo Seiyaku Co., Ltd.'s nonionic reactive emulsifier) of sub-library Asia Lip river BC-10 (Di-ichi Kogyo Seiyaku Co., Ltd.'s nonionic reactive emulsifier) are added into the monomer mixture solution being made of CHMA200 mass parts, MMA102.6 mass parts, 2EHA137.4 mass parts, 50.0 mass parts of normal-butyl methacrylate (hereinafter referred to as n-BMA) and AA10.0 mass parts, pre-emulsion mix 1 is made.20 mass % in the pre-emulsion mix 1 are added in above-mentioned flask, are maintained at after 75 DEG C, 5% 60.0 mass parts of ammonium persulfate aqueous solution are added, start to polymerize.It will be kept at 80 DEG C in reaction system after ten minutes, by the uniform dropwise addition in 90 minutes of remaining pre-emulsion mix.After completion of dropwise addition, with 20 mass parts pure water dropwise adding tanks, cleaning solution is added in above-mentioned flask.During dropwise addition, it will be maintained at 80 DEG C, after completion of dropwise addition in reaction system, kept for 30 minutes at 80 DEG C, 25% 4.3 mass parts of ammonium hydroxide are added, terminates the polymerization in the 1st stage after neutralization.
Then, reaction system is maintained at 80 DEG C, dropped evenly the pre-emulsion mix 2 being made of CHMA200.0 mass parts, MMA102.6 mass parts, 2EHA137.4 mass parts, n-BMA50.0 mass parts, piperidines (A) 10.0,25% aqueous solution, 40 mass parts of sub-library Asia Lip river BC-10,25% aqueous solution, 20 amount part of sub-library Asia Lip river RN-20,115 mass parts of pure water equally manufactured with pre-emulsion 1 with 90 minutes at 80 DEG C.After completion of dropwise addition, dropwise adding tank is washed with 20 mass parts of pure water, cleaning solution is added in above-mentioned flask.Curing in 60 minutes is carried out at 80 DEG C again, terminates the polymerization in the 2nd stage.Then it is cooled down, 25% 5.0 mass parts of ammonium hydroxide is added in the reaction system at 50 DEG C or less and are cooled to room temperature after stirring 10 minutes or more, are filtered with the wire mesh of 100 mesh, obtain polymerization dispersion emulsion.The average grain diameter of obtained acrylic emulsion uses up the measurement of scattering formula particle size determination device, about 130nm.
Above-mentioned acrylic emulsion Production Example 1~2 is summarized in table 2.
Table 2
Acrylic emulsion Production Example 1~2)
| Production Example 1 | Production Example 2 | ||
| (monomer composition) | First stage | Second stage | |
| St | 100.0 | ||
| MMA | 529.0 | 102.6 | 102.6 |
| 2EHA | 361.0 | 137.4 | 137.4 |
| CHAM | 200.0 | 200.0 | |
| n-BMA | 50.0 | ||
| AA | 10.0 | 10.0 | |
| Piperidines (A) | 10.0 | ||
| Meter | 1000.0 | 500.0 | 500.0 |
| (initiator) | |||
| APS | 3.0 | 3.0 | |
| (emulsifier) | |||
| Sub-library Asia Lip river BC-1025 | 20.0 | 10.0 | 10.0 |
| Sub-library Asia Lip river RN-2025 | 10.0 | 5.0 | 5.0 |
| Non-volatile part (%) | 43.0 | 43.0 |
Embodiment 1
25% 0.3 part of ammonium hydroxide and tackifier WR-600 (non-volatile part: 5.0%) 2.9 parts are added in 29.0 parts of the aqueous resin dispersion prepared in suspension polymerisation Production Example 1.Viscosity is 1260mPa.s.100.0 parts of acrylic emulsion polymerizeing in acrylic emulsion Production Example 1, butyl match fine jade Suo Fu/CS-12 (2 as coalescing agent is wherein added, 2,4- trimethyl -1, one isobutyl ester of 3- pentanediol: odd rope Co. Ltd. system)=1/1 5.1 parts of mixed liquor, 0.2 part of foam inhibitor (SN Supreme Being not 777: Sai Nuopuge system of Ma) and dilution water, obtain clear coating composition.Index is non-volatile part 37.0%, viscosity 650mPa.s, pH8.5.
Embodiment 2
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 2, similarly to Example 1.Index is non-volatile part 36.9%, viscosity 650mPa.s, pH8.5.
Embodiment 3
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 3, similarly to Example 1.Index is non-volatile part 37.1%, viscosity 670mPa.s, pH8.6.
Embodiment 4
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 4, similarly to Example 1.Index is non-volatile part 37.1%, viscosity 700mPa.s, pH8.4.
Embodiment 5
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 5, similarly to Example 1.Index is non-volatile part 36.8%, viscosity 680mPa.s, pH8.5.
Embodiment 6
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 6, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 670mPa.s, pH8.5.
Embodiment 7
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 7, similarly to Example 1.Index is non-volatile part 37.3%, viscosity 720mPa.s, pH8.3.
Embodiment 8
Other than replacing acrylic emulsion Production Example 1 to use acrylic emulsion Production Example 2, similarly to Example 1.Index is non-volatile part 37.1%, viscosity 650mPa.s, pH8.5.
Embodiment 9
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 2, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 650mPa.s, pH8.6.
Embodiment 10
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 3, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 36.7%, viscosity 710mPa.s, pH8.7.
Embodiment 11
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 4, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 37.3%, viscosity 700mPa.s, pH8.5.
Embodiment 12
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 5, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 36.8%, viscosity 650mPa.s, pH8.6.
Embodiment 13
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 6, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 36.9%, viscosity 680mPa.s, pH8.4.
Embodiment 14
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 7, used except acrylic emulsion Production Example 2 instead of acrylic emulsion Production Example 1, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 700mPa.s, pH8.6.
Embodiment 15
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 9, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 700mPa.s, pH8.5.
Embodiment 16
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 10, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 690mPa.s, pH8.6.
Embodiment 17
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 11, similarly to Example 1.Index is non-volatile part 37.3%, viscosity 690mPa.s, pH8.5.
Embodiment 18
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 12, similarly to Example 1.Index is non-volatile part 36.7%, viscosity 670mPa.s, pH8.7.
Embodiment 19
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 13, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 690mPa.s, pH8.5.
Embodiment 20
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 14, similarly to Example 1.Index is non-volatile part 37.1%, viscosity 700mPa.s, pH8.4.
Embodiment 21
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 15, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 700mPa.s, pH8.5.
Embodiment 22
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 16, similarly to Example 1.Index is non-volatile part 37.3%, viscosity 670mPa.s, pH8.6.
Embodiment 23
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 9, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.7%, viscosity 700mPa.s, pH8.5.
Embodiment 24
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 10, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 37.1%, viscosity 690mPa.s, pH8.4.
Embodiment 25
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 11, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.8%, viscosity 670mPa.s, pH8.7.
Embodiment 26
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 12, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.9%, viscosity 670mPa.s, pH8.7.
Embodiment 27
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 13, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.8%, viscosity 680mPa.s, pH8.5.
Embodiment 28
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 14, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 37.2%, viscosity 700mPa.s, pH8.5.
Embodiment 29
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 15, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.3%, viscosity 700mPa.s, pH8.6.
Embodiment 30
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 16, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 37.3%, viscosity 710mPa.s, pH8.6.
Comparative example 1
Other than replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 8, similarly to Example 1.Index is non-volatile part 37.0%, viscosity 650mPa.s, pH8.5.
Comparative example 2
In addition to replacing suspension polymerisation Production Example 1 to use suspension polymerisation Production Example 8, used except acrylic acid silicone emulsion Production Example 2 instead of acrylic emulsion manufacture embodiment 1, similarly to Example 1.Index is non-volatile part 36.8%, viscosity 680mPa.s, pH8.5.
Comparative example 3
(non-volatile part: 5.0%) 2.9 parts, 0.2 part of foam inhibitor (Fu Ma -777: Sai Nuopuge system of SN Supreme Being), 1.0 parts of dispersing agent (5027: Sai Nuopuge system of SN Supreme Being Yi Sibasaituo) and dilution water obtain clear coating composition to 100.0 parts of acrylic emulsion, the tackifier WR-600 prepared in addition acrylic emulsion Production Example 1 in 4.4 parts of silica p-526 (marshy land chemistry system).Index is non-volatile part 37.3%, viscosity 920mPa.s, pH8.2.
Comparative example 4
It is same as comparative example 3 other than replacing suspension polymerisation Production Example 1 to use acrylic emulsion Production Example 2.Index is non-volatile part 37.2%, viscosity 900mPa.s, pH8.1.
The physical property of above Examples 1 to 30 and comparative example 1~4 is indicated in table 3 and table 4.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Suspension polymerisation Production Example A | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 |
| Acrylic emulsion Production Example | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 2 | 2 | 2 |
| (coating physical property) | ||||||||||
| Appearance extinction | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The transparency | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Absorptivity (%) | 6 | 6 | 5 | 6 | 5 | 5 | 6 | 5 | 5 | 5 |
| Appearance after heatproof water test | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Weatherability MWOM | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ |
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| Suspension polymerisation Production Example A | 4 | 5 | 6 | 7 | 9 | 10 | 11 | 12 | 13 | 14 |
| Acrylic emulsion Production Example | 2 | 2 | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 |
| (coating physical property) | ||||||||||
| Appearance extinction | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The transparency | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Absorptivity (%) | 6 | 5 | 5 | 5 | 5 | 4 | 4 | 3 | 4 | 7 |
| Appearance after heatproof water test | ○ | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | ◎ | △ |
| Weatherability MWOM | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 4
| Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | |
| Suspension polymerisation Production Example A | 15 | 16 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| Acrylic emulsion Production Example | 1 | 1 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| (coating physical property) | ||||||||||
| Appearance extinction | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The transparency | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Absorptivity (%) | 4 | 7 | 5 | 4 | 3 | 3 | 4 | 6 | 4 | 6 |
| Appearance after heatproof water test | ○ | △ | ○ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ |
| Weatherability MWOM | ○ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Suspension polymerisation Production Example A | 8 | 8 | Use silica | Use silica |
| Acrylic emulsion Production Example | 1 | 2 | 1 | 2 |
| (coating physical property) | ||||
| Appearance extinction | ○ | ○ | ○ | ○ |
| The transparency | ○ | ○ | × (gonorrhoea) | × (gonorrhoea) |
| Absorptivity (%) | 9 | 8 | 13 | 14 |
| Appearance after heatproof water test | ○ | ○ | × | × |
| Weatherability MWOM | △ | ○ | × | × |
Embodiment 31
(non-volatile part: 5.0%) 10 parts (viscosity 1260mPa.s), observation is at room temperature until the time of sedimentation for 1 part of the ammonium hydroxide and tackifier RW-600 that 25% is added in 100 parts of the aqueous dispersion prepared in suspension polymerisation Production Example 1.After sedimentation, sediment is stirred with stirring rod, whether there is or not hard bondings shape (redispersibility) for confirmation.
Comparative example 5
It is added in 100 parts of the aqueous dispersion prepared in suspension polymerisation Production Example 1 and matches 5.1 parts of mixed liquor of fine jade Suo Fu/CS-12=1/1 (viscosity 15mPa.s) as the butyl of coalescing agent, observation is at room temperature until the time of sedimentation.After sedimentation, sediment is stirred with stirring rod, whether there is or not hard bonding shapes for confirmation.
Time of the observation up to the sedimentation of 1 100 parts of aqueous dispersion (viscosity 10mPa.s) of Production Example.After sedimentation, sediment is stirred with stirring rod, whether there is or not hard bonding shapes for confirmation.
Test method
<non-volatile part>
Weigh obtained aqueous dispersion and coating composition about 1g.1 hour is dried at 105 DEG C with air drier, and using dry residual as non-volatile part, the ratio relative to dry preceding weight is indicated with weight %.
<pH>
The value at 25 DEG C is measured with pH meter (Horida, Ltd.'s system " F-23 ").
<viscosity>
It is measured at 30rpm, 25 DEG C with BM type viscosimeter (Tokyo Keiki Inc.'s system).And according to viscosity rotor selected to use.
<average grain diameter>
The average grain diameter of suspension polymer measures
With Kou Erde counter (Beckman Kou Erde company (Beckman Coulter Inc.) system, machine；Compound sizing machine II) measurement.
The average grain diameter of acrylic emulsion measures
Light scatters formula particle size determination device (U.S.'s Particale Sizing Systems corporation, machine；NICOMP380)
<appearance extinction>
Obtained coating composition is coated on the acrylic panel (too right machine material system) of black with 4mil liquid feeder.It arranges at room temperature after five minutes, with the gloss (light) of gloss meter (60 ° of Gloss) measurement dry 10 minutes coating-application plates in 100 DEG C of air drier.
GL25 or less --- zero, GL26 or more --- ×
The transparency for the coating-application plate that<transparency>is manufactured with colour difference meter measurement with method same as above-mentioned appearance extinction.
10 or less L value --- 11 or more zero, L value --- ×
<absorptivity>
It is sticked on a glass from mould paper, manufactures the template of 1 gummy item thick (about 300 microns of thickness) on it.Manufactured coating composition is flowed into the template, casting mold is made.It is 10 minutes dry in 100 DEG C of air drier after arrangement in 5 minutes, experimental film is made.After the experimental film is placed 24 hours at room temperature, it is cut into 4cm × 4cm, is measured weight (WO).Then, it submerges in normal-temperature water and is impregnated, after 1 week, take out, wipe the water on surface, measure the weight (W1) of film immediately.The experimental film is dried to 1 hour in 150 DEG C of air drier again, measures its weight (W2).By following formula, the water absorption rate of film is calculated.
Water absorption rate (%)=((W1-W2)/W2) × 100
<heatproof water test>
It after the coating-application plate manufactured with the same method of above-mentioned appearance extinction is placed 25 hours at room temperature, submerges in 60 DEG C of warm water and is impregnated, promote coating-application plate after 1 week, be dried at room temperature for 1 day.The appearance of coating-application plate after drying and not test (N.T.) plate (initial stage plate) are compared.
<weatherability (M-WOM)>
Solvent sealing material is coated on asbestos board, makes dry 20 microns/m2.After being dried at room temperature for 1 day, the primary coat coating prepared below is coated with 4mil liquid feeder and carries out drying in 10 minutes in 100 DEG C of air drier after 5 minutes arrange.After placing 1 day at room temperature, the coating composition coated with 4mil liquid feeder is 10 minutes dry in 100 DEG C of air drier after 5 minutes arrange, and manufactures coating-application plate.Super promotion weatherability test is carried out using the coating-application plate after manufacture by 1 day.
(super to promote weatherability test: M-WOM condition)
Exempt from the coating-application plate that above-mentioned manufacture is placed on Ta Luwuhuizha-testing machine in the Da Yipula of Da Yipulawuyi dike this corporation, with irradiation 6 hours (63 DEG C-humidity 50% of temperature), shower 10 seconds, 2 hours (95% or more 30 DEG C-humidity of temperature) of moisture condensation, be a circulation within shower 10 seconds, 700 hours are tested repeatedly.
Appearance of film was without exception in 1000 hours --- ◎, appearance of film was without exception in 700 hours --- zero, film color change --- △, cracks on film --- ×
(cooperation of primary coat coating)
◎ acrylic emulsion (Pu Kurui celestial being support EX-35: Japanese catalyst corporation): 300 parts by weight,
◎ white paste (following adjustment paste): 135 parts by weight,
● dispersing agent (Supreme Being's hair dew EP: KAO. Corp. SA's system): 60 parts by weight, (Supreme Being Yi Sigetuo N-14: Di-ichi Kogyo Seiyaku Co., Ltd.'s system): 50 parts by weight,
● wetting agent (Hui Malugu 909: KAO. Corp. SA's system): 10 parts by weight,
● ethylene glycol: 60 parts by weight,
● deionized water: 210 parts by weight,
● titanium oxide (CR-95: Shi Yuan industry companies): 1000 parts by weight,
● foam inhibitor (8034L: Sai Nuopuge corporation of promise Pu brother): 10 parts by weight,
● bead: 500 parts by weight,
Above-mentioned material is cooperated under divider 3000rpm stirring.Stirring is all added to be adjusted within 60 minutes.
◎ coalescing agent (butyl matches fine jade Suo Fu): 15 parts by weight
◎ (CS-12: odd rope Co. Ltd. system): 15 parts by weight
◎ black paste object (Niu Nilangtuo 88: horizontal creek is melted into company): 10 parts by weight
◎ foam inhibitor (8034L: Sai Nuopuge corporation of promise Pu brother): 1.5 parts by weight
Claims (2)
1, aqueous resin composition, aqueous resin dispersion by (A) containing 1~100 micron of average grain diameter of the resin particle that will have the monomer mixture suspension polymerisation of multifunctional 0.1~20 mass % of cross-linkable monomer of 50~99 mass % of (methyl) acrylate, (b) and 0~49.9 mass % of (d) other monomers of naphthenic base and/or tert-butyl to generate containing (a), wherein (a), (b) and (d) adds up to 100 mass %, and (B) is constituted containing average grain diameter for the aqueous resin dispersion of 0.01~1 micron of resin particle.
2, the manufacturing method of aqueous resin composition, it is characterized in that will have 50~99 mass % of (methyl) acrylate of naphthenic base and/or tert-butyl containing (a) containing, (b) in the aqueous resin dispersion for 1~100 micron of average grain diameter of the resin particle that the monomer mixture suspension polymerisation of multifunctional 0.1~20 mass % of cross-linkable monomer and 0~49.9 mass % of (d) other monomers generate, (C) tackifier are added, and mix the aqueous resin dispersion for the resin particle that (B) is 0.01~1 micron containing average grain diameter, wherein (a), (b) and (d) adds up to 100 mass %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002302536 | 2002-10-17 | ||
| JP302536/2002 | 2002-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101024221A Division CN100509885C (en) | 2002-10-17 | 2003-10-17 | Hydroresion dispersion, hydroresin composition and manufacturing method of said composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1931917A true CN1931917A (en) | 2007-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101024221A Expired - Fee Related CN100509885C (en) | 2002-10-17 | 2003-10-17 | Hydroresion dispersion, hydroresin composition and manufacturing method of said composition |
| CNA2006101416255A Pending CN1931917A (en) | 2002-10-17 | 2003-10-17 | Aqueous resin dispersion, aqueous resin composition and method for producing aqueous resin composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| CNB2003101024221A Expired - Fee Related CN100509885C (en) | 2002-10-17 | 2003-10-17 | Hydroresion dispersion, hydroresin composition and manufacturing method of said composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP2008138217A (en) |
| KR (1) | KR100732615B1 (en) |
| CN (2) | CN100509885C (en) |
| TW (1) | TW200406474A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443148A (en) * | 2011-01-14 | 2013-12-11 | 艾利丹尼森公司 | Removable composition with polymer microspheres |
| US9468224B2 (en) | 2011-08-31 | 2016-10-18 | Avery Dennison Corporation | Removable polymer compositions |
| CN112771012A (en) * | 2018-09-27 | 2021-05-07 | 陶氏环球技术有限责任公司 | Coating composition for porous building materials |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100890428B1 (en) * | 2007-08-20 | 2009-03-26 | 주식회사 선진화학 | Polymer composite particles containing sunscreen agents for cosmetic composition and the method for preparing thereof |
| US20110045301A1 (en) * | 2008-01-31 | 2011-02-24 | Mitsubishi Plastics, Inc. | Gas barrier film having excellent weather resistance |
| CN102219877A (en) * | 2010-04-16 | 2011-10-19 | 品青企业股份有限公司 | Macromolecule particle with ultraviolet absorption function group and cosmetic material containing same |
| US20140221568A1 (en) * | 2011-07-20 | 2014-08-07 | Nippon Shokubai Co., Ltd. | Molding material |
| KR101611210B1 (en) * | 2011-09-28 | 2016-04-11 | 세키스이가세이힝코교가부시키가이샤 | Resin particles, method for producing resin particles, and use of resin particles |
| CN103030731B (en) * | 2011-09-29 | 2016-08-24 | 积水化成品工业株式会社 | Resin particle and application thereof |
| JP6595863B2 (en) * | 2015-09-18 | 2019-10-23 | 株式会社日本触媒 | Resin emulsion for paint |
| CN109135445A (en) * | 2018-08-09 | 2019-01-04 | 深圳市前海奇迹新材料有限公司 | A kind of styrene-acrylic emulsion priming paint |
| CN113831790A (en) * | 2021-10-19 | 2021-12-24 | 黄明彦 | Preparation method of environment-friendly water-based paint |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3977536B2 (en) * | 1997-12-19 | 2007-09-19 | 松本油脂製薬株式会社 | Resin particles and method for producing the same |
-
2003
- 2003-09-26 TW TW092126752A patent/TW200406474A/en unknown
- 2003-10-15 KR KR1020030071659A patent/KR100732615B1/en not_active IP Right Cessation
- 2003-10-17 CN CNB2003101024221A patent/CN100509885C/en not_active Expired - Fee Related
- 2003-10-17 CN CNA2006101416255A patent/CN1931917A/en active Pending
-
2007
- 2007-12-28 JP JP2007340880A patent/JP2008138217A/en not_active Withdrawn
- 2007-12-28 JP JP2007340888A patent/JP2008138218A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443148A (en) * | 2011-01-14 | 2013-12-11 | 艾利丹尼森公司 | Removable composition with polymer microspheres |
| CN103443148B (en) * | 2011-01-14 | 2016-08-17 | 艾利丹尼森公司 | There is the Removable composition of polymer microballoon |
| US9783627B2 (en) | 2011-01-14 | 2017-10-10 | Avery Dennison Corporation | Removable composition with polymer microspheres |
| US9468224B2 (en) | 2011-08-31 | 2016-10-18 | Avery Dennison Corporation | Removable polymer compositions |
| CN112771012A (en) * | 2018-09-27 | 2021-05-07 | 陶氏环球技术有限责任公司 | Coating composition for porous building materials |
| US12071560B2 (en) | 2018-09-27 | 2024-08-27 | Dow Global Technologies Llc | Coating composition for pourous construction materials |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100732615B1 (en) | 2007-06-27 |
| JP2008138218A (en) | 2008-06-19 |
| CN100509885C (en) | 2009-07-08 |
| KR20040034458A (en) | 2004-04-28 |
| JP2008138217A (en) | 2008-06-19 |
| TW200406474A (en) | 2004-05-01 |
| CN1497000A (en) | 2004-05-19 |
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