WO2001085859A1 - Water-based sealer composition - Google Patents
Water-based sealer composition Download PDFInfo
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- WO2001085859A1 WO2001085859A1 PCT/JP2001/003628 JP0103628W WO0185859A1 WO 2001085859 A1 WO2001085859 A1 WO 2001085859A1 JP 0103628 W JP0103628 W JP 0103628W WO 0185859 A1 WO0185859 A1 WO 0185859A1
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- macromonomer
- sealer composition
- water
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a sealer composition, and more particularly to an aqueous sealer yarn composition for inorganic materials.
- inorganic building materials such as slate, calcium silicate plate, cement mortar, etc. are used.
- these building materials are coated with various top coats.
- a topcoat is applied directly to these building materials, the coating is liable to peel or deteriorate, making it difficult for the topcoat to exhibit its original performance.
- an undercoat agent called a sealer is usually applied to the base material before forming the top coat.
- a sealer for undercoating a synthetic resin thread containing an organic solvent has been used.
- an aqueous synthetic resin composition containing little or no organic solvent is preferable in order to reduce toxicity and danger of ignition.
- An object of the present invention is to provide an aqueous sealer composition that forms a coating film having excellent adhesion to a base material.
- the present invention provides a macromonomer having a carboxyl group.
- An aqueous sealer composition comprising an aqueous dispersion containing a vinyl polymer obtained by polymerizing a vinyl monomer in the presence of a nomer is provided.
- the Mac monomer includes a monomer having a carboxyl group and a hydrophobic monomer.
- the monomers constituting the macromonomer 10 to 75 mass of a monomer having a carboxyl group. It is preferably contained at a ratio of / 0 .
- the macromonomer is preferably obtained by radical polymerization of a monomer mixture containing a monomer having a carboxyl group at a reaction temperature of 180 to 350 ° C.
- an aqueous sealer composition applied to an inorganic material.
- the aqueous sealer composition includes an aqueous dispersion containing an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent.
- the aqueous dispersion is produced by emulsion polymerization of a vinyl monomer in the presence of a macromonomer having a carboxyl group.
- a method of making an aqueous sealer composition applied to an inorganic material includes a step of preparing a macromonomer having a carboxyl group, and a step of obtaining an aqueous dispersion by emulsion-polymerizing a Bier monomer in the presence of the macromonomer.
- the aqueous dispersion includes an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent.
- the main component or active ingredient of the aqueous sealer composition of the present invention is an aqueous dispersion, and the aqueous dispersion is obtained by polymerizing a vinyl monomer in the presence of a macromonomer having a carboxyl group.
- the macromonomer having a carboxyl group has an ethylenically unsaturated bond at at least one terminal of the macromolecule molecule, and has a carboxyl group or a carboxylate in the macromonomer molecule.
- Mac mouth monomers essentially have carboxyl group-containing monomers.
- Hydrophobic monomer units may be included in the monomer units constituting the macromonomer.
- the proportion of the monomer unit having a boxyl group is preferably from 10 to 75% by mass. In particular, when the proportion is 10 to 60% by mass, the stability of the aqueous dispersion is better.
- the macromonomer is produced from a carboxyl group-containing monomer, if necessary, a hydrophobic monomer and / or an optional monomer.
- the carboxyl group-containing monomer is a compound having a carboxyl group and an ethylenically unsaturated bond.
- unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, atalyloxypropionic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, cyclohexanedicarboxylic acid, etc.
- Unsaturated dibasic acids can be used.
- Unsaturated acid anhydrides that generate carboxyl groups by hydrolysis of acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride can also be used.
- acrylic acid is particularly preferable because it has good polymerizability and forms an aqueous dispersion having excellent stability.
- the hydrophobic monomer refers to a monomer having a solubility in water at 20 ° C. of 2% by mass or less.
- methacrylic acid esters having 1 to 22 carbon atoms such as perfluoroalkyl (meth) acrylate and atalylic acid esters having 2 to 22 carbon atoms can be used, and butyl propionate and polystyrene can be used. Can also be used.
- the optional monomer is a monomer other than the monomer containing a propyloxyl group and the hydrophobic monomer.
- Specific examples of the optional monomer include biel acetate, (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, and arylphosphonic acid. Acids, bierphosphonic acid and the like can be used.
- the method for producing a macromonomer is described in, for example, Japanese Patent Application Laid-Open No.
- a known method disclosed in Japanese Patent Application Laid-Open No. Hei 11-181210 and "O99 / 077755" can be adopted.
- the gazette discloses a method of converting a specific group of a vinyl polymer having a radical polymerizable group bonded to one end to a carboxyl group, and Japanese Patent Application Laid-Open No.
- a method of reacting a dicarboxylic anhydride with a hydroxyl group-containing macromonomer having a radical polymerizable group is disclosed.
- WO 99/07755 discloses a monomer containing a carboxyl group-containing monomer A method for radically polymerizing a mixture at a high temperature of 180 ° C. or higher will be disclosed.
- radical polymerization initiator In producing the macromonomer, a known radical polymerization initiator can be used. Specific examples of the radical polymerization initiator include hydrogen peroxide, alkyl hydroxide peroxide, dialky peroxide, perester, percarbonate, persulfate, ketone peroxide, azo initiator and the like.
- solvents are those that dissolve the raw material monomers (carboxyl group-containing monomer, hydrophobic monomer, optional monomer) and can avoid precipitation of the produced polymer.
- aromatic alcohols such as benzyl alcohol, aliphatic alcohols such as isopropanol and butanol, ethylene glycol monoalkyl ethers such as methyl sorb and butyl sorb, diethylene glycol monoalkyl ethers such as carbitol
- Solvents such as ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and diglycol alkyl ethers such as diglycol methyl ether are preferred.
- the macromonomer is preferably produced by subjecting a monomer mixture containing a monomer having a carboxyl group (raw material mixture) to radical polymerization at a reaction temperature of 180 to 350 ° C. It is particularly preferred that the radical polymerization reaction be performed continuously. According to such a macromonomer, an aqueous dispersion having excellent dispersion stability and excellent permeability to the underlying substrate can be obtained. In addition, an aqueous sealer in which the coating film after film formation has excellent adhesion to the base can be obtained. A more preferred reaction temperature is 220 to 350 ° C., which is particularly preferred. The reaction temperature is between 270 and 320C. According to such a macromonomer, an aqueous dispersion and an aqueous sealer having remarkable performance can be obtained.
- the number average molecular weight of the macromonomer is preferably from 500 to 100,000. According to such a macromonomer, a water-based sealer composition that forms a coating film having excellent adhesion to a base can be obtained.
- the macromonomer preferably has a carboxyl group neutralized by a base.
- Such macromonomers provide aqueous dispersions with excellent dispersion stability.
- Preferred bases are ammonia or low boiling amine compounds having a boiling point of below 140 ° C.
- the low-boiling amine compound trimethylamine, getylamine, triethynoleamine, dimethinoleethynoleamine, N-methynolemonorephorin, t-butanolamine, morpholine, dimethylethanolamine and the like can be used.
- the neutralization of the macromonomer may be partial neutralization. The preferred neutralization ratio is 50 to 100%.
- the main component or the active ingredient of the aqueous sealer composition is an aqueous dispersion of a vinyl polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a Macmouth monomer or a neutralized product thereof.
- the macromonomer functions as an emulsifier.
- the usage amount of the macromonomer is preferably 5 to 300 parts by mass, more preferably 10 to 150 parts by mass, per 100 parts by mass of the vinyl monomer. If the amount of the macromonomer is too small, the stability of the vinyl polymer is low, and the permeability of the aqueous dispersion into the substrate is relatively low.
- such an aqueous sealer yarn composition has a relatively low wettability with the substrate, and thus has a relatively low adhesion between the substrate and the coating film.
- the amount of the macromonomer used is too large, the polymerization reaction is unstable.
- such an aqueous sealer composition forms a coating film having low water resistance.
- the type of the vinyl monomer is not particularly limited. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethyl (meth) acrylate. Hexyl, stearyl (meth) acrylate, lauri (meth) acrylate And (meth) acrylic acid esters having 1 to 22 carbon atoms, such as isobornyl (meth) acrylate and perfluoroalkyl (meth) acrylate.
- Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyacrylonitrile, vinyl acetate, styrene, glycidyl (meth) acrylate, diacetone acrylamide, N-methylol acrylamide, N-alkoxymethyl acrylamide and the like can be used.
- Emulsion polymerization of a vinyl monomer can be performed by a known method. For example, a method in which a macromonomer and a vinyl monomer are charged and polymerized in an aqueous medium, a method in which a macromonomer and a vinyl monomer are continuously or intermittently dropped and polymerized in an aqueous medium, There is a method in which water is added to a vinyl monomer to prepare a monomer emulsion, and this is continuously or intermittently dropped into an aqueous medium and polymerized. In the emulsion polymerization reaction, a known polymerization initiator can be used. The method of adding the polymerization initiator is not particularly limited.
- the polymerization initiator may be added all at once at the start of the polymerization, or may be added sequentially, or the polymerization initiator may be dissolved in the monomer mixture and dropped together with the monomer mixture. Further, two or more kinds of addition methods may be used in combination.
- the polymerization initiator examples include azo-based initiators such as azobisisobutyronitrile and azobispallet nitrile, and organic initiators such as benzoyl peroxide, lauryl peroxide and t-butyl peroxide.
- Inorganic peroxide initiators such as peroxide initiators, hydrogen peroxide, ammonium persulfate, persulfuric acid lime, and sodium persulfate can be used.
- a redox initiator using a reducing agent such as Rongalit, L-ascorbic acid, or an organic amine in combination may be used.
- One of these initiators may be used alone, or two or more of them may be used in combination.
- the amount of the polymerization initiator to be used is about 0.05 to 10% by mass, preferably about 0.1 to 5% by mass, based on the weight of the monomer.
- a chain transfer agent may be used during the emulsion polymerization reaction.
- various mercaptans, ⁇ -methylstyrene, alkyl halides and the like can be used.
- the amount of the chain transfer agent is 0 0 1 based on the monomers:.
- L is about 0 wt%, rather preferably is 0 0 5-3 mass 0/0 approximately..
- the emulsion polymerization temperature is preferably from 20 to 95 ° C, more preferably from 40 to 90 ° C.
- the emulsion polymerization time is preferably about 10 minutes to 10 hours.
- the glass transition temperature (T g) of the vinyl polymer obtained by emulsion polymerization is 120 to 100. C, more preferably 0 to 100 ° C. The reason is that if the transition temperature Tg is too low, such an aqueous sealer composition has poor adhesion to inorganic materials, and a coating film having low water resistance is formed. On the other hand, if the transition temperature Tg is too high, it is difficult to form a coating from such an aqueous sealer composition.
- a general-purpose emulsifier may be added to the sealer composition of the present invention as long as the characteristics are not impaired.
- the amount of the general-purpose emulsifier is preferably 50% by mass or less of the macromonomer.
- general-purpose emulsifiers include anionic surfactants such as sodium dodecyl sulfate, sodium anoalkyl benzene sulfonate, sodium polyoxyethylene alkyl sulfate, sodium dialkyl quinole sulfosuccinate, and formalin condensate of naphthalene sulfonic acid.
- anionic surfactants such as polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester and sorbitan fatty acid ester are used, and high molecular emulsifiers such as polyvinyl alcohol and formalin condensate of sodium naphthalene sulfonate are used.
- These general-purpose emulsifiers may be used in combination as an emulsifier for emulsion polymerization at the time of polymerization of a vinyl monomer, or may be added after polymerization of milk.
- the sealer composition of the present invention preferably has a vinyl polymer concentration of 5 to 50% by mass in an aqueous medium, more preferably 10 to 30% by mass.
- the sealer composition of the present invention may contain a pigment, a filler, a wetting agent, a dispersing agent, a preservative, an antifungal agent, and a plasticizer, if necessary.
- the sealer composition is a polyhydrazide compound that can crosslink with carbonyl, epoxy, urethane, and carboxyl groups. It may contain a crosslinking agent such as a substance or a metal. The content of these additives was 50 mass in the sealer composition. It is preferable that / 0 be the following.
- a water-swellable clay mineral may be added to prevent warpage and decay of the base material. Such a sealer composition can be used as a moisture-proof sealer.
- Water-swellable clay minerals that effectively improve the moisture resistance of the sealer composition include layered silicate minerals belonging to the genus Smectite, such as montmorillonite, beidelite, nontronite, saponite, hectorite, and synthetic fluoromica-based minerals. , Stevensite and bentonite. Further, a swellable fluoromica-based mineral synthesized by the method described in Japanese Patent Application Laid-Open No. 5-270815 is exemplified.
- the size of the water-swellable clay mineral when dispersed in water is preferably 1 to 20 ⁇ m, more preferably 3 to 20 ⁇ m.
- a preferable addition amount of the water-swellable clay mineral is 50% by mass or less in the sealer composition.
- the sealer composition of the present invention may contain a low-boiling solvent to promote drying after application and to improve wettability with respect to a substrate or a substrate.
- a low-boiling solvent are, for example, alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone and methyl ethyl ketone.
- the amount of the low boiling solvent added is preferably not more than 40% by mass based on the aqueous sealer composition.
- the sealer composition may contain a film-forming aid for assisting the formation of a film.
- a film-forming aid for assisting the formation of a film.
- dialkyl esters of aromatic dibasic acids such as dibutyl phthalate and dioctyl phthalate can be used.
- aliphatic dialkyl esters such as dibutyl succinate and dioctyl succinate can be used.
- Cellosolve compounds such as ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, etc. can be used.
- a pyrene glycol ether ether compound such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can be used, and a canolebitonele resin such as diethylene glycol monobutyl ether ethyl ether and diethylene glycol monobutyne iron ether can be used.
- Compounds can be used, and triglycol ether compounds such as triethylene dalicol monomethyl ether and trippyrene glycol monomethyl ether can be used.
- the amount of the film forming aid used is preferably about 1 to 10% by mass with respect to the bull polymer in the aqueous sealer composition.
- the sealer composition of the present invention has excellent permeability to inorganic materials such as slate, calcium silicate plate and cement mortar. Then, the sealer composition forms a film having excellent adhesion to the base after evaporation of volatile components such as water.
- sealer composition of the present invention exhibits the above-mentioned excellent characteristics is presumed as follows. That is, since the macromonomer has a high emulsifying power and has a copolymerizability with a vinyl monomer, an aqueous dispersion having a hydrophilic component can be obtained.
- A— 1. Production of Macromonomer MM1 and Mac Mouth Monomer Neutralized Product MM1N A 300 ml pressurized stirred tank reactor equipped with an electric heater is filled with 3-ethoxypropionate. Was. The temperature in the reactor was set at 275 ° C.
- a monomer mixture was prepared by mixing 65 parts of butyracrylate (hereinafter referred to as BA), 35 parts of acrylic acid (hereinafter referred to as AA), and 0.08 part of di-tert-butyl peroxide. The monomer mixture was stored in a raw material tank. While maintaining the pressure in the reactor at a predetermined value, the monomer mixture was continuously supplied from the raw material tank to the reactor.
- the feed rate was set so that the residence time of the monomer mixture in the reactor was 12 minutes.
- a reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet of the reactor.
- the temperature inside the reactor was set to 288 to 300. C maintained. 90 minutes after the start of the monomer mixture supply, The collection of the reaction solution was started. Use a thin film evaporator to remove unreacted monomers in the reaction solution.
- the macromonomer MM 1 was obtained.
- the molecular weight in terms of polystyrene of the macromonomer MM1 was measured by gel permeation chromatography using a tetrahydrofuran solvent (hereinafter referred to as GPC).
- the number average molecular weight (Mn) of the macromonomer MM 1 was 156, and the weight average molecular weight (M w) was 610.
- Mn number average molecular weight
- M w weight average molecular weight
- the canolepoxinole group of the macromonomer MM1 is neutralized, and the macromonomer neutralized product MM IN (aqueous solution with a solid concentration of 40%) is obtained. Obtained.
- a macromonomer MM2 was produced in the same manner as in A-1, except that a monomer mixture was prepared from 0.08 parts of BA80, 20 parts of AA, and 0.08 parts of tert-butyl peroxide. What is the molecular weight of macromonomer MM2? ⁇ 11 was 1500, Mw was 3,000, and the terminal double bond introduction rate was 80%.
- the carboxyl group of the macromonomer MM2 is neutralized by adding ammonia and water in the same amount as the acid value of the macromonomer MM2, and the macromonomer neutralized product MM2N (aqueous solution having a solid concentration of 40%) is obtained. Obtained.
- A— 3 Production of McMouth Monomer MM 3 and Macromonomer Neutralized Product MM 3 N
- 80 parts of cyclohexyl acrylate (hereafter referred to as CHA) 0 parts of AA20
- a macromonomer MM3 was produced in the same procedure as in A-1, except that a monomer mixture was prepared from 0.08 parts of butyl peroxide.
- the molecular weight of the macromolecule MM3 was Mn 144, Mw 390, and the terminal double bond introduction rate was 75%.
- the acid value of the macromonomer M M4 was 1.67 meqZg, the number average molecular weight (Mn) was 3600, the weight average molecular weight (Mw) was 8000, and the terminal double bond introduction rate was 98%.
- Mn number average molecular weight
- Mw weight average molecular weight
- the terminal double bond introduction rate was 98%.
- a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 725 parts of water and 500 parts of MM IN (40% aqueous solution), a Mac-mouth monomer neutralized product.
- the temperature of the mixed solution was raised to 80 ° C. while stirring under a nitrogen stream.
- Two parts of ammonium persulfate were added to the flask.
- a monomer mixture comprising 75 parts of styrene, 175 parts of methyl methacrylate, 50 parts of 2-hydroxyxyl methacrylate, and 200 parts of isoptyl acrylate was dropped into the flask over 3 hours. After dripping, 9 0.
- Emulsion was obtained by continuing the polymerization reaction for 1 hour.
- the ion exchange water was added to the emulsion to adjust the solid concentration in the emulsion to 20%.
- An aqueous sealer composition S1 was produced by adding 5% of isopropyl alcohol and 5% of diethylene glycol monobutyl ether to the emulsion.
- An aqueous sealer composition S 2 was produced in the same procedure as in Example 1, except that the macromonomer neutralized product MM 2 N used in Example 1 was replaced by a macromonomer neutralized product MM 2 N.
- the monomer emulsion was dropped into the flask over 3 hours. After completion of dropping, 90. The temperature was raised to C, and 0.5 parts of ammonium persulfate was added to the flask.
- Emulsion was obtained by continuing the polymerization reaction for 1 hour. Ion-exchanged water was added to the emulsion to adjust the solid concentration in the emulsion to 20 %.
- An aqueous sealer composition S3 was produced by adding 5% of isopropyl alcohol and 5% of diethylene glycol monobutyl ether to the emulsion.
- An aqueous sealer composition S4 was produced in the same procedure as in Example 3, except that the macromonomer neutralized product MM3N used in Example 3 was replaced by a macromonomer neutralized product MM3N.
- Example 5 Production of aqueous sealer composition S5 The neutralized macromonomer MM3ND (30% aqueous solution) was diluted to prepare a diluted macromonomer neutralized product MM3ND (30% aqueous solution). Water consists of 250 parts, diluted macromonomer neutralized product MM 3 ND 17 parts, styrene 300 parts, 2-hydroxyethyl methacrylate 25 parts, 2-ethylhexyl acrylate 175 parts A monomer emulsion was prepared by emulsifying the monomer mixture using a homomixer.
- Swellable fluoromica (degree of swelling 29 m 1 Z 2 g, force thione exchange capacity 60 mg Z 100 g) is dispersed in ion-exchanged water so as to have a solid content of 4% by mass and brought to 80 ° C.
- the mixture was heated and stirred with a homogenizer for 1.5 hours to obtain a mica dispersion.
- the mica dispersion was added to the sealer composition S4 of Example 4 to obtain an aqueous sealer composition S7.
- Aqueous sealer set The content ratio of mica to the total solid content of the product S7 was 5% by mass.
- An aqueous sealer composition S8 was produced in the same procedure as in Example 3, except that the macromonomer neutralized product MM4N used in Example 3 was replaced with a macromonomer neutralized product MM4N.
- aqueous sealer composition S9 of Comparative Example 1 was produced in the same procedure as in Example 1 except that 5 parts of sodium dodecyl sulfate was used in place of the macromonomer neutralized product MM 1 N used in Example 1. Manufactured.
- Comparative Example 3 a commercially available aqueous sealer composition S11 was used.
- aqueous sealer compositions of the examples and comparative examples were evaluated as follows. 1. Dry adhesion with sealer coating alone
- each sealer composition was applied on a calcium silicate plate at a thickness of 100 g / m 2 .
- the sealer film was formed by allowing to stand at room temperature for 24 hours.
- the adhesion between the sealer coating and the calcium silicate plate was tested as follows.
- the sealer film on the calcium silicate plate was cut into a grid at intervals of 4 mm using a force cutter to form 25 cells.
- Adhesive tape (Nichiban Mouth tape). The adhesive tape was peeled off at a stretch. From the area (number of cells) of the sealer coating piece remaining on the calcium silicate plate without peeling, the adhesion was evaluated according to the following formula. Table 1 shows the results. The closer the value is to 100, the better the adhesion.
- Adhesion (%) Number of remaining cells Z 25 X 100
- Each sealer composition was applied on a calcium silicate plate at a thickness of 100 g / m 2 .
- the sealer coating was formed by allowing to stand at room temperature for 24 hours.
- the sealer film together with the calcium silicate plate was immersed in warm water at 60 ° C for 24 hours and allowed to stand at room temperature for 24 hours. Thereafter, the adhesion was tested in the same manner as in (1). The results are shown in Table 1.
- Each sealer composition was coated on a calcium silicate plate having a thickness of 1 00 gZm 2.
- the sealer coating was formed by allowing to stand at room temperature for 24 hours.
- a commercially available water-based overcoat was applied to the sealer coating to a thickness of 75 gZm 2 and dried at room temperature for 3 days. After that, the adhesion was tested in the same manner as in (1). Table 1 shows the results.
- Each sealer composition was coated on a calcium silicate plate having a thickness of 100 gZm 2.
- the sealer coating was formed by allowing to stand at room temperature for 24 hours.
- a commercially available water-based overcoat was applied to the sealer coating to a thickness of 75 gZm 2 and dried at room temperature for 3 days. Thereafter, the water adhesion resistance was tested in the same manner as in section (2). Table 1 shows the results.
- the sealer composition S7 was applied on the upper surface of the sheet I at a rate of 100 g / m 2 .
- the sealer film was formed by allowing to stand at room temperature for 24 hours.
- the sealer composition S7 was not applied to the lower surface and side surfaces of the slate plate, but was sealed with a waterproof material.
- the slate plate was left in a constant temperature and humidity chamber at 40 ° C and 90% RH for 24 hours to test the moisture proof property.
- the moisture proof was determined from the weight change of the slate before and after the test.
- the moisture resistance of the sealer composition S7 was 45 gZm 2 .
- a comparative slate plate without the sealer composition S7 was tested. Its moisture resistance was 200 gZm 2 . This result indicated that the sealer composition S7 had excellent moisture resistance.
- An aqueous primer is provided that has high adhesion to inorganic materials such as slate, calcium silicate plate, and cement.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001252602A AU2001252602A1 (en) | 2000-05-12 | 2001-04-26 | Water-based sealer composition |
KR1020027015102A KR20020094035A (en) | 2000-05-12 | 2001-04-26 | Water-based sealer composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000139324 | 2000-05-12 | ||
JP2000-139324 | 2000-05-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001085859A1 true WO2001085859A1 (en) | 2001-11-15 |
Family
ID=18646788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/003628 WO2001085859A1 (en) | 2000-05-12 | 2001-04-26 | Water-based sealer composition |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR20020094035A (en) |
CN (1) | CN1427875A (en) |
AU (1) | AU2001252602A1 (en) |
WO (1) | WO2001085859A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008038383A (en) * | 2006-08-02 | 2008-02-21 | Yabuhara Sangyo Kk | Reinforcing agent for weak substrate and its manufacturing method |
JP2008201915A (en) * | 2007-02-21 | 2008-09-04 | Toyo Ink Mfg Co Ltd | Aqueous resin dispersion for elastic coating material, its production method and aqueous elastic coating material for construction |
JP2012046737A (en) * | 2010-07-27 | 2012-03-08 | Yokohama Rubber Co Ltd:The | Tire puncture sealing material |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103333572A (en) * | 2013-07-02 | 2013-10-02 | 宁波清风纳米涂料有限公司 | Real stone paint |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0762268A (en) * | 1993-08-20 | 1995-03-07 | Kansai Paint Co Ltd | Primer-coated steel plate and primer composition to be used therefor |
JPH07331118A (en) * | 1994-05-31 | 1995-12-19 | Kansai Paint Co Ltd | Composition for coating and method of formation of coating film using the same |
JPH09169806A (en) * | 1995-12-20 | 1997-06-30 | Arakawa Chem Ind Co Ltd | Production of aqueous coating polymer dispersion and dispersion obtained thereby |
JPH11247099A (en) * | 1997-12-30 | 1999-09-14 | Arakawa Chem Ind Co Ltd | Undercoating agent for release paper |
-
2001
- 2001-04-26 CN CN 01809279 patent/CN1427875A/en active Pending
- 2001-04-26 WO PCT/JP2001/003628 patent/WO2001085859A1/en active Application Filing
- 2001-04-26 KR KR1020027015102A patent/KR20020094035A/en not_active Application Discontinuation
- 2001-04-26 AU AU2001252602A patent/AU2001252602A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0762268A (en) * | 1993-08-20 | 1995-03-07 | Kansai Paint Co Ltd | Primer-coated steel plate and primer composition to be used therefor |
JPH07331118A (en) * | 1994-05-31 | 1995-12-19 | Kansai Paint Co Ltd | Composition for coating and method of formation of coating film using the same |
JPH09169806A (en) * | 1995-12-20 | 1997-06-30 | Arakawa Chem Ind Co Ltd | Production of aqueous coating polymer dispersion and dispersion obtained thereby |
JPH11247099A (en) * | 1997-12-30 | 1999-09-14 | Arakawa Chem Ind Co Ltd | Undercoating agent for release paper |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008038383A (en) * | 2006-08-02 | 2008-02-21 | Yabuhara Sangyo Kk | Reinforcing agent for weak substrate and its manufacturing method |
JP4723433B2 (en) * | 2006-08-02 | 2011-07-13 | ヤブ原産業株式会社 | Fragile substrate reinforcing agent and method for producing the same |
JP2008201915A (en) * | 2007-02-21 | 2008-09-04 | Toyo Ink Mfg Co Ltd | Aqueous resin dispersion for elastic coating material, its production method and aqueous elastic coating material for construction |
JP2012046737A (en) * | 2010-07-27 | 2012-03-08 | Yokohama Rubber Co Ltd:The | Tire puncture sealing material |
Also Published As
Publication number | Publication date |
---|---|
KR20020094035A (en) | 2002-12-16 |
AU2001252602A1 (en) | 2001-11-20 |
CN1427875A (en) | 2003-07-02 |
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