WO2001092432A1 - Emulsion de resine synthetique et composition d'impermeabilisant contenant cette emulsion pour surpeinture - Google Patents
Emulsion de resine synthetique et composition d'impermeabilisant contenant cette emulsion pour surpeinture Download PDFInfo
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- WO2001092432A1 WO2001092432A1 PCT/JP2001/004667 JP0104667W WO0192432A1 WO 2001092432 A1 WO2001092432 A1 WO 2001092432A1 JP 0104667 W JP0104667 W JP 0104667W WO 0192432 A1 WO0192432 A1 WO 0192432A1
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- synthetic resin
- alkyl
- resin emulsion
- acrylate
- monomer
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- 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
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- the present invention relates to a synthetic resin emulsion used as a main component of a water-based sealer composition (primer composition) for recoating a coating film, particularly a resin-based old coating film.
- inorganic materials such as slate-calcium silicate are used as exterior materials for buildings.
- these exterior materials are further coated with various overcoating materials for the purpose of aesthetics and protection.
- Form a coating In many cases, acrylic resin paint is used as such a topcoat material.
- the coating film is occasionally stained and deteriorates due to factors such as ultraviolet rays and rain. Therefore, it is necessary to repair the deteriorated coating film, that is, the old coating film.
- organic solvent-based sealers have been mainly used as sealers used for recoating, and ordinary water-based sealers have problems with adhesion to aqueous single-layer elastic paints.
- organic solvent-based sealers are excellent in adhesion, they contain a large amount of organic solvents, and their use tends to be restricted.
- a water-based sealer that does not contain an organic solvent as the sealer for repainting.
- a water-based sealer after re-emulsification of chlorinated polyolefin is used. I have.
- the post-emulsification requires dissolving the chlorinated polyolefin with a large amount of an organic solvent, and the use of an organic solvent cannot be eliminated at all.
- the specific gravity of the chlorinated polyolefin is large, sedimentation is likely to occur, and there may be a problem in storage stability.
- this sealer requires a chlorinated polyolefin resin and a large amount of an emulsifier, so that the raw material cost is lower than that of a normal aqueous acrylic emulsion or aqueous styrene / acrylic emulsion. Tend to be higher. In recent years, there has been a strong demand for dechlorination due to growing concern about environmental issues, and it has been desired to reduce or eliminate the use of chlorinated polyolefins containing chlorine in sealers.
- the present inventors have recently proposed an aqueous elastomer prepared by using a specific emulsifier and copolymerizing a monomer having a specific composition, and using an emulsion that satisfies specific conditions. Although it does not contain an organic solvent having a low boiling point such as xylene or toluene, it has been found that it exhibits excellent physical properties equivalent to that of a solvent-based sealer, for example, adhesion to an old coating film surface. The present invention is based on this finding.
- an object of the present invention is to provide a synthetic resin emulsion used in a water-based sealer composition having excellent adhesion to an old coating film and a top coating film.
- the synthetic resin emulsion of the present invention is obtained by dispersing synthetic resin particles in water, which is used as a main component of a sealer composition for coating recoating,
- (a) (meth) acrylic acid alkyl ester (here, an alkyl group having 4 or less carbon atoms contains 50% by weight or more based on all (meth) acrylic acid alkyl esters); 99.5% by weight,
- the glass transition temperature (T g) is 15 to 50 ° C, and the dispersed synthetic resin particles The particles have an average particle diameter of 0.01 to 0.2 ⁇ m.
- a sealer composition for recoating a coating film of the present invention comprises the synthetic resin emulsion.
- the synthetic resin emulsion according to the present invention is used as a main component of a sealer composition for repainting an old coating film.
- the old coating film is a coating film formed of various resin paints applied to the surface of the exterior material of a building, and the stains adhere to the coating over time, or are exposed to ultraviolet light, rain, etc. Refers to a coating film deteriorated by the influence.
- any resin-based paint may be used regardless of whether it is a solvent-based paint or a water-based paint.
- acrylic resin paint and vinyl acrylate acetate Resin paint examples include acrylic resin paint and vinyl acrylate acetate Resin paint, acrylic / styrene resin paint, vinyl chloride resin paint, alkyd resin paint, urethane resin paint, and the like.
- acrylic resin paint or an acrylic / vinyl acetate resin paint is preferred.
- the sealer composition for repainting the old paint film refers to the adhesion between the top coat film (or exterior paint) provided to modify or protect the exterior material of the building and the old paint film on the exterior material surface. To be applied to the old coating film for the purpose of improving the paint quality and appearance of the top coating film.
- the overcoating material may be any type of water-based or solvent-based, and specifically includes, for example, an elastic paint such as a single-layer elastic paint and a multi-layer elastic paint, an acrylic resin paint, and an acrylostyrene. Resin paints, acrylic resin paints, silicone resin paints, acrylic urethane resin paints, and urethane resin paints. Of these, a single-layer elastic paint, which is generally used for repainting, is preferred.
- the synthetic resin emulsion according to the present invention is obtained by dispersing synthetic resin particles in water,
- (a) (meth) acrylic acid alkyl ester (where the alkyl group has 4 carbon atoms) The following are contained in the total (meth) acrylic acid alkyl ester in an amount of 50% by weight or more), 20 to 99.5% by weight,
- (c) A monomer obtained by copolymerizing 0 to 79.5% by weight of a monomer copolymerizable with the above (a) and (b) using an alkyl diphenyl ether disulfonate as an emulsifier. It is.
- the glass transition temperature (T g) of the synthetic resin emulsion is 15 to 50 ° C., and the average particle diameter of the synthetic resin particles dispersed therein is 0.01 to 0.2. ⁇ m.
- the synthetic resin emulsion according to the present invention has excellent permeability to the deteriorated old paint film of various resin systems, and has excellent adhesion to paints such as a single-layer elastic paint and a multi-layer elastic paint used as a recoating material for repainting, especially water resistance. Excellent adhesion. Therefore, so-called blistering does not occur at the interface between the topcoat material and the sealer and at the interface between the sealer and the old coating film, and the topcoat film does not peel off. Further, according to the synthetic resin emulsion according to the present invention, it is possible to prepare an aqueous sealer composition having the same level of adhesion to an old coating film as a solvent system without containing an organic solvent such as a low boiling point solvent.
- the synthetic resin emulsion of the present invention the use of chlorinated polyolefins can be avoided or the amount thereof can be reduced, so that the odor of the conventional water-based sealer can be improved.
- the chlorine content in the sealer composition can also be reduced.
- the alkyl diphenylterdisulfonic acid salt is used as an emulsifier at the time of copolymerization or is added after the copolymerization so as to be contained in the synthetic resin emulsion of the present invention.
- the synthetic resin emulsion it is preferable to use the synthetic resin emulsion as an emulsifier at the time of copolymerization.
- the alkyl diphenyl ether disulfonic acid salt is a compound represented by the following formula (I).
- R represents an alkyl group
- sodium (Na) is preferred because it is easily available. Therefore, as the alkyl diphenyl ether disulfonate used as the emulsifier in the present invention, sodium alkyl diphenyl ether disulfonate is preferable.
- the alkyl diphenyl ether disulfonate used in the present invention has an effect of imparting alkali resistance to the synthetic resin emulsion. Therefore, the use of the alkyl diphenyl ether disulfonate is advantageous in that the sealer and the overcoating material can be protected from alkali derived from an inorganic base material.
- the alkyl diphenyl sodium terdisulfonate is a trade name of Relex SSL, Relex SSH (all manufactured by Kao Corporation), Dowfax2Al, Newcol 271 A, or Newcol 271 S (all, Japanese emulsifier)
- the product can be obtained as such.
- alkyldiphenyl-terdisulfonic acid ammonium can be obtained, for example, under the trade name Newcol 271 NH (manufactured by Japan Emulsifier).
- the amount of the alkyldiphenylterdisulfonic acid salt to be used is preferably from 0.1 to 20% by weight, more preferably from 0.3 to 10% by weight, based on all monomers. It is preferable that the amount of the alkyl diphenyl ether disulfonate to be used is within the above range from the viewpoint of more excellent adhesion and water resistance as a sealer.
- surfactants can be used in combination with the alkyl diphenyl monoterdisulfonate as an emulsifier.
- surfactants examples include anion-based surfactants used in ordinary emulsion polymerization. Examples include surfactants, nonionic surfactants, cationic surfactants, and radical polymerizable surfactants having a radical polymerizable unsaturated bond in the structure. These may be used alone or in combination of two or more.
- anionic surfactant examples include sodium alkylbenzene sulfonate, sodium alkyl sulfonate, sodium polyoxyethylene alkyl ether sulfonate, and the like.
- nonionic surfactants include, for example, those of polyoxyethylene alkyl ether type, polyoxyethylene alkyl ether type, polyoxyethylene glycol type or polyoxypropylene glycol type.
- the radically polymerizable surfactant can be appropriately selected from known ones, and examples thereof include anionic surfactants and nonionic reactive surfactants. Specific examples of the radically polymerizable surfactant include the following compounds 1) to 15).
- R 1 , R 2 H, CH 3
- R 3 C 7 - 21 alkyl, an alkenyl group
- M alkali metal, ammonium group, amine
- R1 R 1 H, CH 3
- H2 A an alkylene group of C 2 ⁇ 4, substituted alkylene group
- n 0, positive number
- R 2 unsubstituted or substituted hydrocarbon group, amino group, etc.
- R 3 H propenyl group
- A an alkylene group, a substituted alkylene group of C 2 4,
- R 1 H. CH 3
- R 2 hydrocarbon group having C 8 24, etc.
- A an alkylene group of C 2 -4
- M H, Al metal, Al earth metal, Ammonium group, etc.
- R hydrocarbon group having C 8 ⁇ 22,
- R hydrocarbon group having C 8 ⁇ 22,
- M Al-Li metal, ammonium group
- CHCOOM M ammonium, ammonium, alkali metal
- R1 CH3 R 1, 2: H. CH 3, x 0 ⁇ 100s) CH2 i; cCOOOO ((CC22HH 44 00)) xx ((CCIHCH20) y (C 2 H40) zR2 y: 0 ⁇ : 100, z: 0 to L 00,
- R 1 an alkyl group having C 6 ⁇ 18, etc.
- R 2 H, alkyl group of C 6 ⁇ 18, etc.
- R 3 H, propenyl group
- n 1 to 200
- CH 2 CCOO (AlO) mRl R 1 , R 2 : H, C 20 Hydrocarbon group, acyl group,
- the amount of such another surfactant to be used is preferably 0 to 15% by weight, more preferably 0.1 to 10% by weight, based on all monomers.
- the amount of the other surfactant used is within the above range, generation of aggregates during polymerization can be suppressed, and remarkable decrease in water resistance of the emulsion can also be suppressed.
- the synthetic resin emulsion according to the present invention is obtained by polymerizing at least an alkyl (meth) acrylate, an ethylenically unsaturated carboxylic acid, and a monomer copolymerizable therewith, as monomers. is there.
- the alkyl acrylate that can be used as such a monomer for polymerization (meth) is not particularly limited and can be appropriately selected according to the purpose.
- an alkyl (meth) acrylate an acrylate or a methyl acrylate in which the alkyl group has 1 to 12 carbon atoms is preferable.
- the alkyl (meth) acrylate having an alkyl group having 4 or less carbon atoms is contained in an amount of 50% by weight or more based on the total amount of the alkyl (meth) acrylate used. It is more preferably contained in an amount of 0% by weight or more.
- an alkyl (meth) acrylate having an alkyl group having 4 or less carbon atoms is similar to the resin composition of the elastic coating material as the top coating material, and thus is obtained by using the synthetic resin emulsion according to the present invention. This is advantageous because the adhesion between the colorant and the topcoat material is good. In this case, it is also advantageous in that it has excellent resistance to water adhesion.
- alkyl group having 4 or less carbon atoms examples include a methyl group, an ethyl group, an n-butyl group, and a t-butyl group. Therefore, as the alkyl (meth) acrylate having an alkyl group having 4 or less carbon atoms, methyl methacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, and ethyl methacrylate are preferred. be able to. These may be used alone or in combination of two or more.
- methyl methacrylate and butyl acrylate are more preferred in view of weather resistance, transparency of the film, water resistance and toughness of the obtained film.
- the amount of the alkyl (meth) acrylate to be used is usually 20 to 99.5% by weight based on all monomers. It is preferable that the amount of the (meth) acrylic acid alkyl ester be within the above range, since it can prevent delamination with the overcoat film and various adhesion defects.
- the ethylenically unsaturated carboxylic acid which is a monomer used for forming the emulsion, is not particularly limited and can be appropriately selected depending on the purpose.
- the obtained synthetic resin emulsion can be more stable.
- Examples of the ethylenically unsaturated carboxylic acid in the present invention include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and cinnamic acid, and dicarboxylic acids. No. These may be used alone or in combination of two or more.
- acrylics are preferred in terms of easy availability, copolymerizability, storage stability of the resulting emulsion, and good adhesion to the top coat when used as a sealer.
- Acids and methacrylic acid are preferred.
- the amount of the ethylenically unsaturated carboxylic acid to be used is preferably 0.5 to 10.0% by weight, more preferably 1.0 to 6.0% by weight, based on all monomers.
- amount of the ethylenically unsaturated carboxylic acid used is within the above range, it is advantageous from the viewpoint of the stability of the obtained emulsion, and is preferable in that the water resistance when applied as a sealer is more excellent.
- the monomer copolymerizable with the alkyl (meth) acrylate and the ethylenically unsaturated carboxylic acid used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Those having an unsaturated bond are preferred.
- copolymerizable monomer a functional group-containing monomer, a crosslinkable monomer, and the like can also be used.
- Examples of the functional group-containing monomer include a functional group selected from a glycidyl group, a ureido group, an acetoacetoxy group, an acetoacetyl group, an amide group, an aryl group, a silyl group, a nitrile group, and a hydroxyl group.
- the following monomers can be used.
- the functional group in the emulsion can chemically act on the old coating film and the topcoat material, and the adhesion between these and the sealer and the water-resistant adhesion can be improved.
- the monomer copolymerizable with the alkyl (meth) acrylate and the ethylenically unsaturated carboxylic acid used in the present invention include, for example, ethylene, vinyl chloride, vinylidene chloride, styrene, and methyl.
- Aromatic vinyl compounds such as styrene, vinyl acetate, vinyl acetate, vinyl propionate, vinyl laurate, vinyl esters such as beova (vinyl vasate), vinyl phosphate, acrylonitrile, acrylamide, methylacrylamide C, N-methylol acrylic amide, glycidyl acrylate, glycidyl methacrylate, aryl glycidyl ether, acetoacetoxyalkyl (meth) acrylate, acetoacetate And 2-hydroxyalkyl acrylate, alkoxyethyl acrylate, and methyl acrylamide ethyl ethylene perylene.
- vinyl esters such as beova (vinyl vasate), vinyl phosphate, acrylonitrile, acrylamide, methylacrylamide C, N-methylol acrylic amide, glycidyl acrylate, glycidyl methacrylate, aryl glycidyl ether, aceto
- vinylalkoxy silanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinyl (2-methoxyethoxy) silane, and vinyltriacetoxysilane; Epoxyalkoxysilanes such as cidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, epoxyalkoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, and 3,4-epoxycyclohexylethyldimethoxysilane , Mercaptoalkoxysilanes, mercaptoalkoxysilanes such as mercaptopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and acryloxycarbonyl B pills triethoxysilane, etc. can also be mentioned.
- styrene is preferably used as the copolymerizable monomer.
- the use of styrene is advantageous in that it improves the water resistance and alkali resistance of the obtained sealer and can adjust the glass transition temperature of the synthetic resin emulsion. Further, the use of styrene is preferable from the viewpoint of cost reduction.
- acetoacetoxyalkyl (meth) acrylate when a functional group-containing monomer is used as a copolymerizable monomer, it is preferable to use acetoacetoxyalkyl (meth) acrylate.
- the acetoacetoxyalkyl (meth) acrylate is an alkyl acrylate or methacrylate containing an acetoethoxy group.
- acetoacetoxyalkyl (meth) acrylate can be used as a copolymerizable monomer in combination with the styrene described above.
- acetoacetoxyalkyl (meth) acrylate is more preferably acetoacetoxyalkyl methacrylate.
- Preferred examples of the crosslinkable monomer include monomers having two or more polymerizable unsaturated groups.
- Examples of such monomers having two or more polymerizable unsaturated groups include divinyl compounds, di (meth) acrylate compounds, tri (meth) acrylate compounds, tetra (meth) acrylate compounds, and diaryl compounds. Compounds, triallyl compounds, tetraaryl compounds and the like.
- crosslinkable monomers has the advantage of improving the water resistance, alkali resistance, chemical resistance, etc. of the resulting synthetic resin emulsion, but increases the crosslink density and decreases the adhesion to the topcoat paint, In the long term, there is a risk that the crosslinking point may be deteriorated by ultraviolet rays and the physical properties may be sharply reduced.
- the amount of such a copolymerizable monomer used can be appropriately changed depending on the type of the copolymerizable monomer used, the amount of other monomers used, and the like.
- the content is 0 to 79.5% by weight, preferably 0 to 70% by weight or less.
- a body its use amount is preferably from 0.1 to 10% by weight, more preferably from 0.3 to 5.0% by weight, based on all monomers.
- the amount of the monomer containing the functional group is within the above range, it is advantageous from the viewpoints of adhesion and water resistance between the sealer, the old coating film and the topcoat material. It is also excellent from the viewpoint of the stability of the synthetic resin emulsion.
- auxiliary components that can be used in the synthetic resin emulsion according to the present invention are not particularly limited, and can be appropriately selected according to the purpose.
- Such usable components include, for example, a polymerization initiator, a film-forming aid, an MFT adjuster, a chain transfer agent, a surface tension reducing agent, an aqueous medium, a pH adjuster (or a neutralizing agent), a thickener.
- Known additives such as antifreezing agents, defoamers, and preservatives are included.
- polymerization initiator examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate (APS); organic peroxides such as hydrogen peroxide and butyl peroxide; And a redox polymerization initiator in combination with an agent. These may be used alone or in a combination of two or more.
- persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate (APS)
- organic peroxides such as hydrogen peroxide and butyl peroxide
- a redox polymerization initiator in combination with an agent may be used alone or in a combination of two or more.
- the chain transfer agent is not particularly limited, and can be appropriately selected from known ones.
- Examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol, acetone, methyl ethyl ketone, cyclohexane, acetofenone, acetaldehyde, propionaldehyde, n-butylaldehyde, and furfural.
- carboxylic acids having 2 to 8 carbon atoms such as benzaldehyde, and mercaps, such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octyl thioglycolate, and thioglycerol. These may be used alone or in combination of two or more.
- the sealer may be repelled by the old paint film at the time of applying the sealer, making it difficult to paint.
- a surface tension reducing agent may be added to the synthetic resin emulsion used in the sealer composition.
- the surface tension lowering agent examples include organic solvents such as alcohol having surface tension lowering ability, and surfactants having surface tension lowering ability. From the viewpoint of odor and safety, the surface tension reducing agent has the surface tension lowering ability. Surfactants are preferred. Examples of the surfactant having a surface tension lowering ability include difluoroalkyl sulfonates, difluoroalkyl carboxylate, and perfluoroalkyl phosphate such as difluoroalkyl phosphate.
- Surfactants for example, cationic fluorosurfactants such as perfluoroalkyltrimethylammonium salt; amphoteric surfactants such as perfluoroalkylbenzoin; Nonionic fluorine-based fields such as polyalkylamine oxides and perfluoroalkylethylene oxide adducts
- Surfactants for example, alkylsulfosuccinates such as dioctylsulfosuccinate, polyoxyalkylene alkyl ether phosphonates, polyoxyalkylene alkyl ether phosphates such as polyoxyalkylene alkyl ether phosphate, etc.
- alkyl sulfates Ter, alkylaryl sulfonates and condensates thereof, alkyl sulfates; for example, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers, polyoxyethylene alkyls Phenyl ether, polyoxyethylene sorbine fatty acid ester, and the like. These may be used alone or in combination of two or more.
- the synthetic resin emulsion according to the present invention preferably has a minimum film forming temperature (M F T) of 0 ° C. or lower.
- MFT can be measured by using an MFT measuring device (manufactured by Tester Sangyo Co., Ltd.).
- the minimum film forming temperature means that water in the emulsion evaporates as the drying proceeds, and the synthetic resin particles are densely packed, and these particles are fused and diffused to form a continuous film. Is the minimum temperature required for
- the sealer composition using the synthetic resin emulsion according to the present invention is usually applied at indoor and outdoor construction sites.
- MFT is 0 ° C or less, it is advantageous in that a film can be always formed at a normal environmental temperature.
- a high-boiling solvent as a film-forming aid or an MFT adjuster can be used in the synthetic resin emulsion. Therefore, a film-forming auxiliary can be used to keep the MFT at 0 ° C. or lower.
- the film forming aid is not particularly limited and may be appropriately selected from known ones. Examples thereof include a hydrocarbon solvent, an alcohol solvent, ether alcohol and an ether solvent, an ester and an ether ester solvent. And the like.
- the high boiling point solvent is preferably an organic solvent having a boiling point of 150 ° C. or more.
- examples of the hydrocarbon-based solvent include mineral spirits and petroleum-based solvents.
- examples of the alcohol-based solvent include benzyl alcohol.
- examples of the ether-based alcohol and the ether-based solvent include ethylene glycol monobutyl ether (butyl sorb). To ethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (DPM), propylene glycol n-butyl ether (PnB), dipropylene glycol n-butyl ether (DPnB), and ethylene glycol mono-2-ethyl Xyl ether (EHG) and the like.
- ester and ether ester solvents examples include diethylene glycol monobutyl ether acetate (BCA), 2,2,4-trimethyl-1,3-pentendiol monoisobutylate (Texanol), and the like. .
- Texanol, EHG, DPnB or the like is preferable as the film-forming auxiliary, and Texanol is more preferable, from the viewpoints of easy entry into the emulsion particles, MFT lowering effect, stability after addition, and the like.
- the synthetic resin emulsion according to the present invention preferably has a glass transition temperature (Tg) of 15 to 50 ° C, preferably 20 to 45 ° C.
- Tg glass transition temperature
- the glass transition temperature refers to a temperature at which the synthetic resin particles in the synthetic resin emulsion undergo a phase change from a hard and brittle glass state to a soft rubber state.
- the glass transition temperature in the present invention can be obtained by calculating the following FOX equation.
- W1, W2, W3, ⁇ , Wn mean the weight fraction of each monomer
- T gu T g 2, T gs ⁇ ⁇ , T g n denotes a glass transition point of each homopolymer one (absolute temperature). ] It is preferable that the glass transition temperature is within the above range, since the adhesion between the sealer and the overcoat film is excellent. When the glass transition temperature is within such a temperature range, the amount of the film-forming aid used to reduce the MFT to 0 ° C or less can be reduced, so that the film-forming aid in the synthetic resin emulsion is used. The content can be relatively reduced, and as a result, the water resistance and stability of the synthetic resin emulsion can be improved.
- the amount of the film-forming aid used to reduce the MFT to 0 ° C or less may be small, but the adhesion between the sealer and the topcoat film is low. It may decrease. If the glass transition temperature is higher than 50 ° C, the amount of the film-forming aid used to reduce the MFT to 0 ° C or less increases, and the stability of the synthetic resin emulsion decreases. Further, since the film-forming aid remains in the sealer film in excess, the water resistance of the film may be reduced. Average particle size of synthetic resin particles dispersed in emulsion
- the average particle diameter of the synthetic resin particles dispersed in the synthetic resin emulsion according to the present invention is from 0.01 to 0.2 m, preferably from 0.05 to 0.15 m.
- the average particle diameter of the synthetic resin particles dispersed in the synthetic resin emulsion can be measured by a principle generally called a photon correlation method. It can be measured using NICOMP MODEL 370 submicron particle sizer ( Pacific Scientific). Method for producing synthetic resin emulsion
- the synthetic resin emulsion according to the present invention can be copolymerized with at least an alkyl (meth) acrylate, an ethylenically unsaturated carboxylic acid, and a monomer as monomers in the presence of an alkyl diphenyl ether disulfonic acid salt as an emulsifier. It can be produced by copolymerizing with a simple monomer.
- the polymerization method There is no particular limitation on the polymerization method.
- Examples thereof include a method of emulsifying a monomer to be dropped with an emulsifier and water in advance, and then dropping the emulsified monomer.
- the monomers and auxiliary components used for the polymerization can be appropriately selected from the above-mentioned monomers and / or auxiliary components.
- the polymerization reaction conditions are not particularly limited, and can be appropriately selected according to the type and purpose of the copolymer component. Sealer composition
- the sealer composition according to the present invention comprises the above-described synthetic resin emulsion according to the present invention.
- the sealer composition according to the present invention may contain various conventional components as long as it comprises the above-mentioned synthetic resin emulsion.
- the sealer composition according to the present invention may further include an aqueous chlorinated polyolefin dispersion.
- the sealer composition containing the synthetic resin emulsion according to the present invention and the aqueous dispersion of chlorinated polyolefin is excellent even in a very deteriorated old coating film or a special resin-based old coating film. Excellent adhesion and water resistance can be exhibited.
- the synthetic resin emulsion and the aqueous chlorinated polyolefin dispersion can be advantageously used together in the sealer composition as described above, in the conventional aqueous sealer containing the aqueous chlorinated polyolefin dispersion as a main component, By using the synthetic resin emulsion of the present invention, the odor can be reduced, and the product cost can be reduced.
- the sealer composition according to the present invention may further contain other auxiliary agents.
- auxiliary agents include an antifoaming agent, a wetting agent, a deicing agent, a preservative, a viscosity modifier, Examples include dispersants, film-forming aids, plasticizers, coloring agents such as pigments, gypsum, cement, and fillers.
- a small amount of a solvent may be further incorporated for the purpose of improving the drying property and the coating property.
- auxiliaries for example, pigment paste
- an outer package comprising: applying the sealer composition according to the present invention to an old coating film on the surface of an exterior material, and then applying an overcoat material thereon.
- a method for repainting a coating film on a material surface is provided.
- Emulsion polymerization is carried out by dropping. After completion of the polymerization, the mixture was cooled, neutralized with ammonia water (10 ammonia), and 196 parts of Texanol as a film-forming aid were added thereto. Then, water was added to obtain emulsion 1 having a nonvolatile content adjusted to about 45%. The glass transition temperature (Tg: calculated value) of the obtained emulsion was 36 ° C. Emulsion 2 ⁇ 11
- emulsion 2 was prepared in the same manner as emulsion 1 -11 was prepared. All values in Table 1 represent parts by weight.
- MFT (° C) 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less 0 or less
- Sealer compositions 1 to 13 were prepared with the formulations shown in Table 2.
- the pigment paste was obtained by dispersing and mixing the components shown in Table 3 using a sand mill. All values in Tables 2 and 3 represent parts by weight. Evaluation method
- a slate plate was coated with a commercially available solvent-based acryl / vinyl acetate-based paint and cured at 50 ° C for 3 days to be thermally degraded to form an old paint film.
- the sealer compositions 1 to 13 were applied to the old coating film so as to have a solid content of 10 to 12 g / m 2 , respectively, and dried at room temperature.
- a commercially available single-layer elastic coating material 8 a commercially available single-layer elastic coating material 6, and a main material C of a commercially available multi-layer elastic coating material were coated 1 mm in a wet state, and this was applied at room temperature. The specimen was dried for one week to obtain a test body.
- Formulation of pigment paste Formulation j Water 20 Tyrose 2% aqueous solution of MH2,000K (methylhydroxyethylcellulose) 100 10% aqueous solution of sodium hexametaphosphate 5 Dispersant (Additol XW-330 (dispersant)) (Nopco8034 (Sannobuco)) 2 Preservative (Mergal KM101A) 2 Titanium oxide (To Thailand ° -C R-820 (manufactured by Ishihara Sangyo Co., Ltd.)) 150 Calcium carbonate (Dacal 5) 150 Cray (NN Light Kaolin Kure- (Manufactured by Tsuchiya Kaolin)) 50
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Sealing Material Composition (AREA)
- Polymerisation Methods In General (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01934506A EP1236781B1 (en) | 2000-06-01 | 2001-06-01 | Synthetic resin emulsion and sealer composition containing the same for recoating |
DE60105387T DE60105387T2 (de) | 2000-06-01 | 2001-06-01 | Synthetische harzemulsion und siegelzusammensetzung, die diese für die wiederbeschichtung enthält |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-164663 | 2000-06-01 | ||
JP2000164663A JP4700167B2 (ja) | 2000-06-01 | 2000-06-01 | 合成樹脂エマルジョン、およびそれを用いた塗膜塗り替え用シーラー組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001092432A1 true WO2001092432A1 (fr) | 2001-12-06 |
Family
ID=18668252
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/004667 WO2001092432A1 (fr) | 2000-06-01 | 2001-06-01 | Emulsion de resine synthetique et composition d'impermeabilisant contenant cette emulsion pour surpeinture |
Country Status (5)
Country | Link |
---|---|
US (1) | US20030114587A1 (ja) |
EP (1) | EP1236781B1 (ja) |
JP (1) | JP4700167B2 (ja) |
DE (1) | DE60105387T2 (ja) |
WO (1) | WO2001092432A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7022785B2 (en) * | 2002-03-01 | 2006-04-04 | Equistar Chemicals L.P. | Diimine complexes for olefin polymerization |
CN110964425A (zh) * | 2018-10-01 | 2020-04-07 | 日信化学工业株式会社 | 涂敷组合物和层叠体 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7795343B2 (en) * | 2005-12-13 | 2010-09-14 | Rohm And Haas Company | Polymer composition |
EP1798246A1 (de) * | 2005-12-15 | 2007-06-20 | VESTOLIT GmbH & Co. KG | Verfahren zur Herstellung von wässrigen Vinylchlorid-(Meth)Acrylat-Copolymerisaten und deren Verwendung in wässriger Form |
US8426632B2 (en) | 2007-08-31 | 2013-04-23 | The Nippon Synthetic Chemical Industry Co., Ltd. | Crosslinking agent, crosslinked polymer, and uses thereof |
JP2009149798A (ja) * | 2007-12-21 | 2009-07-09 | Dic Corp | 樹脂水性分散体 |
EP2668236A1 (de) * | 2011-01-25 | 2013-12-04 | BASF Coatings GmbH | Basislacke für überbrannte mehrschichtlackierungen |
EP2731975B1 (de) * | 2011-07-14 | 2016-04-20 | Basf Se | Verfahren zur herstellung wasserabsorbierender polymerpartikel mit hoher anquellgeschwindigkeit |
US9950306B2 (en) | 2011-07-14 | 2018-04-24 | Basf Se | Process for producing water-absorbing polymer particles with high free swell rate |
JP6656046B2 (ja) * | 2016-03-29 | 2020-03-04 | 株式会社日本触媒 | ひび割れ補修用シーラー用樹脂組成物 |
CN107325224A (zh) * | 2017-08-08 | 2017-11-07 | 芜湖通全科技有限公司 | 一种沥青涂料改性用乳液的制备方法 |
CN110003728A (zh) * | 2019-04-04 | 2019-07-12 | 南京瑞固聚合物有限公司 | 一种改性水性丙烯酸树脂分散体及其制备方法 |
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JPH03134078A (ja) * | 1989-10-19 | 1991-06-07 | Asahi Denka Kogyo Kk | 下地塗材組成物 |
JPH09302270A (ja) * | 1996-03-14 | 1997-11-25 | Kansai Paint Co Ltd | 水性塗料及びこれを用いた塗装仕上げ方法 |
JPH11124545A (ja) * | 1997-10-27 | 1999-05-11 | Kansai Paint Co Ltd | 水性塗料組成物及びこれを用いた塗装仕上げ方法 |
EP0952161A2 (de) * | 1998-04-24 | 1999-10-27 | Basf Aktiengesellschaft | Emulgatorgemisch für die Emulsionspolymerisation |
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JPH01190764A (ja) * | 1988-01-27 | 1989-07-31 | Showa Highpolymer Co Ltd | 弾性塗料用下塗り組成物 |
JP3128005B2 (ja) * | 1991-04-10 | 2001-01-29 | ジェイエスアール株式会社 | 水性共重合体ラテックス |
US5102946A (en) * | 1991-06-27 | 1992-04-07 | E. I. Du Pont De Nemours And Company | Stabilized chlorinated resin latex |
JPH07207220A (ja) * | 1994-01-25 | 1995-08-08 | Kansai Paint Co Ltd | 水性塗料組成物及びそれを用いた塗装法 |
JP3207112B2 (ja) * | 1996-03-28 | 2001-09-10 | エスケー化研株式会社 | サーフェーサー |
DE19621574A1 (de) * | 1996-05-29 | 1997-12-04 | Basf Ag | Bindemittel für emissionsarme Beschichtungsmassen |
JPH10101987A (ja) * | 1996-10-03 | 1998-04-21 | Toray Ind Inc | アクリルシリコーンエマルジョン組成物 |
JPH115922A (ja) * | 1997-04-21 | 1999-01-12 | Toray Ind Inc | アクリルシリコーンエマルジョン組成物 |
JP3455065B2 (ja) * | 1997-06-23 | 2003-10-06 | 日本エヌエスシー株式会社 | 重ね塗り塗り替え用塗料組成物 |
JP3721549B2 (ja) * | 1997-07-17 | 2005-11-30 | 東レ・ファインケミカル株式会社 | アクリルシリコーンエマルジョン組成物 |
DE19801442A1 (de) * | 1998-01-16 | 1999-07-22 | Basf Ag | Verfahren zur Verbesserung der Stabilität wässriger Polymerisatdispersionen |
JP2000026691A (ja) * | 1998-07-08 | 2000-01-25 | Toray Ind Inc | アクリルシリコーンエマルジョン組成物 |
JP2000084480A (ja) * | 1998-09-10 | 2000-03-28 | Sekisui Chem Co Ltd | 屋根材再塗装方法 |
-
2000
- 2000-06-01 JP JP2000164663A patent/JP4700167B2/ja not_active Expired - Fee Related
-
2001
- 2001-06-01 DE DE60105387T patent/DE60105387T2/de not_active Expired - Fee Related
- 2001-06-01 US US10/048,089 patent/US20030114587A1/en not_active Abandoned
- 2001-06-01 EP EP01934506A patent/EP1236781B1/en not_active Expired - Lifetime
- 2001-06-01 WO PCT/JP2001/004667 patent/WO2001092432A1/ja active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH03134078A (ja) * | 1989-10-19 | 1991-06-07 | Asahi Denka Kogyo Kk | 下地塗材組成物 |
JPH09302270A (ja) * | 1996-03-14 | 1997-11-25 | Kansai Paint Co Ltd | 水性塗料及びこれを用いた塗装仕上げ方法 |
JPH11124545A (ja) * | 1997-10-27 | 1999-05-11 | Kansai Paint Co Ltd | 水性塗料組成物及びこれを用いた塗装仕上げ方法 |
EP0952161A2 (de) * | 1998-04-24 | 1999-10-27 | Basf Aktiengesellschaft | Emulgatorgemisch für die Emulsionspolymerisation |
Non-Patent Citations (1)
Title |
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See also references of EP1236781A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7022785B2 (en) * | 2002-03-01 | 2006-04-04 | Equistar Chemicals L.P. | Diimine complexes for olefin polymerization |
CN110964425A (zh) * | 2018-10-01 | 2020-04-07 | 日信化学工业株式会社 | 涂敷组合物和层叠体 |
Also Published As
Publication number | Publication date |
---|---|
DE60105387D1 (de) | 2004-10-14 |
JP2001342219A (ja) | 2001-12-11 |
EP1236781A1 (en) | 2002-09-04 |
EP1236781B1 (en) | 2004-09-08 |
DE60105387T2 (de) | 2005-09-22 |
EP1236781A4 (en) | 2003-01-15 |
US20030114587A1 (en) | 2003-06-19 |
JP4700167B2 (ja) | 2011-06-15 |
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