WO2009091064A1 - Emulsifiant contenant du titane - Google Patents

Emulsifiant contenant du titane Download PDF

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Publication number
WO2009091064A1
WO2009091064A1 PCT/JP2009/050684 JP2009050684W WO2009091064A1 WO 2009091064 A1 WO2009091064 A1 WO 2009091064A1 JP 2009050684 W JP2009050684 W JP 2009050684W WO 2009091064 A1 WO2009091064 A1 WO 2009091064A1
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Prior art keywords
resin composition
water
aqueous resin
double bond
ethylenic double
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PCT/JP2009/050684
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English (en)
Japanese (ja)
Inventor
Keiko Ide
Yoshio Yoshida
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Henkel Technologies Japan Ltd.
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Publication of WO2009091064A1 publication Critical patent/WO2009091064A1/fr

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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
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

  • the present invention relates to an aqueous resin composition obtained using a titanium-containing emulsifier, and more particularly to a titanium-containing aqueous resin composition excellent in coating property, film forming property and photocatalytic effect.
  • This composition can be used for water-based paints, inks, adhesives, surface coating agents and the like having a photocatalytic effect.
  • titanium alkoxide reacts with a compound having a hydroxyl group and a carboxyl group in the molecule as a crosslinking agent, it is used as an adhesion improver, a coating crosslinking agent, a coating heat resistance improving agent, and the like.
  • titanium oxide fine particles are synthesized by a sol-gel method or the like and used as a white pigment or a pigment having a photocatalytic function.
  • paints having a VOC decomposing function such as formaldehyde, antifouling paints capable of decomposing adhering contaminants, and antifogging paints utilizing surface hydrophilization by photocatalytic functions, etc. Applied.
  • a technique for forming a photocatalytic coating on a substrate using titanium oxide having an excellent photocatalytic effect has been proposed.
  • titanium alkoxide has a very high hydrolyzability, insoluble matters are easily generated by moisture in the air during operation and storage.
  • titanium alkoxide it is necessary to use a large amount of an organic solvent, and the environmental load is extremely high. For this reason, an aqueous titanium composition has been studied as an aqueous titanium compound having a low environmental load and resistance to hydrolysis.
  • Patent Document 1 proposes a water-soluble titanium hydroxycarboxylate chelate compound obtained by reacting hydroxycarboxylic acid and titanium tetraalkoxide in the presence of water.
  • this water-soluble titanium hydroxycarboxylate chelate compound has problems in coating properties, film-forming properties, substrate adhesion, and the like, and is difficult to use as it is as a coating agent.
  • Patent Document 2 proposes a coating composition in which a titanium oxide particulate having a photocatalytic function is mixed with an aqueous emulsion coating. Above all, it is excellent from the viewpoint of environmental sanitation, fire prevention, resource saving, etc. of painting work, and it can be applied to various substrates by mixing titanium oxide fine particles with photocatalytic function into aqueous emulsion paint. Can stably immobilize titanium oxide. However, in the method of mixing titanium oxide fine particles having the photocatalytic function described above with an aqueous emulsion paint, the dispersibility and stability of the titanium oxide fine particles in the aqueous emulsion paint are poor. There is a problem that it is difficult to obtain a film.
  • the present invention has been made to solve such problems and problems of the prior art. That is, an object is to obtain a titanium-containing aqueous resin composition that is excellent in coating property, film-forming property, and substrate adhesion and is stable for a long period of time. Furthermore, it aims at obtaining the aqueous resin composition which can form a uniform film, although a high photocatalytic function is obtained.
  • the present inventors have surprisingly found that when a mixture obtained by mixing titanium alkoxide, an organic acid and water is used, polymerization having an ethylenic double bond is performed. It has been found that a polymerizable monomer can be polymerized in an aqueous medium, that is, a mixture obtained by mixing titanium alkoxide, an organic acid and water can function as an emulsifier for emulsion polymerization. Therefore, the manufacturing method of the aqueous resin composition which superpose
  • the aqueous resin composition produced by this production method has excellent coating properties, film-forming properties, dispersibility, and long-term stability, and by applying this aqueous resin composition to a substrate, It has also been found that a film showing excellent uniformity and substrate adhesion is formed. In addition, the obtained aqueous resin composition was found to have a high photocatalytic effect, and the present invention was completed.
  • an emulsifier for emulsion polymerization comprising a mixture obtained by mixing titanium alkoxide, an organic acid and water. Furthermore, in another aspect of the present invention, (A) a polymerizable monomer having an ethylenic double bond is polymerized in the presence of a mixture obtained by mixing (A) a titanium alkoxide, an organic acid and water. A method for producing an aqueous resin composition (or an aqueous emulsion composition) is provided.
  • the polymerizable monomer having an ethylenic double bond comprises an alkoxysilyl group-containing monomer having an ethylenic double bond.
  • An aqueous resin composition and a method for producing the same are provided.
  • the other aspect of this invention provides the said aqueous resin composition whose titanium alkoxide is titanium tetraisopropoxide, and its manufacturing method.
  • the preferable aspect of this invention provides the water-based coating material, ink, adhesive agent, and surface coating agent which comprise the said water-based resin composition.
  • the “aqueous resin” means a state in which the polymer particles are present in the aqueous medium, preferably a state in which they are dispersed. Therefore, the “aqueous resin composition” means the polymer particles and the aqueous medium. It means a composition comprising both.
  • the aqueous resin composition according to the present invention includes (A) a monomer having an alkoxysilyl group and an ethylenic double bond in the presence of a mixture obtained by mixing titanium alkoxide, an organic acid and water. (B) Since it is obtained by polymerizing a polymerizable monomer having an ethylenic double bond, it is excellent in coating property, film-forming property, substrate adhesion, stable for a long time, and formed. The coated film is excellent in uniformity and substrate adhesion, and can exhibit a high photocatalytic effect and high water resistance.
  • the water-based paint according to the present invention comprises the above-described water-based resin composition according to the present invention, it is excellent in coating property, film-forming property, substrate adhesion, and stable for a long time.
  • the coating composition according to the present invention can form a uniform film having excellent substrate adhesion when applied to a substrate, and can exhibit a high photocatalytic effect and high water resistance. Furthermore, it is possible to form a film in which titanium oxide is uniformly dispersed, and a higher photocatalytic effect can be exhibited.
  • the photocatalytic effect of the aqueous resin composition and the aqueous paint according to the present invention is further improved.
  • the present invention will be specifically described below.
  • (A) a mixture obtained by mixing a titanium alkoxide, an organic acid and water (hereinafter also referred to as“ (A) mixture ”)” is used as it is or as necessary.
  • the emulsifier for emulsion polymerization containing the (A) mixture may be the (A) mixture itself, and may contain water and other additives as appropriate for adjusting the concentration.
  • emulsion polymerization refers to radical polymerization in which an oil-soluble monomer is emulsified in water using an emulsifier and then used with a water-soluble polymerization initiator.
  • the mixture used as an emulsifier for emulsion polymerization can be obtained by mixing titanium alkoxide, an organic acid and water, but the order of mixing titanium alkoxide, organic acid and water is not particularly limited. .
  • the temperature and pressure at the time of mixing are not particularly limited, the mixing is usually performed at room temperature (about 25 ° C.) under atmospheric pressure, followed by heating and stirring at 70 ° C. In general, stirring is preferable, and the stirring time is usually about 5 to 24 hours, but the stirring time can be adjusted as necessary.
  • the mixing ratio of titanium alkoxide, organic acid, and water is not particularly limited as long as the target mixture can be used as an emulsifier for emulsion polymerization, but the molar ratio of titanium to organic acid is 0.1: 1. Is preferably ⁇ 5: 1, more preferably 0.5: 1 to 1.5: 1, and particularly preferably 1: 1.
  • the amount of water contained in the mixture is not particularly limited as long as the mixture can be used as an emulsifier for emulsion polymerization, and is appropriately adjusted, but is 0.1 to 60% by weight based on the entire mixture. It is preferably 3 to 40% by weight, more preferably 5 to 30% by weight.
  • titanium alkoxide more specifically refers to a titanium tetraalkoxide represented by the following formula (1).
  • Examples of the compound represented by the formula (1) include titanium tetramethoxide [Ti (OMe) 4 ], titanium tetraethoxide [Ti (OEt) 4 ], titanium tetraisopropoxide [Ti (OiPr) 4 ], Examples thereof include titanium tetrabutoxide [Ti (OBu) 4 ] and derivatives thereof.
  • titanium tetraisopropoxide is preferred as the titanium alkoxide because it is generally easily available and easy to handle and has a good photocatalytic effect.
  • organic acid means an organic compound having acidity, and examples thereof include carboxylic acid.
  • examples thereof include carboxylic acid.
  • lactic acid, oxalic acid, citric acid, tartaric acid and the like are preferable, and lactic acid which is generally easy to obtain and handle is particularly preferable.
  • An organic acid may be used independently and may use 2 or more types together.
  • Water for preparing the mixture is not particularly limited, and mainly refers to so-called water such as pure water, distilled water and ion-exchanged water, but is a water-soluble organic solvent, for example, Acetone and lower alcohols may be included as appropriate.
  • (B) a polymerizable monomer having an ethylenic double bond (hereinafter also referred to as “(B) polymerizable monomer”) is polymerized in the presence of the mixture (A).
  • ethylenic double bond refers to a compound having a double bond between carbon atoms capable of undergoing at least one polymerization reaction (radical polymerization) in one molecule.
  • Examples of such a functional group having an ethylenic double bond include a vinyl group (CH 2 ⁇ CH—), a (meth) allyl group (CH 2 ⁇ CH—CH 2 — and CH 2 ⁇ C (CH 3 ) — CH 2 —), (meth) acryloyloxy groups (CH 2 ⁇ CH—COO— and CH 2 ⁇ C (CH 3 ) —COO—), —COO—CH ⁇ CH—COO— and the like can be exemplified.
  • acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”, and acrylic acid ester and methacrylic acid ester are collectively referred to as “(meth) acrylic acid ester” or “(meth)”.
  • Acrylate The same applies to allyl groups and acryloyloxy groups.
  • (B) a polymerizable monomer having an ethylenic double bond is a monomer having an ethylenic double bond and capable of radical polymerization (preferably emulsion polymerization). It can be used as appropriate according to the properties of the intended aqueous resin composition.
  • a “polymerizable monomer having an ethylenic double bond” for example, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as dodecyl (meth) acrylate and cyclohexyl (meth) acrylate (including (meth) acrylic acid cycloalkyl esters); (Meth) acrylic acid esters having an epoxy group such as glycidyl (meth) acrylate; Compounds having a carboxyl group and an ethylenic double bond, such as acrylic acid, methacrylic acid, itaconic acid, crot
  • the polymerizable monomer having an ethylenic double bond preferably contains an alkoxysilyl group and a monomer having an ethylenic double bond.
  • the “monomer having an alkoxysilyl group and having an ethylenic double bond” mainly forms a cross-linked structure inside the emulsion polymer or between the emulsion polymers.
  • membrane obtained from this emulsion composition, base-material adhesiveness, etc. is said.
  • the resin may be a homopolymer or a copolymer. That is, the resin obtained is a homopolymer of “a monomer containing an alkoxysilyl group and having an ethylenic double bond”, or the above-mentioned “ethylenic double bond other than this monomer and this monomer”. Any of the copolymer with a "polymerizable monomer having”.
  • Alkoxysilyl group means a silicon-containing functional group that hydrolyzes to give a hydroxysilyl group (Si—OH) bonded to silicon, such as a trimethoxysilyl group, a triethoxysilyl group, a dimethoxysilyl group, Examples thereof include alkoxysilyl groups such as diethoxysilyl group, monomethoxysilyl group, monoethoxysilyl group, triisopropoxysilyl group, diisopropoxysilyl group and monoisopropoxysilyl group.
  • the “ethylenic double bond” is as described above.
  • monomers having an alkoxysilyl group and having an ethylenic double bond include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethyl.
  • These monomers containing an alkoxysilyl group and having an ethylenic double bond can be appropriately selected according to the properties of the emulsion, and can be used alone or in combination.
  • Monomers having an alkoxysilyl group and having an ethylenic double bond include ⁇ -methacryloxypropyltrimethoxysilane, tris ( ⁇ -methoxyethoxy) vinylsilane, ⁇ -methacryloxypropylmethyldimethoxylane, and vinyltriisopropoxy.
  • Silane is preferred, and ⁇ -methacryloxypropyltrimethoxysilane is particularly preferred.
  • an alkoxysilyl group is contained.
  • the monomer having an ethylenic double bond is preferably contained in the polymerizable monomer (B) in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, in the polymerizable monomer (or reaction mixture). More preferably, the content is 0.5 to 10% by weight.
  • the polymerizable monomer having an ethylenic double bond is generally a (meth) acrylic acid alkyl ester, optionally a styrene and a derivative of styrene, optionally a compound having a carboxyl group and an ethylenic double bond, In some cases, it preferably contains a monomer containing an alkoxysilyl group and having an ethylenic double bond.
  • the (meth) acrylic acid alkyl ester is at least one selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Is preferable, and a combination of methyl methacrylate and butyl acrylate is particularly preferable.
  • the styrene and the styrene derivative are preferably at least one selected from styrene and vinyltoluene, and more preferably styrene.
  • the compound having a carboxyl group and an ethylenic double bond is preferably at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and fumaric acid, and particularly preferably acrylic acid.
  • Monomers containing an alkoxysilyl group and having an ethylenic double bond are ⁇ -methacryloxypropyltrimethoxysilane, tris ( ⁇ -methoxyethoxy) vinylsilane, ⁇ -methacryloxypropylmethyldimethoxylane and vinyltriisopropoxy. It is preferably at least one selected from silanes, particularly preferably ⁇ -methacryloxypropyltrimethoxysilane.
  • aqueous medium is not particularly limited, and mainly refers to so-called water such as pure water, distilled water and ion-exchanged water, but water-soluble organic solvents such as acetone and lower alcohols. May be included as appropriate.
  • the polymerization reaction conditions such as reaction temperature, reaction time, type of aqueous solvent, type and concentration of monomer mixture, stirring speed, and type and concentration of polymerization initiator depend on the characteristics of the desired aqueous resin composition. It can be selected as appropriate.
  • (A) a polymerizable monomer is polymerized in the presence of a mixture obtained by mixing titanium alkoxide, an organic acid and water. That is, in order to polymerize a polymerizable monomer in an aqueous medium, a mixture obtained by mixing (A) titanium alkoxide, an organic acid and water is used as an emulsifier for emulsion polymerization. Therefore, it is considered that the polymerization of the polymerizable monomer according to the present invention is so-called emulsion polymerization.
  • the mixture obtained by mixing the (A) titanium alkoxide, organic acid and water used for polymerizing the polymerizable monomer is used in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer. It is preferably 1 to 15 parts by weight, more preferably 3 to 13 parts by weight.
  • the weight part of (A) mixture is based on the weight part of the part which does not contain water.
  • the amount of water in the mixture can be appropriately adjusted in consideration of mechanical stability, long-term stability, etc., and should be 0.1 to 60% by weight based on the entire mixture. It is preferably 3 to 40% by weight, more preferably 5 to 30% by weight.
  • a general “emulsifier” is used for the purpose of improving the polymerizability of the polymerizable monomer (B) in an aqueous medium and the long-term stability of the resulting aqueous resin composition (emulsion). be able to.
  • an “emulsifier” a surfactant known to those skilled in the art can be used.
  • the emulsifier has the ability to emulsify the monomer, and forms a micelle in the course of polymerization to provide a polymerization field for the monomer. Further, during or after the polymerization, it is immobilized on the surface of the resulting polymer particles to improve the dispersion stability of the particles.
  • the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant.
  • anionic surfactants include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate, ammonium alkyl sulfates such as sodium dodecyl polyglycol ether sulfate, and ammonium dodecyl sulfate, sodium sulfosinoate, and alkali metal of sulfonated paraffin.
  • alkyl sulfonates such as ammonium salt of sulfonated paraffin, fatty acid salts such as sodium laurate, trietalamine oleate, trietalamine abiate, sodium dodecylbenzenesulfonate, alkali metal sulfate of alkali phenol hydroxyethylene, etc.
  • polyoxyethylene alkyl ether sulfate salt sodium salt
  • Latemul WX trade name
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride such as monolaurate of glycerol, polyoxyethyleneoxypropylene copolymer Examples thereof include condensation products, condensation products of ethylene oxide and aliphatic amines, amides or acids.
  • Examples of the cationic surfactant include monoalkyl ammonium salts, dialkyl ammonium salts, and ethylene oxide addition type alkyl ammonium salts.
  • Examples of amphoteric surfactants include amidopropyl betaine and aminoacetic acid betaine.
  • Examples of the polymer surfactant include sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, poly (meth) acrylate and the like. Further examples include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, aqueous polyurethane resins, water-soluble acrylic resins, polyvinyl pyrrolidone resins, and polyvinyl alcohol.
  • a reactive surfactant can be used as an emulsifier.
  • reactive surfactants for example, polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate ester salt (Adekalya soap SE series (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.), ⁇ -sulfo- ⁇ - (1- (alkoxy) ) Ammonium salt of methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (Adeka Soap SR series (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene (or Alkylene) alkyl (or alkenyl) ether sulfate ammonium salt (PD series (trade name) manufactured by Kao Corporation), sulfosuccinic acid type reactive activator (Latemuru 180 series (trade name) manufactured by Kao Corporation), alkyl
  • Reactive emulsifiers can be used alone or in combination of two or more.
  • alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2 (trade name) manufactured by Sanyo Chemical Industries)
  • alkyl ether sulfate ammonium salt (Aqualon KH series (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) preferable.
  • a polymerizable monomer is polymerized in the presence of a mixture obtained by mixing a titanium alkoxide, an organic acid, and water.
  • the above-mentioned general surfactants can be used in combination for polymerization.
  • the general surfactant used for emulsion polymerization of the polymerizable monomer is (B) 0.1 to 6 parts by weight with respect to 100 parts by weight of the polymerizable monomer having an ethylenic double bond. It is preferable to use 1 to 3 parts by weight.
  • a polymerization initiator can be used to polymerize the polymerizable monomer (B) having an ethylenic double bond.
  • “Polymerization initiator” refers to a compound that can cause a polymerization reaction of a monomer by addition of a small amount, and is preferably a compound that can be used in an aqueous medium. Examples of such a polymerization initiator include hydrogen peroxide, a water-soluble inorganic peroxide, a combination of a water-soluble reducing agent and a water-soluble inorganic peroxide, and a combination of a water-soluble reducing agent and an organic peroxide. .
  • water-soluble inorganic peroxide for example, a water-soluble reducing agent usually used as a radical redox polymerization catalyst can be used.
  • a water-soluble reducing agent usually used as a radical redox polymerization catalyst.
  • examples of such a reducing agent include sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ferrous lactate, ferrous ammonium sulfate, ferrous pyrophosphate, sulfinic acid, L-ascorbic acid And its sodium salt, potassium salt and calcium salt, ethylenediaminetetraacetic acid and its sodium salt and potassium salt, ethylenediaminetetraacetic acid or its salt and heavy metals and complex compounds such as iron, copper or chromium, and reducing sugar.
  • water-soluble organic peroxide examples include cumene hydroperoxide, p-cymene hydroperoxide, t-butylisopropylbenzene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, decalin hydroperoxide, t-amyl hydroperoxide And t-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, trichlorobromomethane and the like.
  • the glass transition temperature (Tg) of the film obtained from the aqueous resin composition of the present invention is preferably ⁇ 50 to 100 ° C., in order to obtain an aqueous resin composition with higher water resistance and substrate adhesion of the film.
  • the glass transition temperature of the coating is preferably -30 to 50 ° C.
  • the “glass transition temperature” of the coating refers to a DSC curve of a sample of 5 to 10 mg using a differential operation calorimeter (specifically, SII nanotechnology DSC6220 manufactured by SII Nanotechnology). Is measured at a rate of temperature increase of 5 ° C./min, and refers to the temperature at the inflection point of the obtained DSC curve.
  • the titanium-containing aqueous resin composition according to the present invention may be blended with an appropriate amount of other additives as long as the characteristics of the present invention are not impaired.
  • Other additives include, for example, Curing catalysts such as metal alkoxides added for the purpose of rapid curing; Diluting solvents such as water, alcohols, ketones and glycols added for the purpose of adjusting viscosity; Inorganic fillers such as glass, quartz, aluminum hydroxide, alumina, kaolin, talc, calcium carbonate, calcium silicate, magnesium hydroxide, titanium oxide; Organic fillers such as acrylic resin powder, epoxy resin powder, and polyester resin powder; Colorants represented by pigments or dyes such as carbon black, bengara, phthalocyanine blue, chrome yellow, titanium dioxide; Other neutralizers, thickeners, dispersants, antifoaming agents, film increasing aids, antiseptics, antifungal agents, antibacterial agents, antifreezing agents, UV absorbers, metal powders, lubricants, mold release agents
  • the aqueous resin composition according to the present invention is excellent in coating property and film forming property, and can form a uniform film.
  • the formed film is excellent in substrate adhesion and can exhibit an excellent photocatalytic function.
  • the aqueous resin composition according to the present invention can be suitably used for water-based paints, inks, adhesives, surface coating agents and the like having a photocatalytic effect.
  • (A) An emulsifier for emulsion polymerization comprising a mixture obtained by mixing titanium alkoxide, an organic acid and water. 2.
  • (B) The polymerizable monomer which has an ethylenic double bond is as follows. (B-1) Methyl methacrylate (B-2) Styrene (B-3) Butyl acrylate (B-4) Acrylic acid (B-5) ⁇ -Methacryloxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd., SZ6030) Product name)) (C) Other emulsifiers are as follows: (C-1) Polyoxyethylene alkyl ether sulfate salt (sodium salt) (Kao Corporation, Latemul WX (trade name)) (D) Photocatalytic material composed of anatase-type titanium oxide fine particles (D-1) Tynock A-6 (Taki Chemical Co., Ltd., Tynock A-6 (trade name))
  • A) Mixture Production Examples 1-2 (A) Production of mixture obtained by mixing titanium alkoxide, organic acid and water (A) Mixture obtained by mixing titanium alkoxide, organic acid and water can be obtained by any known method such as international publication. It can be produced according to the method described in 2005/094978. (A-1) A mixture obtained by mixing titanium tetraisopropoxide, lactic acid and water was prepared by adding 478 parts by weight of water to 90 parts by weight of lactic acid (manufactured by Alfa Aesar) and dissolving the lactic acid in water.
  • aqueous resin composition of Example 1 41.8 parts by weight of distilled water and 0.5 part by weight of (C-1) surfactant in a four-necked flask equipped with a stirring blade, a thermometer and a reflux condenser (Kao Corporation, Latem WX (trade name)) was added. Stirring while blowing nitrogen gas, the liquid temperature was kept at 70 ° C.
  • aqueous resin composition was produced in the same manner as in Example 1 except that each component was changed as shown in Table 1.
  • the test results of the obtained aqueous resin composition are shown in Table 1.
  • Comparative Example 2 Each component was changed as shown in Table 1, and (A-1) a photocatalytic material composed of fine particles of anatase-type titanium oxide instead of the mixture (T-1 Chemical Co., Ltd., Tynock A-6 (trade name) )) was used to produce an aqueous resin composition using the same method as in Example 1.
  • the test results of the obtained aqueous resin composition are shown in Table 1.
  • Comparative Example 3 An aqueous resin composition was produced in the same manner as in Example 1 using the component (B) and the component (C) shown in Table 1. 0.05 parts by weight of (D-1) a photocatalytic material (Taki Chemical Co., Ltd., Tynock A-6 (trade name)) composed of fine particles of anatase-type titanium oxide is added to 0.5 parts by weight of the obtained aqueous resin composition. In addition, an aqueous resin composition of Comparative Example 3 was obtained. The test results are shown in Table 1.
  • the obtained aqueous resin composition was evaluated as follows. 1. Polymerizability The state of the aqueous resin composition after synthesis was visually observed, focusing on (B) the polymerizable monomer and the polymer derived therefrom. A: (B) Good without aggregation, precipitation, separation, etc. of the polymerizable monomer and the polymer derived therefrom. ⁇ : Aggregation, precipitation, separation, etc. of the (B) polymerizable monomer and the polymer derived therefrom are observed in less than 30% of the whole. ⁇ : (B) the polymerizable monomer and it in 30% or more of the whole Aggregation, precipitation, separation, etc. of the derived polymer are observed.
  • A The mixture (mainly water-soluble titanium) is satisfactory without aggregation, precipitation, separation, etc.
  • A Aggregation, precipitation, separation, etc. of the mixture (A) are observed in less than 30% of the total.
  • X Aggregation, precipitation, separation, etc. of the mixture (A) are observed in 30% or more of the whole.
  • Photocatalytic function Dye fading An aqueous resin composition was applied on a glass plate to a thickness of 5 to 10 ⁇ m and dried at 105 ° C. for 5 minutes to form a coating. Thereafter, 0.05 g of a 0.1 wt% methylene blue ethanol solution was applied on the film and allowed to stand at room temperature for 2 hours. The glass plate coated with the coating film and the pigment was irradiated with a 15 W UV lamp for an arbitrary time. The absorbance (Abs) of UV light at 665 nm was measured with a spectrophotometer before and after UV irradiation.
  • Absorbance after UV irradiation based on the absorbance before UV irradiation was defined as the undecomposed ratio of the methylene blue dye. It means that the lower the undecomposition rate, the faster the methylene blue dye is decomposed by the coating formed on the glass plate, that is, the higher the photocatalytic function relating to the pigment decomposition of the coating. (Double-circle): The undecomposition rate is less than 40%, the fading of a big pigment
  • Undecomposed rate is 40% to 60%, fading of the dye is observed, and the coating has a photocatalytic function.
  • X Undecomposed rate is greater than 60%, fading of the dye is insufficient, and the photocatalytic function of the coating is small.
  • Photocatalytic function contact angle An aqueous resin composition was applied on a glass plate to a thickness of 5 to 10 ⁇ m and dried at 105 ° C. for 5 minutes to form a coating. Thereafter, the glass plate was irradiated with a 15 W UV lamp for an arbitrary time. Thereafter, the contact angle between the painted plate and water was measured with a contact angle meter. A smaller contact angle means higher photocatalytic function.
  • a contact angle is larger than 50 degree
  • aqueous resin compositions of Examples 1 to 5 were excellent in polymerizability and dispersibility, were excellent in the uniformity of the resulting film and the photocatalytic function, and were improved in overall performance. Comparative Examples 1 to 3 had insufficient performance and were found to be inferior in overall properties.
  • the aqueous resin composition of the present invention is excellent in polymerizability and dispersibility, and can form a uniform film. Furthermore, it has a photocatalytic effect and can be suitably used as an aqueous resin composition having antifouling properties.
  • the present invention provides a titanium-containing aqueous resin composition that is excellent in coating properties, film-forming properties, and substrate adhesion properties, and is stable for a long period of time, and even though a high photocatalytic function is obtained, a uniform film A water-based resin composition capable of forming is provided.

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  • Paints Or Removers (AREA)

Abstract

L'invention porte sur une composition aqueuse de résine contenant du titane ayant une excellente aptitude au revêtement, une excellente aptitude à la formation d'un film et une excellente adhésion à des bases, qui est stable pendant une longue période de temps. L'invention porte également sur une composition aqueuse de résine qui permet la formation d'un film de revêtement uniforme ayant une fonction photocatalytique élevée. De façon spécifique, un mélange (A) obtenu par mélange d'un alcoolate de titane, d'un acide organique et d'eau, sert d'émulsifiant pour la polymérisation en émulsion. Une composition aqueuse de résine peut être obtenue par polymérisation d'un monomère polymérisable (B) ayant une double liaison éthylénique en présence du mélange (A). La composition aqueuse de résine obtenue par le procédé peut être utilisée pour une matière aqueuse de revêtement. La matière de revêtement ainsi obtenue présente une excellente aptitude au revêtement, une excellente aptitude à la formation d'un film et une excellente adhésion à des bases et elle est stable pendant une longue période de temps. De plus, lorsque la matière aqueuse de revêtement est appliquée sur une base, il peut se former un film de revêtement uniforme ayant une excellente adhérence à la base et un effet photocatalytique élevé.
PCT/JP2009/050684 2008-01-17 2009-01-19 Emulsifiant contenant du titane WO2009091064A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008007805A JP2010275330A (ja) 2008-01-17 2008-01-17 チタン含有乳化剤
JP2008-007805 2008-01-17

Publications (1)

Publication Number Publication Date
WO2009091064A1 true WO2009091064A1 (fr) 2009-07-23

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PCT/JP2009/050684 WO2009091064A1 (fr) 2008-01-17 2009-01-19 Emulsifiant contenant du titane

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Country Link
JP (1) JP2010275330A (fr)
WO (1) WO2009091064A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018059007A (ja) * 2016-10-06 2018-04-12 株式会社日本触媒 樹脂組成物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5734045B2 (ja) * 2011-03-25 2015-06-10 東海旅客鉄道株式会社 感光性金属アルコキシド、塗布液、及びパターン化膜の形成方法
JP6107352B2 (ja) * 2013-04-12 2017-04-05 三菱化学株式会社 異方性色素膜用色素、該色素を含む組成物、異方性色素膜及び偏光素子

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5398393A (en) * 1977-02-09 1978-08-28 Teijin Ltd Production of polyester
WO2004031258A1 (fr) * 2002-10-03 2004-04-15 Toray Industries, Inc. Compositions de resine polyester, catalyseurs pour la production de polyester, film polyester et support d'enregistrement magnetique
WO2005094978A1 (fr) * 2004-03-18 2005-10-13 Gifu University Composition de dispersion de particules, composition contenant des particules dispersees, procede de production associe, et produit compact fritte d'oxyde de titane d'anatase

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5398393A (en) * 1977-02-09 1978-08-28 Teijin Ltd Production of polyester
WO2004031258A1 (fr) * 2002-10-03 2004-04-15 Toray Industries, Inc. Compositions de resine polyester, catalyseurs pour la production de polyester, film polyester et support d'enregistrement magnetique
WO2005094978A1 (fr) * 2004-03-18 2005-10-13 Gifu University Composition de dispersion de particules, composition contenant des particules dispersees, procede de production associe, et produit compact fritte d'oxyde de titane d'anatase

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018059007A (ja) * 2016-10-06 2018-04-12 株式会社日本触媒 樹脂組成物

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