WO2009091064A1 - Titanium-containing emulsifier - Google Patents

Titanium-containing emulsifier 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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WIPO (PCT)
Prior art keywords
resin composition
water
aqueous resin
double bond
ethylenic double
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PCT/JP2009/050684
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French (fr)
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/en

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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.

Abstract

Disclosed is a titanium-containing aqueous resin composition having excellent coatability, excellent film formability and excellent adhesion to bases, which is stable for a long time. Also disclosed is an aqueous resin composition which enables formation of a uniform coating film having a high photocatalytic function. Specifically, a mixture (A) obtained by mixing a titanium alkoxide, an organic acid and water functions as an emulsifier for emulsion polymerization. An aqueous resin composition can be produced by polymerizing a polymerizable monomer (B) having an ethylenic double bond in the presence of the mixture (A). The aqueous resin composition produced by the method can be used for an aqueous coating material. The thus-obtained coating material excels in coatability, film formability and adhesion to bases, and is stable for a long time. In addition, when the aqueous coating material is applied over a base, there can be formed a uniform coating film having excellent adhesion to the base and a high photocatalytic effect.

Description

チタン含有乳化剤Titanium-containing emulsifier
　本発明は、チタン含有乳化剤を用いて得られる水性樹脂組成物に関し、特に塗工性、造膜性及び光触媒効果に優れるチタン含有水性樹脂組成物に関する。この組成物は、光触媒効果を有する水系の塗料、インキ、接着剤及び表面コート剤等に利用できる。 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.
　チタンアルコキシドは、架橋剤として、分子中に水酸基及びカルボキシル基等を有する化合物と反応するため、接着改良剤、塗料の架橋剤及び塗料の耐熱向上剤等に利用されている。また、ゾル－ゲル法等により酸化チタン微粒子を合成し、白色顔料、光触媒機能を有する顔料として利用されている。特に、光触媒機能を利用した用途では、ホルムアルデヒド等のＶＯＣに対する分解機能を有した塗料や付着した汚染物を分解できる耐汚染性塗料及び光触媒機能による表面親水化作用を利用した防曇性塗料などに応用されている。光触媒効果に優れる酸化チタンを利用し、基材に光触媒性被膜を形成する技術が提案されている。しかし、チタンアルコキシドは非常に高い加水分解性を有するので、作業中や保存中に、空気中の水分によって不溶物を生じやすい。また、チタンアルコキシドを使用する際には有機溶媒を大量に使用する必要があり、環境負荷が極めて高い。このため、環境負荷が低く耐加水分解性を有する水系チタン化合物として、水系のチタン組成物が検討されてきた。 Since 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. Further, 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. In particular, in applications using photocatalytic functions, 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. However, since titanium alkoxide has a very high hydrolyzability, insoluble matters are easily generated by moisture in the air during operation and storage. In addition, when using 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.
　例えば、特許文献１には、ヒドロキシカルボン酸とチタンテトラアルコキシドを水の共存下で反応させた水溶性チタンヒドロキシカルボン酸塩キレート化合物が提案されている。しかし、この水溶性チタンヒドロキシカルボン酸塩キレート化合物では、塗工性、造膜性及び基材密着性等に問題があり、そのままコーティング剤として使用することは困難である。 For example, Patent Document 1 proposes a water-soluble titanium hydroxycarboxylate chelate compound obtained by reacting hydroxycarboxylic acid and titanium tetraalkoxide in the presence of water. However, 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.
　例えば、特許文献２には、光触媒機能を有する酸化チタン粒子状物を水性エマルジョン塗料に混合した塗料組成物が提案されている。中でも塗装作業の環境衛生、火災防止、省資源等の観点からも優れ、光触媒機能を有する酸化チタン微粒子を水性エマルジョン塗料に混合することで、種々の基材への塗布が可能であり、塗布後は安定に酸化チタンを固定化することが可能である。
　しかし、上記記載の光触媒機能を有する酸化チタン微粒子を水性エマルジョン塗料に混合する方法には、水性エマルジョン塗料中での酸化チタン微粒子の分散性、安定性が悪いため、酸化チタンが凝集し均一な塗膜を得られにくいという問題がある。また、得られた塗料組成物中で酸化チタンの分離、沈降等が生じるため、光触媒効果が部分的にしか得られない、同じように塗布しても効果に差を生じ得る、従って、長期間安定的に使用できない等の問題がある。 For example, 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. In addition, because separation and sedimentation of titanium oxide occurs in the obtained coating composition, a photocatalytic effect can be obtained only partially, and even if applied in the same way, a difference in effect can be produced. There is a problem that it cannot be used stably.
特公昭５０－５１７７号公報Japanese Patent Publication No. 50-5177 特開２００２－１４６２９３号公報JP 2002-146293 A
　本発明はこのような従来技術の問題、課題を解決するためになされたものである。即ち、塗工性、造膜性及び基材密着性に優れ、かつ長期間安定なチタン含有水性樹脂組成物を得ることを目的とする。更に、高い光触媒機能が得られるにもかかわらず、均一な被膜を形成することができる水性樹脂組成物を得ることを目的とする。 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.
　本発明者らは、上記課題を解決する為、種々検討した結果、驚くべきことに、チタンアルコキシド、有機酸及び水を混合することによって得られる混合物を用いると、エチレン性二重結合を有する重合性単量体を水性媒体中で重合することができること、即ち、チタンアルコキシド、有機酸及び水を混合することによって得られる混合物が、乳化重合用乳化剤として機能し得ることを見出した。従って、チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、エチレン性二重結合を有する重合性単量体を重合する水性樹脂組成物の製造方法を見出した。更に、この製造方法で製造した水性樹脂組成物は、優れた塗工性、造膜性、分散性及び長期間安定性を有し、この水性樹脂組成物を基材に塗工することによって、優れた均一性と基材密着性を示す被膜を形成することも見出した。また、この得られた水性樹脂組成物は、高い光触媒効果を有することも見出して、本発明を完成した。 As a result of various investigations to solve the above problems, 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 | polymerizes the polymerizable monomer which has an ethylenic double bond in presence of the mixture obtained by mixing a titanium alkoxide, an organic acid, and water was discovered. Furthermore, 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.
　従って、本発明の一の要旨において、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物を含む乳化重合用乳化剤を提供する。
　更に、本発明の他の要旨において、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合する水性樹脂組成物（又は水性エマルジョン組成物）の製造方法を提供する。 Accordingly, in one aspect of the present invention, there is provided (A) 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.
　また、本発明の好ましい要旨において、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合することで得られる水性樹脂組成物を提供する。 Further, in a preferred aspect of the present invention, (A) in the presence of a mixture obtained by mixing titanium alkoxide, organic acid and water, (B) polymerizing a polymerizable monomer having an ethylenic double bond. The aqueous resin composition obtained in the above.
　更にまた、本発明の一の態様において、（Ｂ）エチレン性二重結合を有する重合性単量体は、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成る上記水性樹脂組成物及びその製造方法を提供する。
　更に、本発明の他の態様において、チタンアルコキシドが、チタンテトライソプロポキシドである上記水性樹脂組成物及びその製造方法を提供する。
　また、本発明の好ましい態様において、上記水性樹脂組成物を含んで成る水性塗料、インキ、接着剤及び表面コート剤を提供する。 Furthermore, in one embodiment of the present invention, (B) 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.
Furthermore, the other aspect of this invention provides the said aqueous resin composition whose titanium alkoxide is titanium tetraisopropoxide, and its manufacturing method.
Moreover, 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.
　尚、本明細書において「水性樹脂」とは、ポリマー粒子が水性媒体中に存在する状態、好ましくは分散する状態を意味し、従って、「水性樹脂組成物」とは、ポリマー粒子と水性媒体の両方を含む組成物を意味する。 In the present specification, 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.
　本発明に係る水性樹脂組成物は、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、アルコキシシリル基を有しエチレン性二重結合を有する単量体を含んで成る（Ｂ）エチレン性二重結合を有する重合性単量体を重合することで得られるので、塗工性、造膜性、基材密着性に優れ、長期間安定であり、また、形成される被膜は、均一性と基材密着性に優れ、高い光触媒効果と高い耐水性を発現することができる。 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.
　本発明に係る水性塗料等は、上述の本発明に係る水性樹脂組成物を含んで成るので、塗工性、造膜性、基材密着性に優れ、長期間安定であり、また、本発明に係る塗料は、基材に塗工すると均一で基材密着性に優れる被膜を形成することができ、高い光触媒効果と高い耐水性を発現することができる。
　更に、酸化チタンが均一に分散した膜を形成させることも可能であり、より高い光触媒効果を発現し得る。 Since 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.
　更にまた、本発明に係る水性樹脂組成物及び水性塗料等は、チタンアルコキシドがチタンテトライソプロポキシドである場合、光触媒効果がさらに向上する。 Furthermore, when the titanium alkoxide is titanium tetraisopropoxide, the photocatalytic effect of the aqueous resin composition and the aqueous paint according to the present invention is further improved.
　以下に本発明について具体的に説明する。
　本発明では、乳化重合用乳化剤として、「（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物（以下、「（Ａ）混合物」ともいう）」をそのままで、又は必要に応じて濃度を調節したり、適宜他の添加剤等を加えて用いる。従って、（Ａ）混合物を含む乳化重合用乳化剤は、（Ａ）混合物そのものであってよく、また、適宜濃度調節のため等に水や他の添加剤を含んでよい。 The present invention will be specifically described below.
In the present invention, as an emulsifier for emulsion polymerization, “(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. To adjust the concentration or add other additives as appropriate. Therefore, 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.
　本明細書において、「乳化重合」とは、油溶性の単量体を、乳化剤を用いて水中で乳濁状態とし、水溶性の重合開始剤を用いて行うラジカル重合をいう。 In the present specification, “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.
　この乳化重合用乳化剤として使用する混合物は、チタンアルコキシドと、有機酸と水を混合することによって得ることができるが、チタンアルコキシドと有機酸と水を混合する順序は、特に限定されるものではない。更に、混合する際の温度及び圧力等も特に限定されるものではないが、通常、室温（約２５℃）大気圧下で混合後、更に７０℃で加熱攪拌して行われる。一般的に、攪拌することが好ましく、攪拌時間は、通常、約５～２４時間であるが、必要に応じて攪拌時間は調節することができる。チタンアルコキシドと有機酸と水の混合比は、目的とする混合物が乳化重合用乳化剤として利用できる限り、特に限定されるものではないが、チタンと有機酸とのモル比は、０．１：１～５：１であることが好ましく、０．５：１～１．５：１であることがより好ましく、１：１であることが特に好ましい。混合物に含まれる水分量は、混合物が乳化重合用乳化剤として使用できる限り特に限定されるものではなく、適宜調節されるものであるが、混合物全体を基準として、０．１～６０重量％であることが好ましく、３～４０重量％であることがより好ましく、５～３０重量％であることが特に好ましい。 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. . Furthermore, although 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.
　本明細書において、「チタンアルコキシド」とは、より具体的には、下記式（１）で示されるチタンテトラアルコキシドをいう。
　式（１）：Ｔｉ（ＯＲ）４
［式（１）で、Ｒはアルキル基であって、４つのアルキル基は、同じであっても異なっていてもよい。］
　式（１）で示される化合物としては、例えば、チタンテトラメトキシド〔Ｔｉ（ＯＭｅ）４〕、チタンテトラエトキシド〔Ｔｉ（ＯＥｔ）４〕、チタンテトライソプロポキシド〔Ｔｉ（ＯｉＰｒ）４〕、チタンテトラブトキシド〔Ｔｉ（ＯＢｕ）４〕及びこれらの誘導体を例示できる。これらのなかでも、チタンアルコキシドとして、一般に入手の容易さ及び取り扱いの容易さと、光触媒効果の良好さから、チタンテトライソプロポキシドが好ましい。 In the present specification, the “titanium alkoxide” more specifically refers to a titanium tetraalkoxide represented by the following formula (1).
Formula (1): Ti (OR) 4
[In the formula (1), R is an alkyl group, and the four alkyl groups may be the same or different. ]
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. Among these, titanium tetraisopropoxide is preferred as the titanium alkoxide because it is generally easily available and easy to handle and has a good photocatalytic effect.
　本明細書において、また、「有機酸」とは、有機化合物のうち酸性を有するものをいい、カルボン酸を例示できる。有機酸として、乳酸、シュウ酸、クエン酸、及び酒石酸等が好ましく、一般的に入手、取り扱いが容易な乳酸が特に好ましい。有機酸は、単独で用いてもよいし、２種類以上を併用してもよい。 In the present specification, “organic acid” means an organic compound having acidity, and examples thereof include carboxylic acid. As the organic 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.
　（Ａ）混合物を作るための「水」とは、特に限定されるものではなく、主に、純水、蒸留水及びイオン交換水等のいわゆる水をいうが、水溶性の有機溶剤、例えば、アセトン及び低級アルコール等を適宜含んでもよい。 (A) “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.
　本発明においては、上述の（Ａ）混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体（以下、「（Ｂ）重合性単量体」ともいう）を重合することで水性樹脂組成物を得る。
　本明細書において「エチレン性二重結合」とは、一分子中に少なくとも一つの重合反応（ラジカル重合）し得る炭素原子間の二重結合を有する化合物を言う。そのようなエチレン性二重結合を有する官能基として、例えば、ビニル基（ＣＨ２＝ＣＨ－）、（メタ）アリル基（ＣＨ２＝ＣＨ－ＣＨ２－及びＣＨ２＝Ｃ（ＣＨ３）－ＣＨ２－）、（メタ）アクリロイルオキシ基（ＣＨ２＝ＣＨ－ＣＯＯ－及びＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ－）、及び－ＣＯＯ－ＣＨ＝ＣＨ－ＣＯＯ－等を例示できる。 In the present invention, (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). To obtain an aqueous resin composition.
In the present specification, “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.
　尚、本明細書では、アクリル酸及びメタクリル酸を総称して「（メタ）アクリル酸」といい、アクリル酸エステルとメタクリル酸エステルを総称して「（メタ）アクリル酸エステル」又は「（メタ）アクリレート」という。アリル基及びアクリロイルオキシ基についても同様である。 In this specification, 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.
　本明細書において「（Ｂ）エチレン性二重結合を有する重合性単量体」とは、エチレン性二重結合を有する単量体であって、ラジカル重合（好ましくは乳化重合）できる単量体をいい、目的とする水性樹脂組成物の特性に応じて適宜使用することができる。 In the present specification, “(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.
　このような「エチレン性二重結合を有する重合性単量体」としては、例えば、
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、及びシクロヘキシル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル類（（メタ）アクリル酸シクロアルキルエステル類を含む）；
　（メタ）アクリル酸グリシジル等のエポキシ基を有する（メタ）アクリル酸エステル類；
　アクリル酸、メタクリル酸、イタコン酸、クロトン酸、フマール酸、マレイン酸、マレイン酸の半エステル等のカルボキシル基とエチレン性二重結合を有する化合物及びカルボン酸塩基とエチレン性二重結合を有する化合物；
　アクリルスルホン酸、メタクリルスルホン酸、２－アクリロイルアミノ－２－メチルプロパンスルホン酸、２－メタクリロイルアミノ－２－メチルプロパンスルホン酸、スチレンスルホン酸等のスルホン酸基とエチレン性二重結合を有する化合物及びスルホン酸塩基とエチレン性二重結合を有する化合物；
　（メタ）アクリル酸オキシエチルアミドフォスフェート等のリン酸基及びエチレン性二重結合を有する化合物、並びにリン酸塩基及びエチレン性二重結合を有する化合物；
　スチレン及びビニルトルエン等のスチレン及びスチレンの誘導体類；
　エチレン等のアルケン類、並びにブタジエン、イソプレン等のジエン類；
　酢酸ビニル及びプロピオン酸ビニル等のビニルエステル化合物類；
　塩化ビニル及び塩化ビニレン等の塩素化されたビニル化合物類；
　アクリロニトリル等のシアノ基を有するエチレン性炭素原子間二重結合を有する化合物類；
　アルコキシシリル基を含有し、エチレン性二重結合を有する単量体
を例示できる。
　上述の「エチレン性二重結合を有する単量体」は、単独で又は組み合わせて使用することができる。 As such 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, crotonic acid, fumaric acid, maleic acid, maleic acid half ester, and the like, and compounds having a carboxylate group and an ethylenic double bond;
Compounds having a sulfonic acid group and an ethylenic double bond, such as acrylic sulfonic acid, methacryl sulfonic acid, 2-acryloylamino-2-methylpropane sulfonic acid, 2-methacryloylamino-2-methylpropane sulfonic acid, and styrene sulfonic acid; A compound having a sulfonate group and an ethylenic double bond;
A compound having a phosphate group and an ethylenic double bond, such as (meth) acrylic acid oxyethyl amide phosphate, and a compound having a phosphate group and an ethylenic double bond;
Styrene and styrene derivatives such as styrene and vinyltoluene;
Alkenes such as ethylene, and dienes such as butadiene and isoprene;
Vinyl ester compounds such as vinyl acetate and vinyl propionate;
Chlorinated vinyl compounds such as vinyl chloride and vinylene chloride;
Compounds having a double bond between ethylenic carbon atoms having a cyano group such as acrylonitrile;
A monomer containing an alkoxysilyl group and having an ethylenic double bond can be exemplified.
The above-mentioned “monomers having an ethylenic double bond” can be used alone or in combination.
　（Ｂ）エチレン性二重結合を有する重合性単量体は、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成ることが好ましい。
　本明細書において「アルコキシシリル基を含有し、エチレン性二重結合を有する単量体」とは、主にエマルジョンの重合体内部又はエマルジョンの重合体同士の間に架橋構造を形成し、本発明のエマルジョン組成物から得られる皮膜の耐水性、基材密着性等の向上に寄与し得る化合物をいう。 (B) The polymerizable monomer having an ethylenic double bond preferably contains an alkoxysilyl group and a monomer having an ethylenic double bond.
In the present specification, 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. The compound which can contribute to improvement of the water resistance of the film | membrane obtained from this emulsion composition, base-material adhesiveness, etc. is said.
　本明細書において、「アルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成る（Ｂ）エチレン性二重結合を有する重合性単量体を重合することで得られる」樹脂は単独重合体であっても、共重合体であっても差し支えない。
　即ち、得られる樹脂は、「アルコキシシリル基を含有しエチレン性二重結合有する単量体」の単独重合体、もしくは、この単量体とこの単量体以外の上述の「エチレン性二重結合を有する重合性単量体」との共重合体のいずれであってもよい。 In the present specification, “obtained by polymerizing a polymerizable monomer having an ethylenic double bond (B) comprising an alkoxysilyl group-containing monomer having an ethylenic double bond” 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".
　「アルコキシシリル基」とは、加水分解することによって、ケイ素に結合するヒドロキシシリル基（Ｓｉ－ＯＨ）を与えるケイ素含有の官能基、例えば、トリメトキシシリル基、トリエトキシシリル基、ジメトキシシリル基、ジエトキシシリル基、モノメトキシシリル基、モノエトキシシリル基、トリイソプロポキシシリル基、ジイソプロポキシシリル基及びモノイソプロポキシシリル基等のアルコキシシリル基を例示できる。
　「エチレン性二重結合」は、上述した通りである。 “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.
　本発明では、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体として、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－メタクリロキシプロピルメチルジメトキシラン、γ－メタクリロキシプロピルメチルジエトキシシラン、ビニルトリイソプロポキシシラン、アリルトリメトキシシラン、γ－アクリロキシプロピルトリエトキシシラン、ビニルトリアセトキシシラン及びトリス（β－メトキシエトキシ）ビニルシラン等を例示することができる。これらのアルコキシシリル基を含有し、エチレン性二重結合を有する単量体は、エマルジョンの性質に応じて適宜選択する事ができ、単独で、又は組み合わせて使用する事ができる。 In the present invention, monomers having an alkoxysilyl group and having an ethylenic double bond include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethyl. Ethoxysilane, γ-methacryloxypropylmethyldimethoxylane, γ-methacryloxypropylmethyldiethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltriacetoxysilane and tris (β -Methoxyethoxy) vinylsilane and the like. 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.
　アルコキシシリル基を含有し、エチレン性二重結合を有する単量体として、γ－メタクリロキシプロピルトリメトキシシラン、トリス（β－メトキシエトキシ）ビニルシラン、γ－メタクリロキシプロピルメチルジメトキシラン及びビニルトリイソプロポキシシランが好ましく、γ－メタクリロキシプロピルトリメトキシシランが特に好ましい。 Monomers having an alkoxysilyl group and having an ethylenic double bond include γ-methacryloxypropyltrimethoxysilane, tris (β-methoxyethoxy) vinylsilane, γ-methacryloxypropylmethyldimethoxylane, and vinyltriisopropoxy. Silane is preferred, and γ-methacryloxypropyltrimethoxysilane is particularly preferred.
　本発明では、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体と、上述のその他のエチレン性二重結合を有する単量体を組み合わせて使用する場合、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体は、（Ｂ）重合性単量体（又は反応混合物）中に０．１～２０重量％含まれることが好ましく、０．５～１５重量％含まれることがより好ましく、０．５～１０重量％含まれることが特に好ましい。 In the present invention, when a monomer having an alkoxysilyl group and having an ethylenic double bond is used in combination with the above-mentioned other monomer having an ethylenic double bond, 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.
　（Ｂ）エチレン性二重結合を有する重合性単量体は、一般的に（メタ）アクリル酸アルキルエステル、場合によりスチレン及びスチレンの誘導体、場合によりカルボキシル基とエチレン性二重結合を有する化合物、場合によりアルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成ることが好ましい。 (B) 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.
　（メタ）アクリル酸アルキルエステルは、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及びシクロヘキシル（メタ）アクリレートから選択される少なくとも一種であることが好ましく、メチルメタクリレートとブチルアクリレートの組み合わせであることが特に好ましい。
　スチレン及びスチレンの誘導体は、スチレンとビニルトルエンから選択される少なくとも一種であることが好ましいが、スチレンであることがより好ましい。
　カルボキシル基とエチレン性二重結合を有する化合物は、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、フマール酸から選択される少なくとも一種であることが好ましく、アクリル酸であることが特に好ましい。
　アルコキシシリル基を含有し、エチレン性二重結合を有する単量体は、γ－メタクリロキシプロピルトリメトキシシラン、トリス（β－メトキシエトキシ）ビニルシラン、γ－メタクリロキシプロピルメチルジメトキシラン及びビニルトリイソプロポキシシランから選択される少なくとも一種であることが好ましく、γ－メタクリロキシプロピルトリメトキシシランであることが特に好ましい。 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 γ-methacryloxypropyltrimethoxysilane, tris (β-methoxyethoxy) vinylsilane, γ-methacryloxypropylmethyldimethoxylane and vinyltriisopropoxy. It is preferably at least one selected from silanes, particularly preferably γ-methacryloxypropyltrimethoxysilane.
　重合は、通常の方法を使用して、水性媒体中で適宜触媒等を用いて行うことができる。ここで「水性媒体」とは、特に限定されるものではなく、主に、純水、蒸留水及びイオン交換水等のいわゆる水をいうが、水溶性の有機溶剤、例えば、アセトン及び低級アルコール等を適宜含んでもよい。 Polymerization can be carried out using a catalyst or the like as appropriate in an aqueous medium using a normal method. Here, the “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.
　反応温度、反応時間、水性溶媒の種類、単量体混合物の種類及び濃度、攪拌速度、並びに重合開始剤の種類及び濃度等の重合反応の条件は、目的とする水性樹脂組成物の特性によって、適宜選択され得るものである。 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.
　本明細書においては、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下で、重合性単量体を重合する。即ち、水性媒体中で重合性単量体を重合するために、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物を、乳化重合用乳化剤として使用する。従って、本発明に係る重合性単量体の重合は、いわゆる乳化重合であると考える。 In this specification, (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.
　重合性単量体を重合するため用いる（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物は、重合性単量体１００重量部に対して、０．１～２０重量部用いることが好ましく、１～１５重量部用いることがより好ましく、３～１３重量部用いることがさらに好ましい。（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物が０．１重量部未満の場合、機械的安定性が悪く成り得、２０重量部を超える場合、長期安定性が低下し得る。尚、（Ａ）混合物の重量部は、水を含まない部分の重量部を基準とする。
　（Ａ）混合物中の水の量は、機械的安定性や長期安定性等を考慮して、適宜調整することができるが、混合物全体を基準として、０．１～６０重量％であることが好ましく、３～４０重量％であることがより好ましく、５～３０重量％であることが特に好ましい。 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. (A) When the mixture obtained by mixing titanium alkoxide, organic acid and water is less than 0.1 parts by weight, mechanical stability may be deteriorated, and when it exceeds 20 parts by weight, long-term stability is reduced. obtain. In addition, the weight part of (A) mixture is based on the weight part of the part which does not contain water.
(A) 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.
　本発明においては、（Ｂ）重合性単量体の水性媒体中での重合性と、得られる水性樹脂組成物（エマルジョン）の長期安定性を向上させる目的で、一般的な「乳化剤」を用いることができる。そのような「乳化剤」として、当事者に公知の界面活性剤を使用できる。 In the present invention, 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. As such an “emulsifier”, a surfactant known to those skilled in the art can be used.
　乳化剤は、単量体を乳化する能力を有し、重合の過程ではミセルを形成して単量体に重合の場を提供する。更に、重合中又は重合後は得られるポリマー粒子の表面に固定化して粒子の分散安定性を図る。
　乳化剤として、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤、高分子界面活性剤等を例示できる。 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.
Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant.
　アニオン系界面活性剤として、例えば、ナトリウムドデシルサルフェート、カリウムドデシルサルフェート等のアルカリ金属アルキルサルフェート、ナトリウムドデシルポリグリコールエーテルサルフェート、アンモニウムドデシルサルフェート等のアンモニウムアルキルサルフェート、ナトリウムスルホシノエート、スルホン化パラフィンのアルカリ金属塩、スルホン化パラフィンのアンモニウム塩等のアルキルスルホネート、ナトリウムラウレート、トリエタールアミンオレエート、トリエタールアミンアビエテート等の脂肪酸塩、ナトリウムドデシルベンゼンスルホネ－ト、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェート等のアルキル亜リールスルホネート、高アルキルナフタレンスルホン酸、ナフタレンスルホン酸ホルマリン縮合物、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルエーテルサルフェート塩、ポリオキシエチレンアルキルアリールサルフェート塩等を例示できる。
　本発明では、アニオン系界面活性剤として、ポリオキシエチレンアルキルエーテルサルフェート塩（ナトリウム塩）（花王株式会社製のラテムルＷＸ（商品名））が好適である。 Examples of 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. Salts, 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. Alkyl sulfite sulfonate, high alkyl naphthalene sulfonic acid, naphthalene sulfo Acid-formalin condensates, dialkyl sulfosuccinates, polyoxyethylene alkyl sulfates salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylaryl sulfate salts and the like.
In the present invention, polyoxyethylene alkyl ether sulfate salt (sodium salt) (Latemul WX (trade name) manufactured by Kao Corporation) is suitable as the anionic surfactant.
　ノニオン系界面活性剤として、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセロールのモノラウレート等の脂肪酸モノグリセライド、ポリオキシエチレンオキシプロピレン共重合体、エチレンオキサイドと脂肪族アミン、アミド又は酸との縮合生成物等を例示できる。 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.
　カチオン系界面活性剤として、例えば、モノアルキルアンモニウム塩、ジアルキルアンモニウム塩、エチレンオキサイド付加型アルキルアンモニウム塩を例示できる。
　両性界面活性剤として、例えば、アミドプロピルベタイン、アミノ酢酸ベタイン等を例示できる。
　高分子界面活性剤として、例えば、ポリ（メタ）アクリル酸ナトリウム、ポリ（メタ）アクリル酸カリウム、ポリ（メタ）アクリル酸アンモニウム、ポリ（メタ）アクリレート等を例示できる。
　更に、メチルセルロース、ヒドロキシエチルセルロース、及びカルボキシメチルセルロース等のセルロース誘導体、水性ポリウレタン樹脂、水溶性アクリル樹脂、ポリビニルピロリドン系樹脂、並びにポリビニルアルコール等を例示できる。 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.
　更に、乳化剤として、反応性界面活性剤を使用することができる。
　反応性界面活性剤として、例えば、ポリオキシエチレンアリルグリシジルノニルフェニルエーテルの硫酸エステル塩（旭電化工業社製のアデカリアソープＳＥシリーズ（商品名））、α－スルホ－ω－（１－（アルコキシ）メチル－２－（２－プロペニルオキシ）エトキシ）－ポリ（オキシ－１，２－エタンジイル）のアンモニウム塩（旭電化工業社製のアデカリアソープＳＲシリーズ（商品名））、ポリオキシエチレン（又はアルキレン）アルキル（又はアルケニル）エーテル硫酸アンモニウム塩（花王社製のＰＤシリーズ（商品名））、スルホコハク酸型反応性活性剤（花王社製のラテムル１８０シリーズ（商品名））、アルキルアリルスルホコハク酸ナトリウム塩（三洋化成工業社製のエレミノールＪＳ－２（商品名））、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬社製のアクアロンＨＳシリーズ（商品名））、ポリオキシエチレン－１－（アリルオキシメチル）アルキルエーテル硫酸エステルアンモニウム塩（第一工業製薬社製のアクアロンＫＨシリーズ（商品名））、ポリオキシエチレンアリルグリシジルノニルフェニルエーテル（旭電化工業社製のアデカリアソープＮＥシリーズ（商品名））、ポリオキシエチレンノニルプロペニルエーテル（第一工業製薬社製のアクアロンＲＮシリーズ（商品名））、α－ヒドロ－ω－（１－（アルコキシ）メチル－２－（プロペニルオキシ）エトキシ）－ポリ（オキシ－１，２－エタンジイル）（旭電化工業社製のアデカリアソープＥＲシリーズ（商品名））等を例示できる。 Furthermore, a reactive surfactant can be used as an emulsifier.
As 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.), α-sulfo-ω- (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 allylsulfosuccinate sodium salt (Eleminol JS-2 (trade name) manufactured by Sanyo Chemical Industries, Ltd.), polyoxye Tylene nonylpropenyl phenyl ether sulfate ammonium salt (AQUALON HS series (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd.) Aqualon KH series (trade name)), polyoxyethylene allyl glycidyl nonyl phenyl ether (Adekaria soap NE series (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene nonyl propenyl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) AQUALON RN series (trade name)), α-hydro-ω- (1- (alkoxy) methyl-2- (propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (ADEKA manufactured by Asahi Denka Kogyo Co., Ltd.) Rear soap ER series (trade name)) and the like.
　反応性乳化剤は、単独で又は２種以上併せて用いることができる。これらの中でも、アルキルアリルスルホコハク酸ナトリウム塩（三洋化成工業社製のエレミノールＪＳ－２（商品名））、アルキルエーテル硫酸エステルアンモニウム塩（第一工業製薬社製のアクアロンＫＨシリーズ（商品名））が好ましい。 Reactive emulsifiers can be used alone or in combination of two or more. Among these, 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.
　上述したように、本発明においては、（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、重合性単量体を重合するが、「乳化剤」として、当事者に公知の上記の一般的な界面活性剤を、併用して重合することができる。
　重合性単量体を乳化重合するために用いる上記一般的な界面活性剤は、（Ｂ）エチレン性二重結合を有する重合性単量体１００重量部に対して、０．１～６重量部用いることが好ましく、１～３量部用いることがより好ましい。 As described above, in the present invention, (A) 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.
　本発明では、（Ｂ）エチレン性二重結合を有する重合性単量体を重合するために、重合開始剤を用いることができる。「重合開始剤」とは、少量の添加によって単量体の重合反応を起こさせる事ができる化合物をいい、水性媒体中で使用できるものが好ましい。そのような重合開始剤として、例えば、過酸化水素、水溶性無機過酸化物、並びに水溶性還元剤と水溶性無機過酸化物の組み合わせや水溶性還元剤と有機過酸化物の組み合わせを例示できる。 In the present invention, 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. .
　「水溶性無機過酸化物」として、例えば、通常ラジカル酸化還元重合触媒として用いられる水に可溶性の還元剤を使用できる。そのような還元剤として、例えば、亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、ホルムアルデヒドスルホキシル酸ナトリウム、乳酸第一鉄、硫酸第一鉄アンモニウム、ピロリン酸第一鉄、スルフィン酸、L-アスコルビン酸とそのナトリウム塩及びカリウム塩及びカルシウム塩、エチレンジアミン四酢酸とそのナトリウム塩及びカリウム塩、エチレンジアミン四酢酸もしくはその塩と鉄、銅、もしくはクロム等の重金属と錯化合物、並びに還元糖を例示できる。 As the “water-soluble inorganic peroxide”, for example, a water-soluble reducing agent usually used as a radical redox polymerization catalyst can be used. 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.
　「水溶性有機過酸化物」として、例えば、クメンヒドロペルオキシド、ｐ－サイメンヒドロペルオキシド、ｔ－ブチルイソプロピルベンゼンヒドロペルオキシド、ジイソプロピルベンゼンヒドロペルオキシド、ｐ－メンタンヒドロペルオキシド、デカリンヒドロペルオキシド、ｔ－アミルヒドロペルオキシド、ｔ－ブチルメルカプタン、２－エチルヘキシルチオグリコレート、２－メルカプトエタノール、トリクロロブロモメタン等を例示する事ができる。 Examples of the “water-soluble organic peroxide” 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.
　本発明の水性樹脂組成物から得られる被膜のガラス転移温度（Ｔｇ）は、－５０～１００℃であることが好ましく、被膜の耐水性、基材密着性がより高い水性樹脂組成物を得るためには、被膜のガラス転移温度が－３０～５０℃であることが好ましい。
　本発明では、被膜の「ガラス転移温度」とは、示差操作熱量計（具体的には、エスアイアイナノテクノロジー（株）製のＳＩＩナノテクノロジーＤＳＣ６２２０）を用いて、５～１０ｍｇの試料のＤＳＣ曲線を、５℃／分の昇温速度で測定し、得られたＤＳＣ曲線の変曲点の温度をいう。 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. For this, the glass transition temperature of the coating is preferably -30 to 50 ° C.
In the present invention, 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.
　更に、本発明に係るチタン含有水性樹脂組成物は、本発明の特性を損なわない範囲において、他の添加剤を適量配合して良い。
　他の添加剤としては、例えば、
　硬化を早くする目的で添加される金属アルコキシド等の硬化触媒；
　粘度を調整する目的で添加される水、アルコール類、ケトン類、グリコール類等の希釈溶剤；
　ガラス、石英、水酸化アルミニウム、アルミナ、カオリン、タルク、炭酸カルシウム、珪酸カルシウム、水酸化マグネシウム、酸化チタン等の無機充填剤；
　アクリル樹脂粉、エポキシ樹脂粉、ポリエステル樹脂粉等の有機充填剤；
　カーボンブラック、ベンガラ、フタロシアニンブルー、クロ－ムイエロー、二酸化チタン等の顔料または染料に代表される着色剤；
　その他の中和剤、増粘剤、分散剤、消泡剤、増膜助剤、防腐剤、防カビ剤、抗菌剤、凍結防止剤、紫外線吸収剤、金属粉、滑剤、離型剤、界面活性剤、カップリング剤等を例示できるが、これらに限定されるものではない。 Furthermore, 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, interfaces Although an activator, a coupling agent, etc. can be illustrated, it is not limited to these.
　本発明に係る水性樹脂組成物は、塗工性及び造膜性に優れ、均一な被膜を形成することができる。形成される被膜は、基材密着性に優れ、更に優れた光触媒機能を発揮することができる。本発明に係る水性樹脂組成物は、光触媒効果を有する水系の塗料、インキ、接着剤及び表面コート剤等に好適に使用することができる。 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.
　本発明の主な態様を以下に記載する。
　１．
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物を含む乳化重合用乳化剤。
　２．
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合する水性樹脂組成物の製造方法。
　３．
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合することで得られる水性樹脂組成物。
　４．
　（Ｂ）エチレン性二重結合を有する重合性単量体は、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成る上記３に記載の水性樹脂組成物。
　５．
　チタンアルコキシドが、チタンテトライソプロポキシドである上記３又は４に記載の水性樹脂組成物。
　６．
　上記３～５のいずれかに記載の水性樹脂組成物を含んで成る水性塗料、インキ、接着剤又は表面コート剤。 The main aspects of the present invention are described below.
1.
(A) An emulsifier for emulsion polymerization comprising a mixture obtained by mixing titanium alkoxide, an organic acid and water.
2.
(A) A method for producing an aqueous resin composition in which (B) a polymerizable monomer having an ethylenic double bond is polymerized in the presence of a mixture obtained by mixing a titanium alkoxide, an organic acid and water.
3.
(A) An aqueous resin composition obtained by polymerizing a polymerizable monomer having an ethylenic double bond in the presence of a mixture obtained by mixing titanium alkoxide, an organic acid and water.
4).
(B) The aqueous resin composition according to 3 above, wherein the polymerizable monomer having an ethylenic double bond contains an alkoxysilyl group and a monomer having an ethylenic double bond.
5).
5. The aqueous resin composition according to 3 or 4 above, wherein the titanium alkoxide is titanium tetraisopropoxide.
6).
An aqueous paint, ink, adhesive or surface coating agent comprising the aqueous resin composition according to any one of 3 to 5 above.
　以下、本発明を実施例および比較例により具体的にかつ詳細に説明するが、これらの実施例は本発明の一態様にすぎず、本発明はこれらの例によって何ら制限されるものではない。また、実施例及び比較例において重量部及び重量％は特に記載しない限り、媒体（溶媒）を含まない部分を基準とする。 Hereinafter, the present invention will be described specifically and in detail with reference to examples and comparative examples, but these examples are only one aspect of the present invention, and the present invention is not limited to these examples. In Examples and Comparative Examples, parts by weight and% by weight are based on parts not containing a medium (solvent) unless otherwise specified.
　表１に記載した割合で各成分を用いて、実施例１～５、及び比較例１～３の混合物を製造した。但し、使用した（Ａ）チタンテトラアルコキシド、有機酸及び水を混合することによって得られる混合物、（Ｂ）エチレン性二重結合を有する重合性単量体、（Ｃ）他の一般的な乳化剤、（Ｄ）アナターゼ型酸化チタンの微粒子からなる光触媒材料を、以下に示す。
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物は下記の通りである。
　（Ａ－１）チタンテトライソプロポキシド、乳酸及び水を混合することによって得られる混合物
　（Ａ－２）チタンテトラノルマルブトキシド、乳酸及び水を混合することによって得られる混合物 Mixtures of Examples 1 to 5 and Comparative Examples 1 to 3 were produced using each component in the proportions shown in Table 1. However, (A) the titanium tetraalkoxide used, a mixture obtained by mixing an organic acid and water, (B) a polymerizable monomer having an ethylenic double bond, (C) other common emulsifiers, (D) A photocatalytic material composed of fine particles of anatase-type titanium oxide is shown below.
(A) The mixture obtained by mixing a titanium alkoxide, an organic acid, and water is as follows.
(A-1) Mixture obtained by mixing titanium tetraisopropoxide, lactic acid and water (A-2) Mixture obtained by mixing titanium tetranormal butoxide, lactic acid and water
　（Ｂ）エチレン性二重結合を有する重合性単量体は下記の通りである。
　（Ｂ－１）メチルメタクリレート
　（Ｂ－２）スチレン
　（Ｂ－３）ブチルアクリレート
　（Ｂ－４）アクリル酸
　（Ｂ－５）γ－メタクリロキシプロピルトリメトキシシラン（東レ・ダウコーニング株式会社、ＳＺ６０３０（商品名））
　（Ｃ）他の乳化剤は下記の通りである
　（Ｃ－１）ポリオキシエチレンアルキルエーテルサルフェート塩（ナトリウム塩）（花王株式会社、ラテムルＷＸ（商品名））
　（Ｄ）アナタ－ゼ型酸化チタンの微粒子からなる光触媒材料
　（Ｄ－１）タイノックＡ－６（多木化学株式会社、タイノックＡ－６（商品名）） (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) γ-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）混合物の製造例１～２
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の製造
　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物は、既知の任意の方法、例えば、国際公開第２００５／０９４９７８号に掲載の方法等にしたがって製造する事ができる。
　（Ａ－１）チタンテトライソプロポキシド、乳酸及び水を混合することによって得られる混合物は、乳酸（Ａｌｆａ　Ａｅｓａｒ製）９０重量部に４７８重量部の水を加えて乳酸を水に溶解後、この乳酸水溶液に室温でチタンテトライソプロポキシド（和光純薬工業株式会社製）１１５重量部を攪拌しながら加えて溶解した。更に、７０℃で加熱攪拌して（Ａ－１）混合物を得た。
　（Ａ－２）チタンテトラノルマルブトキシド、乳酸及び水を混合することによって得られる混合物は、チタンテトライソプロポキシドの代わりにチタンテトラノルマルブトキシドを用いた以外は、上述した（Ａ－１）混合物と同様の方法を用いて得た。
　これらの（Ａ－１）混合物と（Ａ－２）を、後述する水性樹脂組成物を製造する際に、添加したところ、乳化重合することができたので、これらが乳化重合用乳化剤として、作用し得ることがわかった。 (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. In an aqueous lactic acid solution, 115 parts by weight of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved at room temperature with stirring. Further, the mixture was heated and stirred at 70 ° C. to obtain a mixture (A-1).
(A-2) The mixture obtained by mixing titanium tetranormal butoxide, lactic acid and water was the same as the mixture (A-1) described above except that titanium tetranormal butoxide was used instead of titanium tetraisopropoxide. Similar methods were used.
When these (A-1) mixture and (A-2) were added in the production of the aqueous resin composition described later, they could be emulsion-polymerized, so that they act as emulsifiers for emulsion polymerization. I knew it could be.
　実施例１の水性樹脂組成物の製造
　攪拌翼、温度計及び還流冷却器を備えた４つ口フラスコに４１．８重量部の蒸留水及び０．５重量部の（Ｃ－１）界面活性剤（花王株式会社、ラテムルＷＸ（商品名））を加えた。窒素ガスを吹き込みながら攪拌し、液温を７０℃に保った。一方、５６．８重量部の蒸留水、５重量部の上述の（Ａ－１）混合物、２．５重量部の（Ｃ－１）界面活性剤（花王株式会社、ラテムルＷＸ（商品名））、６０重量部の（Ｂ－１）メタクリル酸メチル、３９重量部の（Ａ－３）アクリル酸ブチル、１重量部の（Ａ－５）γ－メタクリロキシプロピルトリメトキシシランからなる混合物、並びに０．６重量部の過硫酸アンモニウム及び３０重量部の水から成る水溶液を用意した。上述の混合物の約１０体積％と上述の水溶液の約５体積％の各々を上述の四つ口フラスコに加えて攪拌し、乳化重合を開始させた後、混合物の残部と水溶液の残部を同時に約２時間かけて四つ口フラスコに滴下して加えた。滴下終了後、更に液温を７０℃に保ちつつ約１時間半攪拌を続けた後、得られた反応混合物を室温に冷却した。アンモニア水を加えてｐＨを８に調整して水性樹脂組成物を得た。この水性樹脂組成物は、乳濁しているので乳濁液であり、従って、エマルジョン組成物である。表１に、得られた水性樹脂組成物の試験結果を示す。 Production of 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. On the other hand, 56.8 parts by weight of distilled water, 5 parts by weight of the above-mentioned (A-1) mixture, 2.5 parts by weight of (C-1) surfactant (Kao Corporation, LATEMUL WX (trade name)) , 60 parts by weight of (B-1) methyl methacrylate, 39 parts by weight of (A-3) butyl acrylate, 1 part by weight of (A-5) γ-methacryloxypropyltrimethoxysilane, and 0 An aqueous solution comprising 6 parts by weight of ammonium persulfate and 30 parts by weight of water was prepared. About 10% by volume of the above-mentioned mixture and about 5% by volume of the above-mentioned aqueous solution are respectively added to the above-mentioned four-necked flask and stirred to start emulsion polymerization, and then the remainder of the mixture and the remainder of the aqueous solution are simultaneously reduced to about It was added dropwise to the four-necked flask over 2 hours. After completion of the dropwise addition, stirring was continued for about 1 hour and a half while maintaining the liquid temperature at 70 ° C., and then the resulting reaction mixture was cooled to room temperature. Aqueous resin composition was obtained by adjusting the pH to 8 by adding aqueous ammonia. This aqueous resin composition is an emulsion because it is emulsified, and is therefore an emulsion composition. Table 1 shows the test results of the obtained aqueous resin composition.
　実施例２～５及び比較例１の水性樹脂組成物の製造
　各成分を表１のように変えた他は、実施例１と同様の方法を用いて水性樹脂組成物を製造した。得られた水性樹脂組成物の試験結果を表１に示す。
　比較例２
　各成分を表１のように変え、更に、（Ａ－１）混合物の代わりに（Ｄ－１）アナターゼ型酸化チタンの微粒子からなる光触媒材料（多木化学株式会社、タイノックＡ－６（商品名））を用いた以外は、実施例１と同様の方法を用いて水性樹脂組成物を製造した。得られた水性樹脂組成物の試験結果を表１に示す。
　比較例３
　表１に示される（Ｂ）成分及び（Ｃ）成分を用いて、実施例１と同様の方法で水性樹脂組成物を製造した。得られた水性樹脂組成物０．５重量部に（Ｄ－１）アナターゼ型酸化チタンの微粒子からなる光触媒材料（多木化学株式会社、タイノックＡ－６（商品名））を０．０５重量部加えて、比較例３の水性樹脂組成物を得た。試験結果を表１に示す。 Production of aqueous resin compositions of Examples 2 to 5 and Comparative Example 1 An 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.
　得られた、水性樹脂組成物の評価は以下の様に行った。
　１．重合性
　合成後の水性樹脂組成物の状態を、（Ｂ）重合性単量体及びそれに由来する重合体について注目して、目視で観察した。
　◎：（Ｂ）重合性単量体及びそれに由来する重合体の凝集、沈殿、分離等なく良好である。
　○：全体の３０％未満で（Ｂ）重合性単量体及びそれに由来する重合体の凝集、沈殿、分離などが見られる
　×：全体の３０％以上で（Ｂ）重合性単量体及びそれに由来する重合体の凝集、沈殿、分離などが見られる。 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.
　２．分散性
　合成後の水性樹脂組成物の状態を、（Ａ）混合物について注目して、目視で観察した。
　◎：（Ａ）混合物（主に、水溶性チタン）の凝集、沈殿、分離等なく良好である。
　○：全体の３０％未満で（Ａ）混合物の凝集、沈殿、分離などが見られる。
　×：全体の３０％以上で（Ａ）混合物の凝集、沈殿、分離などが見られる。 2. Dispersibility The state of the aqueous resin composition after synthesis was observed visually, focusing on (A) the mixture.
A: (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.
　３．光触媒機能：色素退色
　ガラス板上に５～１０μｍの厚さになるよう水性樹脂組成物を塗工し、１０５℃で５分間乾燥させて被膜を形成した。その後、０．１ｗｔ％のメチレンブルーのエタノール溶液の０．０５ｇを、被膜上に重ねて塗工し、室温で２時間放置した。この被膜及び色素を塗工したガラス板を１５ＷのＵＶランプで任意の時間照射した。ＵＶ照射の前後で、６６５ｎｍのＵＶ光の吸光度（Ａｂｓ）を分光光度計で測定した。ＵＶ照射前の吸光度を基準とするＵＶ照射後の吸光度（ＵＶ照射後の吸光度／ＵＶ照射前の吸光度）をメチレンブルー色素の未分解率とした。未分解率が低いほど、ガラス板上に形成された被膜によるメチレンブルー色素の分解が速い、即ち、被膜の色素分解に関する光触媒機能が高いことを意味する。
　◎：未分解率が４０％未満であり、大きな色素の退色が観察されており、被膜は優れた光触媒機能を有する。
　○：未分解率が４０％～６０％であり、色素の退色が観察され、被膜は光触媒機能を有する。
　×：未分解率が６０％より大きく、色素の退色は不十分であり、被膜の光触媒機能は小さい。 3. Photocatalytic function: Dye fading An aqueous resin composition was applied on a glass plate to a thickness of 5 to 10 μm 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 (absorbance after UV irradiation / 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 | dye is observed, and a film has the outstanding photocatalytic function.
○: 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.
　４．光触媒機能：接触角
　ガラス板上に５～１０μｍの厚さになるように、水性樹脂組成物を塗工して、１０５℃で５分間乾燥し、被膜を形成した。その後、このガラス板を１５ＷのＵＶランプにて任意の時間照射した。その後、この塗装板と水との間の接触角を接触角計にて測定した。接触角が小さいほど、光触媒機能が高いことを意味する。
　◎：接触角が１０度未満であり、被膜は優れた光触媒機能を有する。
　○：接触角が１０度～５０度であり、被膜は光触媒機能を有する。
　×：接触角が５０度より大きく、被膜の光触媒機能は不十分である。 4). Photocatalytic function: contact angle An aqueous resin composition was applied on a glass plate to a thickness of 5 to 10 μm 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: The contact angle is less than 10 degrees, and the coating has an excellent photocatalytic function.
○: The contact angle is 10 to 50 degrees, and the coating has a photocatalytic function.
X: A contact angle is larger than 50 degree | times and the photocatalytic function of a film is inadequate.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　比較例として例示していないが、実施例１～５に関して、（Ａ）混合物も（Ｃ）その他の乳化剤も使用しない場合、（Ｂ）重合性単量体を水性媒体中に乳化状態にすることができなかった。従って、（Ｂ）重合性単量体を乳化重合することができなかった。
　これに対し、表１の実施例４から、（Ａ）混合物を用いると、（Ｂ）重合性単量体を乳濁状態にすることができ、更に重合することもでき、その結果水性樹脂組成物を得ることができた。即ち、（Ａ）混合物は、乳化重合用乳化剤として作用し得ることが理解できた。 Although not exemplified as a comparative example, regarding Examples 1 to 5, when (A) neither a mixture nor (C) other emulsifier is used, (B) the polymerizable monomer is emulsified in an aqueous medium. I could not. Therefore, (B) the polymerizable monomer could not be emulsion polymerized.
On the other hand, from Example 4 of Table 1, when the mixture (A) is used, the polymerizable monomer (B) can be made into an emulsion state and can be further polymerized, and as a result, the aqueous resin composition I was able to get things. That is, it was understood that the mixture (A) can act as an emulsifier for emulsion polymerization.
　実施例１～５の水性樹脂組成物は、重合性及び分散性に優れ、得られる被膜の均一性と光触媒機能に優れており、総合的な性能が改善されている事が確認された。比較例１～３はその性能が不十分であり、総合的な性質に劣ることが認められた。 It was confirmed that the 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.
　本発明の水性樹脂組成物は、重合性、分散性に優れ、均一な被膜を形成することができる。更に、光触媒効果を有しており、防汚性を有する水性樹脂組成物として好適に使用することができる。 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.
　本発明は、塗工性、造膜性及び基材密着性に優れ、かつ長期間安定なチタン含有水性樹脂組成物を提供し、更に、高い光触媒機能が得られるにもかかわらず、均一な被膜を形成することができる水性樹脂組成物を提供する。
　［関連出願］
　尚、本出願は、２００８年１月１７日に日本国でされた出願番号２００８－７８０６を基礎出願とするパリ条約又は日本国特許法第４１条に基づく優先権を主張する。この基礎出願の内容は、参照することによって、本明細書に組み込まれる。 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.
[Related applications]
This application claims priority under the Paris Convention or Article 41 of the Japanese Patent Law, which is based on the application number 2008-7806 filed in Japan on January 17, 2008. The contents of this basic application are incorporated herein by reference.

Claims (5)

  1. 　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物を含む乳化重合用乳化剤。 (A) An emulsifier for emulsion polymerization containing a mixture obtained by mixing titanium alkoxide, organic acid and water.
  2. 　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合する水性樹脂組成物の製造方法。 (A) A method for producing an aqueous resin composition in which (B) a polymerizable monomer having an ethylenic double bond is polymerized in the presence of a mixture obtained by mixing titanium alkoxide, an organic acid and water.
  3. 　（Ａ）チタンアルコキシド、有機酸及び水を混合することによって得られる混合物の存在下、（Ｂ）エチレン性二重結合を有する重合性単量体を重合することで得られる水性樹脂組成物。 (A) An aqueous resin composition obtained by polymerizing a polymerizable monomer having an ethylenic double bond in the presence of a mixture obtained by mixing titanium alkoxide, an organic acid and water.
  4. 　（Ｂ）エチレン性二重結合を有する重合性単量体は、アルコキシシリル基を含有し、エチレン性二重結合を有する単量体を含んで成る請求項３に記載の水性樹脂組成物。 (B) The aqueous resin composition according to claim 3, wherein the polymerizable monomer having an ethylenic double bond comprises an alkoxysilyl group-containing monomer having an ethylenic double bond.
  5. 　チタンアルコキシドが、チタンテトライソプロポキシドである請求項３又は４に記載の水性樹脂組成物。 The aqueous resin composition according to claim 3 or 4, wherein the titanium alkoxide is titanium tetraisopropoxide.
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JP5734045B2 (en) * 2011-03-25 2015-06-10 東海旅客鉄道株式会社 Photosensitive metal alkoxide, coating liquid, and method for forming patterned film
JP6107352B2 (en) * 2013-04-12 2017-04-05 三菱化学株式会社 Dye for anisotropic dye film, composition containing the dye, anisotropic dye film and polarizing element

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JPS5398393A (en) * 1977-02-09 1978-08-28 Teijin Ltd Production of polyester
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WO2005094978A1 (en) * 2004-03-18 2005-10-13 Gifu University Composition for dispersing of particle, composition having particle dispersed therein, process for producing the same, and sintered compact of anatase titanium oxide

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JPS5398393A (en) * 1977-02-09 1978-08-28 Teijin Ltd Production of polyester
WO2004031258A1 (en) * 2002-10-03 2004-04-15 Toray Industries, Inc. Polyester resin compositions, catalyst for polyester production, polyester film, and magnetic recording medium
WO2005094978A1 (en) * 2004-03-18 2005-10-13 Gifu University Composition for dispersing of particle, composition having particle dispersed therein, process for producing the same, and sintered compact of anatase titanium oxide

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JP2018059007A (en) * 2016-10-06 2018-04-12 株式会社日本触媒 Resin composition

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