WO2010140501A1 - Nouveau monomère d'acide titanique et polymère à base de celui-ci, procédé de production du monomère et du polymère, et utilisation du monomère et du polymère - Google Patents

Nouveau monomère d'acide titanique et polymère à base de celui-ci, procédé de production du monomère et du polymère, et utilisation du monomère et du polymère Download PDF

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WO2010140501A1
WO2010140501A1 PCT/JP2010/058759 JP2010058759W WO2010140501A1 WO 2010140501 A1 WO2010140501 A1 WO 2010140501A1 JP 2010058759 W JP2010058759 W JP 2010058759W WO 2010140501 A1 WO2010140501 A1 WO 2010140501A1
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polymer
agent
acid monomer
acid
monomer
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賢次郎 牧野
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Makino Kenjiro
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule

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  • the present invention relates to a novel titanic acid monomer and polymer, a method for producing the same and uses thereof. More specifically, a protective group is formed on a polyvalent metal typified by titanium, a water-soluble transparent monomer is synthesized, and this monomer is used as a basic raw material to form phosphoric acid, a water-soluble phosphate compound, and a chelate. Reagents Trialkylphosphine oxides or chelating ion exchange resins, such as anion exchange resins, are used for chain transfer polymerization to form transparent polymers, and monomers are used as undercoat agents, brightening agents, self-cleaning agents, and adhesives.
  • the polymer Used as an anti-wear / heat-resistant brightening agent, etc., and the polymer is used as an active catalyst from the dark to the ultraviolet, and the polarity can be freely selected according to the polarity and amount of addition of the chain transfer agent.
  • the equivalent mole when the equivalent mole is used, the activity in the dark is maximized, but it is used for an undercoat agent or a dark catalyst that is less active under ultraviolet light.
  • titanium is a term indicating “a titanic acid monomer having a protecting group and a polymer obtained by chain transfer polymerization”.
  • titanium compounds are mostly in the form of particles (cubic crystals, etc.), and use several nano-50 nanometers to provide glass transparency and antifouling agent (hydrophilic film with a contact angle of 5 degrees or less).
  • Patent Document 1 Japanese Patent Laid-Open No. 10-314598
  • large particles of 50 to 300 nanometers have been used as a photoactive catalyst, dispersed in water, or as a powder, using an adhesive or an undercoat agent. It was.
  • Patent Document 3 Japanese Patent Laid-Open No. 9-714178
  • Peroxide groups exposed on the surface of titanium oxide particles with low activity that is, titanium oxide fine particles, which have been reduced mainly by the activity, are reduced and returned to hydroxyl groups. It seems that either re-agglomerated coarse particles, white flower, or falling off (amorphous peroxytitanate film ⁇ reduction ⁇ titanium hydroxide granular crystal ⁇ white flower ⁇ dropping).
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2004-130195
  • Patent Document 5 Japanese Patent Application No. 2001-111097
  • titanium tetrachloride forms a 1-50 nanoparticle as a titanium oxide of 2% or less, and reacts with IPA.
  • the titanium hydroxide end groups (titanic acid ends) generated on the surface of the particles form an (isopropyl alcohol and protective colloid) system, which is an almost transparent liquid, but this is only a few nano to several tens of nano particles.
  • Hydroxyl group on the surface is a protective colloid, and at the same time adding phosphoric acid, chelating reaction with strong phosphoric acid Then, phosphoric acid binds to hydroxyl groups (titanic acid groups) that exist only on the surface of the titanium oxide crystal particles and precipitates into large particles (precipitates when 100 to 400 nanoparticles are allowed to stand).
  • phosphoric acid binds to hydroxyl groups (titanic acid groups) that exist only on the surface of the titanium oxide crystal particles and precipitates into large particles (precipitates when 100 to 400 nanoparticles are allowed to stand).
  • Shake the solution uniformly, apply it to glass, measure the activity by baking at 700 ° C., apply the separated emulsion to the body, measure the activity, and sell it as titania phosphate, For use at room temperature, it is difficult to use because it separates and precipitates, and it is not widespread.
  • the supernatant liquid is sold as transparent titania phosphate, it has been found that it contains almost no titanium, is close to the phosphoric acid liquid, and the deodorizing effect in the dark is chemical adsorption by phosphoric acid. Therefore, these titanias often expire in about three months, and the disadvantages as particulate titania have not been solved.
  • the reaction product of alcohol and titanium tetrachloride is claimed to be used, but since it is not indicated in the examples,“ high concentration of methoxytitanium forming a protecting group ”of the present invention.
  • an ⁇ acid water-soluble transparent liquid '' and since the alcohol is ⁇ ethanol or isopropyl alcohol is preferred '', ⁇ addition of methanol tetrahydrochloride or alkoxytitanic acid to methanol and hydrochloric acid or methanol without adding water
  • methoxytitanic acid monomers with high concentration of protecting groups dissolve infinitely in water, and dissolve in water and organic solvents as well as monomers that dissolve in hydrophilic and lipophilic solvents such as alcohol and xylene
  • the invention of “a high concentration polymer” has not been achieved.
  • the obtained titania phosphate compound is composed of a hydroxytitanic acid group and a phosphoric acid compound exposed on the surface of a condensate of alkoxyhydroxytitanate Ti (OH) 4 (OR) 4 , alkoxy and hydroxytitanic acid.
  • Protective colloid titanic acid due to the strong protective colloid action of alcohol, especially isopropyl alcohol, and “cannot form alkoxytitanic acid in water”. This is because it is common sense that alkoxytitanic acid is hydrolyzed to titanium hydroxide when exposed to water.
  • Patent Document 6 Japanese Patent Laid-Open No. 2005-82863
  • the protective colloid liquid before adding phosphoric acid is It is only 0.5%, and at the stage of adding phosphoric acid, a precipitate is formed and the filtrate supernatant is filtered and used as a titania metal phosphate composite for membranes.
  • titania phosphate It is extremely small compared to metal and phosphoric acid, and it is difficult to analyze in the same order, so it does not deserve the expression titania phosphate.
  • titania phosphate since it is a compound of a titanium catalyst poison such as sodium, it cannot explain the argument that it is the activity of titania phosphate in light and dark places.
  • Patents and other patents of NITTO TECHNOLOGY CO., LTD. Are hydrated by condensation polymerization of alkylsilane (alcooxirane), etc., and photoactive titanium oxide fine particles are added to it to make the surface of titanium oxide particles porous.
  • colloidal protection does not hurt the substrate (although products from similar companies are on the market), it is the formation of a film with titanium particles and adhesive members, hindering the activity of titania The factor to do is inevitable.
  • Patent Document 1 Japanese Patent Laid-Open No.
  • Patent Document 7 Japanese Patent Laid-Open No. 9-16418
  • Patent Document 8 Japanese Patent Laid-Open No. 2005-104817 used by impregnating a ceramic powder porous body with a titanium phosphate solution and drying it. Not what you want.
  • Patent Document 9 Patent No. 9 of the National Institute of Advanced Industrial Science and Technology
  • JP-A-2008-72003 the Japan Sheet Technology Research Laboratory
  • apatite may be dissolved by acid rain, the outer wall cannot be withstood for a long period of time, and it does not change the use of titania in which the crystals are granular, and does not solve the disadvantages of known titania. .
  • Fujishima the world's first discoverer of titania / Mr. Fujishima, who made the Nissan effect the world's first, is a technology jointly developed by JR Tokai (Patent Document 10: Application of JP2008-72003 or similar technology) Asahi Shimbun was released on April 4, 2008, but as the technology clearly states, known titania can only be particulate titania, it cannot be used for a long time due to dropout, and many undercoat agents have been developed. However, in all cases, the adhesive is not permanent, but it is said that self-cleaning can be maintained permanently by undercoating niobium.
  • titania Patent Document 11: Japanese Patent Laid-Open No. 2002-104876
  • This plate-like titania is coated with a titania phosphate phosphate emulsion developed by Osaka City Institute of Technology and YO Corporation, and is heated and baked at high temperatures.
  • the polarity cannot be freely changed from superhydrophilic to superhydrophobic, and even if a plate-like crystal solution can be prepared and applied using a dispersant, all phenomena of peeling due to stress distortion can be observed. It cannot be solved by the surface of the substrate.
  • Patent Document 12 Japanese Patent Laid-Open No. 11-228140 proposes titania fiber, but its production method and apparatus are complicated, and the titanate polymer of the present invention is spun as it is, This technology can be coated on any surface like a synthetic paint, can form a film for hydrophilic paints and lipophilic paints, and has a function to chemically bond with active groups present on almost all coated surfaces It is not worth comparing with.
  • Patent Document 13 Japanese Patent Laid-Open No. 2005-97395 uses a crystalline titanium phosphate in Patents of anticorrosive pigment composition and Patent Document 14 (Japanese Patent Laid-Open No. 6-55075). An aqueous titanium phosphate solution is not used and is not specified.
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2005-104817 has a “solution containing a titanim phosphate compound”, but its synthesis method, composition, content, mixing ratio of phosphoric acid and titanium, etc. are not clearly stated. It is assumed that it is a slurry-like composition or supernatant similar to the type or YOO type (Patent Document 4: Japanese Patent Application Laid-Open No. 2004-130195, Patent Document 15: Japanese Patent Application Laid-Open No. 2001-111097), and can take the region of granular titania. I don't think so.
  • titanic acid compound such as alkoxy titanic acid, peroxytitanic acid, titanium phosphate, etc.
  • synthesis technique and its polymerization mucus with 2% or more monomer (2% for Saga type)
  • monomer 2% for Saga type
  • titania can be formed only in granular form, and fine particles of 1 to 50 nanometers are used for self-cleaning to form a hydrophilic surface, but photoactivity is low, and opaque sols of 50 to 300 nanometers and emulsion forms are light. Although it showed activity, the adhesiveness was inferior, and even if an adhesive was used, whitening occurred due to falling off, erosion of the base material, and deterioration, and long-term performance could not be maintained.
  • titania phosphate shows dark activity, but the transparent liquid contains almost no titanium, and sol titania phosphate is adhered at room temperature with a coating agent.
  • Saga-type peroxytitanic acid is considered to be 1 to 50 nano particles. It was announced that the technology to pulverize down to 7 nanometers was achieved, but it is not comparable to a monomer or linear polymer with a primary size of 10 to 20 angstroms (1 to 2 nanometers) and transparent. Even so, it is a particle aggregate, and its activity disappears in half a year to a year.
  • Patent Document 16 Japanese Patent Laid-Open No. 2006-206855
  • Patent Document 17 Japanese Patent Laid-Open No. 2006-56866
  • Patent Document 18 Japanese Patent Laid-Open No. 2005-15497
  • Matsumoto Pharmaceutical Co., Ltd. has proposed a technology for synthesizing water-soluble oligomers by reacting alkoxytitanic acid with aliphatic amines, oxyacids, glycols, and silicon alkyls.
  • the acid groups are sealed with a reaction reagent that does not volatilize at room temperature and pressure, and polymerize.
  • a reaction reagent that does not volatilize at room temperature and pressure, and polymerize.
  • Water-soluble resol resin varnish
  • condensation polymerization of phenol resin, melamine resin, and urea resin Condensation oligomers of the 4-sensitive titanate groups, rather than thickening and gelatinizing while forming a linear polymer.
  • Patent Document 19 Japanese Patent Application Laid-Open No. 2008-156280 discloses that alkoxytitanic acid reacts with a chelating agent that does not easily evaporate at room temperature and normal pressure to react with alcohol or form a protective colloid.
  • a method of performing a hydrolysis reaction that is, an oligomer having a hydroxyl group
  • the alkoxytitanic acid formed similar to the YOO patent, has a titanium hydroxide group and is a transparent aqueous solution. Even if it is obtained, the concentration is very small, and it is clear that it forms a completely different molecular composition and structure from the present invention, regardless of whether it is a titanate particle condensate.
  • Patent Document 20 Japanese Patent Application Laid-Open No. 3-1264673 discloses a condensation polymerization in which a chelate is formed with titanic acid and acetaldehyde or octylene glycol (immediately before the gelation insolubilization is caused by polymerizing a multi-sensitive group). Polymerization is used under the condition of stopping, but it is applied to the glass surface and heated at 300 ° C., and it is a heat ray reflective glass manufacturing method. This patent can be used for the same application at room temperature and cannot withstand high temperatures. Since it can be applied to glass, it is not worth comparing.
  • Patent Document 21 Japanese Patent Application Laid-Open No. 2004-182960 proposes a water-soluble compound of a mixture of a titanium compound, a chelating agent and a phosphoric acid compound.
  • the present invention and its object, efficacy, composition, The molecular structure and reaction mechanism are different and do not harm the present invention.
  • a protective group is already formed, and the linear polymer is glued by using this as a chain transfer catalyst without using a chelate bond or a titanium phosphate bond. It is a technology that synthesizes polymers up to the end, dissolves infinitely in water, and provides a transparent liquid that dissolves in organic solvents. The mechanism of the reaction, the spirit, the structure, function, efficacy, and use of the substance of the present invention. It is not something that can be differentiated, and is not comparable.
  • the product of the present invention can be decontaminated and moss-free just by applying directly, high-concentration monomer, polymer synthesis, complete water-solubilization, free activity selection from dark to ultraviolet, hydrophilic -Design freely to hydrophobicity, sharing of glitter, transparency and catalytic activity, water forming protective groups after coating dehydrates, and after film formation, heat, ultraviolet rays, chelating agent, hydrogen peroxide and intramolecular activity Demethylated, activated by post-crosslinking to form titanium oxide network bonds and titanium phosphate bonds, spinning, film molding, natural and synthetic polymers with active ends, and those with chemically active groups on inorganic surfaces There is no titania having a wide range of functions such as reaction modification, electromagnetic wave protection, superconductor, chemical catalyst, and ultraviolet blocking.
  • the present invention solves all of these problems, provides a monomer that has excellent adhesion to all substrates, is synthesized at a high concentration, is infinitely soluble in water, and is transparently soluble in organic solvents. Ions, titanate ions) and methanol and hydrochloric acid or in the presence of hydrogen peroxide and hydrochloric acid, hydrogen peroxide and methanol, chelating agents that form chelates with these monomers, and ion exchange of hydrochloric acid An anion exchange resin that forms a chelate is not used as a chelating agent, but as a chain transfer catalyst, and is subjected to chain transfer polymerization to synthesize a linear polymer.
  • the novel titanic acid monomer and polymer production method of the present invention are: (1) Pure alkoxy titanic acid in a system in which excess alcohol without adding water and a productivity of 2% or more, preferably 15 to 35% of mineral acid coexist with 1/2 mol or more of titanic acid. Adding a monomer or adding titanium tetrachloride to an excess of alcohol without adding water to synthesize an alkoxytitanate monomer having a protective function, or 30% or more of excess hydrogen peroxide without adding water, Preferably, peroxytitanic acid monomer or peroxy acid formed by adding titanium tetrachloride or excess hydrogen peroxide without adding water and pure alkoxy titanic acid monomer to the alcohol system to form a protective function.
  • the alkoxy titanic acid monomer or peroxy titanic acid monomer or peroxy Tokishichitan acid monomer (hereinafter, referred to peroxy titanic acid monomers) in a dilution step of diluting adding an alcohol, especially methanol without adding or water to dilute hydration reaction by adding water, if the polymerization concentration, (3) after the dilution step, adding a chain transfer catalyst containing an ion exchange resin, and polymerizing from a low molecular weight polymer to a polymer reaching a transparent gelation point; (4) a step of demineralizing a polymer polymerized with a chain transfer catalyst with an ion exchange resin; (5) after ion exchange polymerization, adding phosphoric acid or alkylphosphoric acid to form a complex; (6) adding a hydrogen peroxide having a 1 ⁇ 2 molar value or less to 1 mol of titanic acid to the hydrated monomer or
  • the present invention is an alkoxy titanic acid monomer or a peroxy titanic acid monomer obtained by the steps (1) to (2).
  • the present invention is a novel titanic acid polymer obtained by the steps (1) to (4).
  • the excess alcohol is methanol or ethanol and the mineral acid is hydrochloric acid.
  • the excess alcohol is methanol.
  • the present invention is in contact with a chelating agent such as ultraviolet rays, heating and a phosphoric acid compound or hydrogen peroxide in order to show immediate light activity under measurement conditions (short time) by JIS method.
  • a chelating agent such as ultraviolet rays, heating and a phosphoric acid compound or hydrogen peroxide in order to show immediate light activity under measurement conditions (short time) by JIS method.
  • the chelating agent is a phosphate compound or an anion exchange resin.
  • the excess alcohol and the mineral acid coexist with the alkoxy titanic acid monomer from a half-valence mole to an equivalent or less.
  • a compound that contains phosphoric acid, trimethyl phosphoric acid and alkali as a catalyst poison and reacts with the alkoxy titanic acid group of the methoxy titanic acid monomer or polymer in order to prevent degradation of the organic substrate due to the photocatalytic activity It is preferable to further include a coating step in which an acid, an alkali phosphate compound, or a methyl silicate alkali phosphate compound is undercoated and a titanic acid monomer or polymer is applied thereon.
  • the alkali contains sodium and potassium.
  • the alkoxy titanic acid monomer is added with water-free titanium tetrachloride in alcohol without water or alkoxy titanic acid with water-free alcohol at least 2%, preferably 15-35% mineral acid.
  • titanium tetrachloride with no addition of water to 30% or more, preferably 50% or more of hydrogen peroxide without addition of water, or alkoxytitanic acid with water. It is preferably synthesized by a method in which 30% or more, preferably 50% or more of hydrogen peroxide and alcohol are not added.
  • a catalyst from non-light to ultraviolet a titania phosphate film forming agent, peroxyphosphoric acid Titania film-forming agent, intramolecular self-activator, burnt and seizure release agent, PVC cross-linked titania, surface polarity conversion agent, acid-resistant titanium film-forming agent, electromagnetic wave protective agent, superconducting agent, fiber / thread and plastic
  • Anti-static, anti-wear, heat-resistant, bright, highly hydrophilic and highly lipophilic surface treatment agent, lipophilic and hydrophilic coating film forming agent, moss remover, moss preventive, fungicide, fungicides Agent molded product of titanic acid yarn or film, deodorant, NOX-SOX immobilization catalyst, barium titanate synthesis agent for ceramic capacitors, water-soluble chelating agent insolubilizing agent (solidifying agent), clean Agents
  • a catalyst from non-light to ultraviolet a titania phosphate film forming agent, Peroxyphosphate titania film forming agent, intramolecular self-activator, burnt and seizure release agent, PVC cross-linked titania, surface polarity conversion agent, acid-resistant titanium film forming agent, electromagnetic wave protective agent, superconducting agent, fiber / thread Antistatic, plastic, anti-wear, surface treatment agent for imparting wear resistance, heat resistance, brightness, high hydrophilicity and high lipophilic surface, film forming agent for lipophilic and hydrophilic coatings, moss remover, mossproofing agent, fungicide, Antibacterial agent, fungicidal agent, antifungal agent, titanic acid thread or film molding, deodorant, NOX-SOX immobilization catalyst, barium titanate synthesis agent for ceramic capacitors, aqueous transesterification catalyst,
  • the water-soluble alkyl phosphate ester is methyl phosphate, ethyl phosphate, isopropyl phosphate, butyl phosphate and volatile phosphate compounds.
  • This monomer can be chain transfer polymerized to be freely designed to polar and dark activity / light-inactive darkness and light-active darkness inactive / light-active.
  • the activity and polarity By selecting the activity and polarity by simply changing the same, it can be controlled freely, and the whiteness due to peeling due to different affinity (polarity) with the base material, whiteness due to deterioration of the base material, titanium Protects white flower by granulation of acid monomer and polymer (titanium oxide, titanium hydroxide), has chemical bond with the base material, makes the film's strength stability permanent, from dark to under light Active and bright, antifouling, self-cleaning, electromagnetic and electrical Such as Noh and corrosion protection function can be permanently maintained.
  • acid monomer and polymer titanium oxide, titanium hydroxide
  • Example 11 shows the decomposition rate of gas at the time of irradiating with an ultraviolet lamp.
  • Example 11 using 110 degreeC / 2Hr process and the test piece which carried out the phosphoric acid process, it puts into the JIS method tetra bag, and shows the result of having measured the activity in a dark place, and the activity when an ultraviolet lamp is applied. It is a graph.
  • 2% of Saga-type titania TA and Ishihara-type titania STS-01 were applied to a test piece as a comparative example, and 20 ° C.
  • Example 28 It is a graph which shows the result of having test-dried 100 ppm of acetaldehyde by the tetrabag method after hold
  • Example 28 it is a graph which shows the result of having measured the production amount of CO (carbon monoxide) for every time.
  • Example 29 it is a graph which shows the result of having measured the density
  • Example 30 it is explanatory drawing which shows the result of having experimented about the method of selecting affinity for a base surface.
  • 4 is an IR chart of TIPT-MC 2 -P 6 .
  • 3 is an IR chart of TIPT-MC 2 -PM20. It is an IR chart of a YO type suspension. It is an IR chart of Ishihara type STS-01.
  • the “pure” alkoxy titanic acid monomer in the present invention refers to those commercially available for industrial use.
  • the present invention solves the disadvantages of the publicly known titania listed above, reveals a function in which the contact portion applied to the base does not show activity, and the portion that comes into contact with air after application is activated by light. Where there is no activity, the active site of the binding active group formed in the molecular structure shows its own activity and develops its activity over time, and its activity is very small immediately after application (especially JIS).
  • the tetrabag method is small, and the methylene blue erasing method and the erasing activity such as green moss are also moderately) monomers and polymers having protecting groups.
  • the possible mechanism of the activity is an alkoxy titanate group, a phosphate titanate complex (When the peroxytitanic acid group, peroxyphosphoric acid titanic acid complex) or alkoxyphosphoric acid titanic acid complex is applied and dehydrated and dried, the protective group is destroyed and dealkoxy is removed.
  • an active site that generates intramolecular activity is generated by the redox potential of the anode / cathode and yellow phosphorus / red phosphorus generated between the titanium phosphate bonds. Inferred.
  • Undercoat agent titania which is a monomer having a protecting group as a basic base of the present invention, or an undercoat agent in which a catalyst poison and a chelating agent coexist on a base that is easily decomposed (phosphoric acid and sodium silicate (polar),
  • phosphoric acid and sodium silicate (polar) phosphoric acid and sodium silicate (polar)
  • the underlying titania or a compound that binds to titania and titania having an active site is not affected by the self-intramolecular active factor (group) or light.
  • the one-dimensional assumed film thickness is 7 nano particles of Saga as the smallest particles of known granular titania
  • This titania is a linear polymer of 10 to 20 angstroms (1 to 2 nanometers) and is considered to be 1/10 to 1/100 compared to the known one.
  • the polarity can be freely adjusted and converted, so it can be applied to any surface, imparts any polarity surface, and is an ultra-fine network (opposite to particulate titania fine particles) that transmits light and shines.
  • Titanium film-forming agent can provide long fibers that were impossible until now, and can form a mesh-like cloth / film by cross-linking.
  • Titanium film-forming agent electromagnetic wave protective agent, superconducting agent, antistatic of fibers, yarns and plastics, surface treatment agent that imparts abrasion resistance, heat resistance, radiance, high hydrophilicity and high lipophilic surface, lipophilic and hydrophilic paint Film forming agent, moss remover, anti-mossant, antibacterial agent, antibacterial agent, fungicidal agent, anti-fungal agent, titanic acid thread or film molding, deodorant, NOX-SOX immobilization catalyst, for ceramic capacitors Barium titanate synthesis agent, water-based transesterification catalyst, CO 2 , H 2 O decomposition catalyst, particulate titania binding adhesive, polysaccharide hydrolysis catalyst, rust preventive, wood antiseptic ant, pesticide, fish culture , Anti-fouling / anti-fouling (self-cleaning G)
  • Titanium is tetravalent, and it should be noted that it is impossible from chemical theory to create a transparent titanium aqueous solution, even an organic solvent solution, as a single compound of titanic acid, regardless of the chemical reaction. If this can be made possible, the impossible will become possible, and the known theory will be overridden.
  • the literature “Agne 1965 1st edition As a result of examining the composition in which the titanium compound eluted as a transparent aqueous solution is applied to the surface to be coated and evaporated to form a film of titanium oxide and a titanium compound.
  • Titanium tetrachloride or alkoxytitanic acid compound water is not added, (a) concentrated hydrogen peroxide or (b) concentrated hydrogen peroxide and alcohol (methanol) or (c) hydrochloric acid and alcohol (methanol)
  • (a) “peroxytitanic acid”, (b) “peroxyalkoxytitanic acid”, and (c) “alkoxytitanic acid”, which is a monomer compound having a transparent protective group cannot be known (titanium It was possible to synthesize the acid monomer at a high concentration from 2% or more (the highest concentration of the Saga type) up to the highest concentration of methanol to a concentration close to the equimolar value of titanic acid.
  • titanium tetrachloride used as a raw material is 8% or less, it is precipitated as titanium oxide having a white titanium hydroxide (hydroxytitanic acid) group on the surface and cannot be dissolved in water. It is in. It is also known that alkoxytitanic acid does not dissolve in water at all and can be hydrolyzed to the same.
  • Saga-type peroxytitanic acid has 8% or more of titanium tetrachloride added to 1% water and hydrated to form the hydroxytitanic acid sol, and hydrogen peroxide is added to it, resulting in low photoactivity.
  • a transparent liquid is formed, and this is heated at 90 ° C. or less for a long time (nearly 10 hours of 1% transparent peroxytitanic acid (perhaps not orthotitanate peroxide) and becomes active at 2%. However, when it exceeds that, it is concentrated and heat treated to provide transparent, photoactive peroxytitanic acid particles having a limit of 2%.
  • the peroxytitanic acid monomer and alkoxyperoxytitanic acid monomer obtained in the present invention are not present as transparent compounds, and do not exist at a high concentration (the highest value tested is a small excess of alcohol or hydrogen peroxide (alkoxytitanic acid or When titanium tetrachloride (1 mole, tetravalent) is 1 mole, alcohol or hydrogen peroxide is 4 moles (1 mole of titanic acid) + ⁇ , that is, ⁇ is an evaporation decomposition loss of methanol or hydrogen peroxide.
  • the synthesized peroxy titanic acid monomer and alkoxy titanic acid monomer are highly pure tetramethyl titanic acid (c) with very little content of titanium oxide bonds and titanium hydroxide (hydroxytitanium) groups.
  • titanium metal is stabilized by the dissolution of titanium ions, which are dissolved in water indefinitely.
  • the formation of titanium hydroxide (hydroxytitanic acid) groups exposed on the surface of the particles coincides with the fact that titanium metal is immobilized by forming an oxide film (titanium oxide and titanium hydroxide).
  • chelating agents and ion exchange resins act on the protecting groups in (a), (b), and (c), and the protecting groups liberate hydrochloric acid and hydrogen peroxide, adding the chelating agent while opening the ring.
  • this chelating agent is detached, an alkoxy group or a peroxy group remains and grows into a linear polymer.
  • the mechanism of this polymerization is considered to be that the chelating agent does not form a chelate, the ion exchange resin does not form a chelate with titanic acid, and acts as a chain transfer polymerization catalyst to form chain transfer polymerization.
  • reaction system (c) I [Chemical Formula 3] is as follows. It is also conceivable that the hydration protecting group stabilized on the monomer may be as shown in Formula 3.
  • the chain transfer catalyst is not limited to phosphoric acid or a phosphoric acid compound and an ion exchange resin, but the object of the present technology is to generate a redox potential at the point of attachment of titanic acid and phosphoric acid,
  • the examples were limited to phosphate compounds
  • a compound that forms a chelate with a titanium ion including a method of adding a phosphate compound after chain transfer polymerization using an ion exchange resin, the same chain transfer polymerization is performed, and the present invention is described in detail.
  • phosphoric acid with the most polar chain transfer catalyst forms the most hydrophilic film, and when phosphate ester that shifts to non-polarity with a large alkyl group is used, it forms a film with low polarity and is hydrophilic.
  • the surface to be coated can be freely designed so that a hydrophilic product can be used and a hydrophobic (small polarity) product can be used on the lipophilic (water repellent) coated surface.
  • “exfoliation whiteness” that does not match the polarity does not have to worry about “exfoliation whiteness” because a coating test with the surface to be applied is performed and a grade that matches the polarity uniformly can be selected.
  • the most important thing is “erosion white flower”, but it can be obtained by using an alkoxytitanic acid monomer or ion exchange polymerization with a protective group that does not contain phosphoric acid, even if a dark type containing excessive phosphoric acid is used.
  • “erosion whiteness” may occur depending on the chemical composition of the coated surface (the surface of the coating film that is susceptible to oxidative degradation).
  • the titanate compound of the present invention When using an undercoat agent (alkoxyphosphate alkali silicate (lipophilic for nonpolarity) or alkali phosphate silicate (polarity for hydrophilicity)) containing Na and K, which chemically binds and becomes a catalyst poison of titania. Both “exfoliation whiteness” and “erosion whiteness” do not occur, and a longer-term stable film and activity can be maintained.
  • undercoat agent alkoxyphosphate alkali silicate (lipophilic for nonpolarity) or alkali phosphate silicate (polarity for hydrophilicity)
  • Protective groups are stable in the presence of excess alcohol, water, hydrogen peroxide, and hydrochloric acid, but these reactions are accelerated when water or alcohol evaporates to dryness to form a film.
  • the JIS tetratobag method shows a higher value than the concentration of acetaldehyde injected as a source of odor, and decreases with time, completely decomposing and disappearing alkyl groups in the molecule, and also acetaldehyde decomposes. I found out.
  • the peroxy titanic acid monomer like the unheated grade used as an undercoat agent for Saga type peroxy titanate, has little photoactivity, so it can be used as an undercoat agent. Compared to particles of Saga type, this technology is far superior because it is a monomer at a single molecule level.
  • Saga type undercoat agent manufactured by Tio-Techno
  • TK condensation polymerization of granular titania with phosphoric acid compound
  • the activity of Saga type is markedly reduced in 2 to 3 months after application (Saga type has the activity of being a particle type, and the brightness is reduced).
  • Saga type has the activity of being a particle type, and the brightness is reduced.
  • the reason why it falls slightly and the brightness does not change is because it is a linear polymer, and the decrease in activity is thought to correspond to the decay of the oxidizing power of the peroxy group in the reduced portion.
  • the peroxy titanic acid polymer of the present invention is considered to form a titanium oxide bond as the protective group is destroyed by coating and drying dehydration and the coating film elapses.
  • this polymer is extremely high in stringiness (spinnability), excellent in moldability, and elastic by using a solution that forms a protective colloid with titanic acid such as IPA (isopropyl alcohol), or by spinning in hot air. It is possible to form a stretchable yarn and form it into a film by inflation or the like, and applications such as conductive fibers and electromagnetic wave control films are expected.
  • IPA isopropyl alcohol
  • peroxyalkoxy titanate monomers synthesized without using hydrochloric acid or mineral acids, ion exchange polymerized alkoxy titanate polymers, and polymers ion-exchanged after chain transfer polymerization are non-chromium required for automobiles, etc. It has been found that it can be used as an alternative to plating rust preventives, dry lubricants, titanium lining agents and the like.
  • the novel titanic acid monomer and polymer production method of the present invention are: (1) Addition of commercially available alkoxytitanic acid monomer to a system in which excess alcohol, especially methanol, and mineral acid, especially hydrochloric acid coexist without adding water, or titanium tetrachloride in excess alcohol without adding water And adding titanium tetrachloride to a step of synthesizing an alkoxytitanic acid monomer having a protective function or excess hydrogen peroxide (commercially 30% or more, preferably 50% or more reagent) without adding water.
  • a protective function or excess hydrogen peroxide commercially 30% or more, preferably 50% or more reagent
  • a dilution step of diluting with a soluble organic solvent (4) After the dilution step, an ion exchange resin or a chain transfer polymerization catalyst is added to polymerize from a low molecular weight polymer to a transparent gelation point; (5) After the above-described polymerization step without ion exchange, it is dissolved in excess water as it is and passed through an ion exchange tower, or an ion exchange resin is dispersed in excess water, and the polymer is dissolved and ion exchanged.
  • a dissolution step of filtering, desalting and applying to the coating (6) adding 0.5 mol or less of hydrogen peroxide to 1 mol of titanate group to a hydrated monomer or polymer to form methyl peroxytitanate (alkyl); (7) It is characterized by comprising a dissolving step in which it is dissolved in excess water or an organic solvent and completely dissolved in order to be applied after the polymerization step.
  • the step of I is a protective function forming step in which an alkoxytitanic acid monomer, an excess alcohol, particularly methanol, and a mineral acid, particularly hydrochloric acid, coexist to form a protective function on the functional group of the alkoxytitanic acid monomer.
  • III or hydrogen peroxide, methanol and alkoxytitanic acid coexist to form a protective function.
  • the excess alcohol methanol, ethanol or a mixture thereof can be used, but methanol is preferably used from the viewpoint of the stability of the protecting group.
  • the amount of the excess alcohol is an equivalent mole or more with respect to alkoxytitanic acid or titanium tetrachloride, and preferably a little excess or more is necessary for the stable formation of protecting groups, and hydrochloric acid or hydrogen peroxide is used.
  • the alkenyl titanic acid monomer has a valence of at least 1 ⁇ 2 valence to the equivalent.
  • the protective group formation becomes unstable, branching reaction, hydroxytitanium group, titanium oxide bond and titanium phosphate cross-linking occur in the next polymerization step, resulting in cloudiness and precipitation.
  • it becomes difficult to obtain a molecular transparent body and when exceeding the equivalent, it becomes stable as a monomer and chain transfer polymerization becomes difficult, and when heated, polymerization occurs, but linear transfer polymerization hardly occurs, and branch polymerization and cloudy precipitation occur. Therefore, there is a problem that the polymerization is difficult to control.
  • hydrochloric acid As the mineral acid, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, odorous acid, and the like can be used, and hydrochloric acid is preferably used from the viewpoint of the formation stability of the protecting group.
  • the alkoxytitanic acid monomer is added to titanium tetrachloride or alkoxytitanic acid, alcohol without adding water, and a work, productivity of 2% or more, preferably 35% to 10% mineral acid, or It is preferable to synthesize titanium tetrachloride or alkoxytitanic acid by a method of adding hydrogen peroxide without adding water or hydrogen peroxide and alcohol without adding water.
  • the reason for this is not to limit the water content of titanium tetrachloride, hydrogen peroxide, and alcohol used as raw materials, but commercially available industrial products may be used without adding water (hydrogen peroxide is 30%). Or more, more preferably 50% or more, and particularly preferably 70% or more).
  • the functional group of the alkoxy titanic acid monomer may have a protective function as a mineral acid between 1 ⁇ 2 molar equivalent and equimolar relative to tetravalent molar titanic acid, most preferably hydrochloric acid.
  • a monomer having a transparent protective function can be formed without being precipitated in Alternatively, it is considered that a cyclic protective group is formed by hydrogen peroxide and hydrochloric acid, or hydrogen peroxide and methanol.
  • the step (2) is a step of synthesizing a completely soluble alkoxytitanic acid monomer by a dilution step with water after the step (1). If the protective function is not formed, white turbidity / precipitation occurs, so this is judged.
  • the process (3) is a step of diluting by adding water according to the polymerization concentration of the alkoxytitanic acid monomer.
  • the polymerization concentration of the alkoxy titanic acid monomer is preferably 0.5 to 50%. When it is 0.5% or less, there is a problem that productivity is deteriorated, and when it is 50% or more, there is a problem that it is difficult to increase the degree of polymerization.
  • the degree of polymerization increases in viscosity and eventually reaches the gelation point, but a preferred end point can be confirmed by a method in which stirring is loaded and stopped immediately before that, but a viscometer is installed, A safe catalyst amount may be set.
  • the process (4) is a step in which a chain transfer polymerization catalyst or an ion exchange resin is added after the step (3) to polymerize until a transparent gelation point is reached.
  • the chain transfer polymerization catalyst comprises water-soluble phosphoric acid, phosphoric acid alkyl ester, an ion exchange resin having a chelating property represented by anion exchange resin, or a compound that forms a chelate with titanic acid, alone or as a mixture.
  • a water-soluble chelating agent such as EDTA can be used as the chelate-forming compound, but if it is an organic compound that does not evaporate, it will self-decompose when applied to the outer wall, even if this component is bound to the polymer.
  • Inorganic compounds may interfere with catalyst activity or use against the main purpose of this technology.
  • it is considered to be an impurity to be used as an impurity, it is intended to provide a new function when forming titanic acid and titanium oxide, for example, a chip having a protective group of the present technology.
  • phosphate monomers and polymers is chelated water-soluble chelating agent, to form a gel, but using the functional products, such as a chelating agent of a solid water insoluble it is preferable not to use.
  • the water-soluble phosphoric acid compound and phosphoric acid alkyl ester can stably maintain the protective function because, as in structural formulas (a), (b), and (c), methanol and hydrogen peroxide are Preferred from the theory of corrosion in the literature, ethanol is also possible, but since it is preferable to specify methanol, it is preferably a methyl phosphate compound, and whether the transparent gelation point has been reached is determined visually or This can be determined by stopping the stirring load and controlling the viscometer.
  • Example 1 While adding 190 g of tetrachlorotitanium to 264 g (4.4 mol) of isopropyl alcohol, the mixture is cooled with cooling water and reacted at 50 ° C. or lower. After the addition is completed, the reaction is terminated at 30 ° C. or lower.
  • Isopropyl titanate TIPTC4- (1) then tetraisopropoxy titanate molecular weight 284 is set to TIPT (2), and then 190 g of tetrachlorotitanium is added to 160 g of methanol and reacted at 50 ° C. or less, At the time when the temperature dropped to 0 ° C. or lower, tetramethoxytitanate was designated as “TMT-C4- (3)”, and in addition to this, the reagent tetramethyl titanate (molecular weight 172) was designated as “TMT (4)”.
  • TIPT-C4- (1) was added with 1 kg of methanol, reacted at 40 ° C. or lower while cooling with water, and transesterified to form a monomer “TIPT-MC4” having a protecting group, and 36.5% in 1 kg of methanol.
  • TIPT-MC2 is a monomer in which “TIPT- (2)” is added to 200 g of hydrochloric acid and a protective group is formed by transesterification under water cooling to 50 ° C. or lower, and TMT-C4 1 kg of methanol was added to obtain “TMT-MC4” (3), and then TMT was added to a solution of 2 kg of hydrochloric acid in 1 kg of methanol to form a protecting group at 40 ° C. or lower, and “TMT-MC2” It was.
  • a transparent monomer obtained by adding 2 kg of water to POT-OC4 and carrying out a similar reaction was designated as “POT-OC4-10%”. Further, 1 kg of water was added to POT-OM2, and a hydration reaction was performed to obtain a transparent monomer, which was designated as “POT-OM2 10”.
  • each monomer does not cause white precipitation even when a large amount of water is added or a chelating agent is added in a catalytic amount (polymerization concentration ⁇ the amount of catalyst controls the polymerization degree). It is presumed that this is a monomer having a protective group formed thereon.
  • TIPT- (1) MC4, TIPT- (2) MC2, TMT-MC4, and TMT-MC2 are formed by forming a five-membered or six-membered ring of hydrochloric acid, methanol, and titanium.
  • C It is considered that I becomes, while POT-OC4 is considered to have the formula (OT) OM2 of (a) II and (b) III.
  • reaction formula at the time when the monomer was synthesized was estimated from the IR spectrum when it was applied to a salt plate, excess volatiles were removed at room temperature, and a constant weight was reached.
  • the raw material was first grade reagent, and all Wako Pure Chemicals were used.
  • methanol and hydrochloric acid, hydrogen peroxide, and hydrogen peroxide and methanol may form protective groups in the form of titanic acid and complex.
  • alcoholysis replaces low molecular weight alcohol with high molecular weight alcohol, but hydrochloric acid, water and methanol contained in hydrochloric acid are stabilized as methyl titanate hydrochloride by intermolecular bonding, and isopropoxy titanic acid bonding becomes unstable and is considered to cause alcoholysis to methoxytitanate. This is evidenced by the literature on titanium corrosion, where hydrochloric acid and methanol systems are extremely corrosive, followed by ethanol, but with little other alcohol.
  • Titanium tetrachloride is a clear aqueous solution up to 10%, but when diluted by adding water, a white precipitate is formed and becomes a sol when the amount is 8% or less.
  • alkoxytitanic acid typical known and publicly available monomers include tetraisopropoxytitanic acid, tetrabutyloxytitanic acid, and tetramethoxytitanic acid, but they are insoluble in water and alcohol contains alcohol used for monomer synthesis. It dissolves only when it comes into contact with water and becomes a titanium oxide (having a hydroxyl group) sol, so that not only alkoxytitanic acid but also metal alkoxy compounds that do not dissolve in water can be infinitely added to water.
  • This monomer is transparent and can be easily and uniformly applied to any material. It is transparent and can be cross-linked by UV, heat, chelating agent and hydrogen peroxide to form a strong film, such as titanium lining agent. It can be used for spinning and film processing, and can be used for extrusion molding, press molding, casting mold, granulation, lining processing, etc., alone or with a binder, which may open the way for new technologies and new applications. is there.
  • New materials for electromagnetic wave protection and new materials for electrostatic protection can be developed by impregnating cloths, forming into yarns and films, or coating on yarns and films.
  • titanium content 0.5% by weight. It was considered as a protective colloid solution with titanic acid isopropyl and was designated as “Y-TIP”.
  • Example 2 Using 1 mol of a solution corresponding to a 10% monomer formed with a protecting group synthesized in Example 1 (4 mol of hydrochloric acid and equimolar number of hydrochloric acid), 85% phosphoric acid and trimethyl phosphate (phosphorus) were added to the chain transfer polymerization catalyst (chelating agent).
  • Comparative Example 2 When phosphoric acid and trimethyl phosphate were added to the 0.5% solution “Y-TIP” and the 1% solution “S-POT” synthesized in Comparative Example 1, 1 drop of “Y-TIP” was added. As a result, white sediment was formed, and when the filtrate was analyzed, titanium was not contained in the supernatant.
  • both Y-TIP 0.5% liquid and S-POT are transparent liquids of several to 50 nanometers of titanium oxide particles, so that they do not reach a linear polymer, and a crosslinked granular crystal sol for condensation polymerization is obtained. It is clear that it is formed.
  • Example 3 Example of demonstrating that the effects of polymerization concentration and raw materials are similar to TMT and TIPT Monomer TMT-MC2 (hydrochloric acid 2/4 molar value liquid) equivalent to 10%, equivalent to 2% and equivalent to 10% TMT-MC 2 2% equivalent solution with hydrochloric acid added to make 3 ⁇ 4 molar ratio to methoxytitanic acid 10% equivalent of TMT-MC 3 2% equivalent and TMT-MC 4 10% equivalent and 2% equivalent
  • the 1.8 to 2.0 moles of white turbid but non-precipitating polymer is a linear polymer with titanium hydroxide terminated, titanium oxide aggregate grafted, or a linear polymer cross-linked. Conceivable.
  • Example 4 Comparison of phosphoric acid content and white turbidity (containing titanium hydroxide) in light and non-light activity Ishihara Sangyo Co., Ltd., including the polymer synthesized in Example 3 with a monomer concentration equivalent to 2% of the TMT system Using TITANIA STS ⁇ 21 as a comparative example, applying it to a slide, irradiating with UV light with black light 500W for 8 hours, then methylene blue method (by spraying methylene blue liquid on the test piece and drying) and placing under UV light again Table 3 shows the results of determining the order of decomposition (decoloring) speed.
  • a to E the activity under light and light is reversed depending on the phosphoric acid content.
  • F and the monomer do not contain phosphoric acid. Since the monomer does not have an intramolecular self-active function, it is considered that the activity is low because it is difficult to form a titanium oxide bond unless energy for demethylation is given for a long time outdoors by ultraviolet and solar heat.
  • the ultraviolet irradiation methylene blue test method the following values were obtained.
  • Example 5 Add the monomer concentration, use the monomers POT-OC 4 -10 and POT-OM 2 -10 under the same conditions as in Example 2, add phosphoric acid and trimethyl phosphoric acid, and adjust the monomer concentration to the gel point Table 4 shows the results of measuring the phosphoric acid amount and trimethyl phosphoric acid amount.
  • Example 6 Acrylic paint (manufactured by Nippon Paint Co., Ltd.) is applied to the outdoor slate wall surface, and the same as Example 2 using 1 kg of monomer equivalent to 10% on green moss (green moss) grown on the north facing wall after 5 years
  • the test results are shown in Table 5 in which 5% phosphoric acid catalyst and 20g of trimethyl phosphate were used to dilute the alkoxytitanic acid and peroxytitanic acid, which had been terminated by 2%.
  • the wall is facing north and there is a vine shelf on top.
  • Example 7 Results of chain transfer polymerization in an anhydrous system without hydration and solubility in organic solvents.
  • the monomer synthesized under the same conditions as in Example 1 was polymerized using 85% phosphoric acid and trimethyl phosphate as a chain transfer catalyst under the same conditions as in Example 2 without adding water and without hydration. As a result, much more phosphoric acid and trimethyl phosphoric acid were required than the reaction when hydrated. As a result, a darker activity is obtained, and those using phosphoric acid can form a more hydrophilic film, and those using trimethyl phosphate can form a more lipophilic film. It has been found that it can be formed. -20 was added to the end of the obtained one. The organic solvent solubility of the sample polymerized with trimethyl phosphate is shown as wt% at the right end of Table 6.
  • Example 8 Elucidation of reaction mechanism by dehydrochlorination reaction and investigation of alkoxytitanic acid for rust inhibitor Monomer (TMT-MC2-10, TIPT-MC2-10) synthesized under the same conditions as Example 1 and Examples using this The polymer (TIPT-MC2-10-P15.6, TMT-MC2-10-P-14.3), which was polymerized in the same manner as in No. 2, was diluted with water to correspond to 2%, 1%, 0.
  • a 5% equivalent solution was prepared and packed in an ion exchange column 500 mm 30 mm ⁇ packed with weak anion exchange resin (manufactured by Mitsubishi Chemical Corporation), passed 100 cc at a rate of 10 cc for 1 minute, fractions were separated, and silver nitrate Fractions that did not cause white sediment were collected and the viscosity was measured with a B-type viscometer in a constant temperature bath at 20 ° C. ⁇ 0.5 ° C. Moreover, the result of having measured the viscosity after adding 5 cc of 8.5% phosphoric acid to 70 cc of this polymerized liquid was entered in parentheses.
  • the monomer forms a very stable protective group in the form of methyl titanate hydrochloride or methyl titanate hydrochloride complex, but it was predicted that white precipitation would occur immediately when the hydrochloric acid was extracted, but it passed through the ion exchange column. Later, thickening polymerization occurred and a transparent polymer was obtained. It is considered that water molecules were replaced after hydrochloric acid was removed, and chain transfer polymerization was caused by hydration reaction, and the molecular composition was inferred in the following chemical formula 5a. Phosphoric acid was added to the ion exchange resin polymerized solution, but the viscometer did not rise and chelate precipitation did not occur.
  • polymers that have undergone chain transfer polymerization with a chelating agent do not cause white precipitation even after dehydrochlorination and do not thicken.
  • a chelating agent instead of hydrochloric acid, water forms stronger protective groups with methoxy titanate groups, and phosphoric acid The chelate bond is not formed, and a weak bond such as a coordinated complex salt is formed, or water and a protective group are formed, so that white precipitation does not occur, and the molecular composition is estimated in the following chemical formula 5b. did. From this, it is considered that the molecular structure when phosphoric acid is added to the ion exchange polymerized polymer is also represented by the chemical formula 5b.
  • Example 9 Table 8 shows the results of the rust prevention test of the chlorinated sample synthesized in Example 8.
  • a test piece obtained by polishing a bonding steel plate 0.8 mm (degreasing) (Nippon Steel) with a cloth cloth No. 400 is used to apply a non-chlorinated solution by passing an ion exchange resin, and suspended with a hanging thread at 110 ° C./3 hours.
  • the dried sample was immersed in “5 ppm saline”, “Nobeoka tap water”, and “ion-exchanged water”, and the time when the surface was discolored or spotted was compared using an untreated test piece as a comparative example.
  • Example 10 Tests on ultraviolet treatment, heat treatment and self-activation were conducted. Liquid subjected to chain transfer polymerization shown in Example 2 Each sample 2 was used to perform ultraviolet treatment activation treatment, heat treatment activation and self-activation activation tests using (A) TIPT-MC2-10-P15.6 and (B) TIPT-MC2-10-PM29.4 as representative examples. % Sample is spray-coated on a 10 cm ⁇ 10 cm glass plate, and dried samples (A) and (B) are produced in a room at room temperature (20 ° C. ⁇ 1 ° C.) and humidity of 50% for 7 hours. Using (A) and (B), samples dried by aeration at 110 ° C.
  • Example 11 Using the same sample as in Example 10, using a test piece treated with 110 ° C./2Hr and phosphoric acid, put it in a JIS method tetra bag, the activity in the dark, and the activity when the ultraviolet lamp is applied It was measured. (According to JIS method)
  • Phosphoric acid treatment is a sample that is sprayed with 2% phosphoric acid on an untreated test piece and kept in a 50% temperature ventilator for 1 hour with excess methanol / water system and stable methoxytitanium. After the acid polymer is dried, the hydration protecting group is destroyed, and after forming a film, when the phosphoric acid is contacted, the methyl group of the protecting group is demethylated, resulting in a titanium oxide bond (reticulated) or titanium phosphate. The purpose of the test was to assume a combination. The results are shown in FIG.
  • Example 12 The problem that when titania is applied to vinyl chloride cloth, titania is adsorbed and buried in the plasticizer and does not show the photocatalytic effect has been unsolved by the leather company (K Leather). Since the known titania is a particle titania dispersed in water, it has a lot of hydrophilicity and has no adhesive affinity with the lipophilic plasticizer. Even if absorbed, it is not absorbed in the deep layer where no light is applied. It is thought that time could not be given.
  • the sample TIPT-MC4-PM5108 which has the strongest activity in the dark place of the titanium catalyst of the present invention, has high affinity with the plasticizer of the cloth, it shows activity both in absorbed and non-light, and at the end of the plasticizer. It is expected that the ester group and the alkoxytitanium group can be transesterified to form a chemical bond or an intermolecular bond by the hydrochloric acid catalyst and the self-catalytic effect of the titanium phosphate bond and the phosphate group in the molecule. And found to maintain extremely high deodorant activity permanently.
  • this high dark type titanic acid catalyst binds to and associates with the surface of the cloth to form a film.
  • excess or free trimethyl phosphate that exists as a solvent effect in excess of the number of moles required for reaction with the titanic acid polymer chain.
  • the site bonded to the alkoxytitanic acid polymer existing on the surface is exposed, and dealkylated by ultraviolet and intramolecular self-activity, resulting in titanium oxide bonds and phosphorus. It is presumed that it permanently binds to the surface of the cloth to form a titanium acid bond and imparts photoactivity and dark activity, and it shows permanent activity without erosional deterioration or loss.
  • the polymer TIPT-MC4-10-PM518 and TMT-MC2-10PM27 obtained in Example 2 were used for a PVC cloth (a plain cloth manufactured by Kanto Leather Co., Ltd.) cut into 10 cm ⁇ 10 cm, and a Saga type titania TA was used as a comparative example. And 2% of each of Ishihara-type Titania STS-01 were coated, dried at 20 ° C. ⁇ 1 ° C. and humidity of 50% or less for 7 hours, and tested by injecting 100 ppm of acetaldehyde by the tetrabag method. .
  • Example 13 Polarity contrast test and self-cleaning test Samples with the highest hydrophilicity to the highest lipophilicity are arranged as shown below.
  • Saga-type peroxytitanate TA Teo-Techno
  • each 2% solution was added, and each 2% solution.
  • the hydrophilic acrylic coating surface of Asahi Kasei Hebel was added, water was added to the microsyringe, and the droplet was prepared.
  • Table 9 shows values obtained as a result of measuring the amount (ml) of water at the point where the droplet is dropped and the droplet breaks down and spreads.
  • coating 2% hydrogen peroxide water to the surface of the prepared preparation and performing the same drying, the result of having measured the hydrophilicity by the water drop method is shown in ().
  • Example 14 Asahi Kasei Hebel Wall material surface coated with acrylic paint (PB coat (HG) manufactured by Ohashi Chemical Co., Ltd.), aqueous stain (100 cc water, 5 g clay added and colored with 1 cc ink), oily (Mineral oil) After the sample used in Example 13 was brushed on the surface of the blank after adding 5 cc of machine oil to 100 cc of water and colored and shaken with 1 cc of ink, it was naturally dried indoors for 1 week. Table 10 shows the results of a natural drop caused by rainfall and a forced drop test using a tap water nozzle after being left outdoors.
  • PB coat HG
  • aqueous stain 100 cc water, 5 g clay added and colored with 1 cc ink
  • oily Mineral oil
  • Example 15 Preservation of wood and white ants prevention effect
  • Flooring for the outer wall of cedar board (made by Kawakami Timber) is decompressed 700-500 Torr, pressurized 9-10 kg / cm 2 with Yasima Co., Ltd. decompression pressurization type impregnation machine (owned by Lumber Miyazaki Cooperative).
  • Example 16 Automotive Steel Plate Adhesion Test Automotive steel plate test piece (bonded steel plate degreased (manufactured by Nippon Steel) 0.8 mm t cloth finish No. 400), 100 ⁇ 100 mm 2% of the sample synthesized in Example 8 was applied. (Roller) After heat treatment at 180 ° C. for 5 minutes, three test pieces were sprayed onto the vehicle paint (Vilicia PL1000 manufactured by Nippon Paint Co., Ltd.) using Gas PEM-T3 manufactured by Nippon Wagna Co., Ltd. Table 12 shows the results of examining the height at which the 500 g steel ball is dropped and the height at which the paint is peeled off.
  • Example 17 Pesticide antibacterial test The representative sample 2% equivalent solution synthesized in Example 6 was used.
  • Table 13 shows the results of a sterilization recovery test of sweet summer citrus afflicted with black rust (soot) disease. The judgment after one month after application was indicated by complete erasure ⁇ , almost erasure ⁇ , no change ⁇ .
  • Methoxytitanic acid when dried and exposed to ultraviolet light, is thought to bind to the amino groups and bases on the spiked protein surface exposed on the surface of the cells, promoting the decomposition of the cells, and the surface of the plant is Since the material and protective film are formed, there is little damage, and it is remarkable for the degradation and elimination effects of viruses, molds and moss, which are lower organisms, but there is very little damage to the epidermis of plants and animals that are higher organisms, especially the human body Is estimated.
  • Example 18 Decomposition field test of NOX and SOX in tunnel Selected from the sample of Example 6 and tested using a 2% solution.
  • NOX and SOX are lipophilic and are easily adsorbed and fixed in soot.
  • NOX and SOX adsorbed by soot in a tunnel with little light come into contact with the redox action of the anode / cathode and red phosphorus / yellow phosphorus presumed as the mechanism of self-activity in the methoxytitanate phosphate polymer. It is thought that it became extremely strong water-absorbing (hydrophilic) sulfuric acid and nitric acid and accumulated in the lower part.
  • (B) may be considered to be liable to adsorb lipophilic NOX and SOX because of the lipophilic type. Moreover, it was confirmed that the hydrophilic (A) treatment part can be completely washed with tap water pressure. Therefore, if (B) is applied to the undercoat and (A) is applied to the overcoat, more preferable conditions for decomposition and cleaning of NOX and SOX can be provided.
  • Example 19 Test of electromagnetic wave protection effect 2% solution of the sample synthesized in Example 8 was applied to Saran wrap, and a test beaker in which 100 cc of water was put in a 300 cc beaker was covered entirely, and a sample was covered as an untreated Saran wrap as a comparative example.
  • Table 15 shows the results of measuring the time when water was put into a microwave oven (National NE-F3) using a beaker and the time when water started to boil was measured. The number of tests was 3 points.
  • Saran Wrap registered trademark
  • Example 20 From the protective group-forming monomer, a chain transfer polymerization or ion exchange polymerization polymer was applied and dried, and the mechanism leading to the catalytic activity was added to the examples described above and a new chelating agent after dehydrochlorination from the system. It was elucidated in detail using the behavior.
  • phosphoric acid When phosphoric acid is used as the chelating agent (linkage transfer catalyst), phosphoric acid stops (clogs) the chain transfer polymerization polymer terminal, and the excess phosphoric acid is simply in the form of a salt with the polymer. Of titania phosphate proved different to immediately form a precipitated sol.
  • hydrochloric acid has the strongest stoichiometric bond strength, but [H 2 O]> [HPO 3 ]> [HCl] in this order, and methotitanate (protecting group) monomer (I), even if not hydrated (II), by adding water and hydrating, the methoxytitanate group should be hydrolyzed to form the strongest hydration protecting group,
  • this hydration protecting group end does not form a chelate even if phosphoric acid, which is the strongest chelating agent, is added (no white precipitation), and it is stable that the end of the polymer ends.
  • the (sealing) structure is considered that phosphoric acid is stabilized in the form of a complex salt with a titanic acid hydrate protecting group, not a titanium phosphate bond.
  • the estimated chemical formula shown in the terminal formula Estimated chemical formula
  • the following estimated chemical formula shown in the polymer chain equation I is the estimated chemical formula by condensing two methoxy groups It is estimated that it is stabilized in the form of
  • the hydration protecting group becomes more dehydrated and concentrated.
  • the titanium oxide bond and the titanium phosphate bond are formed and further demethylated by high-temperature treatment, hydrogen peroxide treatment or intramolecular redox reaction, or ultraviolet redox reaction, Examples 4, 7, and 10 show that a titanium oxide bond and a titanium phosphate bond are firmly formed, and the former forms a network polymer film exhibiting photoactivity, and the latter forms a titanium phosphate bond exhibiting dark activity. , 11 and 12.
  • Example 21 Spinning test Using the viscous liquid just before the gelation point corresponding to 10% of Example 5 (1) POT-OC 4 -P18.2, (2) POT-OC 4 -PM35, (3) POT-OM 2- Place P9.0, (4) POT-OM 2 -PM18.2 into a pressurized container equipped with a 0.5mm ⁇ spout while controlling the holding pressure of 1kg / cm 2 ⁇ 0.01.
  • the degree of continuous spinning was studied by flowing down into a 2 m high, 100 mm ⁇ Pyrex glass tube held at an air temperature of 200 ° C. ⁇ 5 ° C. (sensor set at the nozzle outlet) with an external heater. The results are shown in Table 16.
  • the homogeneity of the yarn was determined as to whether or not the yarn was spun by deformation.
  • Example 22 Film molding Heat roller 300mm ⁇ , length 300mm, rotation ratio 10:11 processed with Teflon (registered trademark) using the same sample as Example 21 was rotated at a speed of 6r / m while maintaining a gap of 0.2mm.
  • Table 17 shows the results of a test in which the surface temperature was kept at 200 ° C., samples (1), (2), (3), and (4) were caused to flow down to the center of the roller and the film was wound on a winder.
  • the film homogeneity was evaluated as ⁇ for no deformation at all and ⁇ for slight deformation.
  • Example 23 Used Shoe Skin Treatment Test Odor and Mold Test in the Dark Using the sample used in Example 15, applied to the entire used shoe by spray, kept under sunlight for 3 days, humidity 80% / 30 ° C As a result of checking every day until the mold grows in the untreated area, mold odor occurs from the first day, and mold is confirmed on the third day. It was. Both TMT-MC 2 -P6 and TMT-MC 2 -PM20 were retained for 3 months, but were discontinued without change. There was no odor.
  • Example 24 Tooth bright abrasion test TMT-MC 2 -10P14.3N and TIPT-MC 2 -10P15.6N synthesized in Example 8 were applied to the front teeth and dried with a dryer at 40 ° C ⁇ 10 ° C for 10 minutes. Thereafter, 2% phosphoric acid was applied, dried for 10 minutes, and irradiated with black light (Decitron LC, manufactured by Sablon Dental Co.) for 30 minutes. As a result, a strong bright surface was formed. As a result of checking every day and measuring the period during which the radiance decays, the radiance attenuated little by little from 8.5 months at both points.
  • Example 25 Use as dry lubricant A bearing identical to the Iwatani Milser (model IMF-710) plated bearing is manufactured, and the equivalent of 2% of the product used in Example 8 is injected into the metal part for 10,000 revolutions per minute. Then, three points were prototyped by a method of additional injection, and untreated ones were compared with molybdenum disulfide dry lubricant (manufactured by Nippon Dry Slide Co., Ltd.) and shown in Table 18.
  • a film of titanium oxide and titanium phosphate is formed, and like the dry lubricant of molybdenum disulfide used under absolute vacuum such as spacecraft, the formed film peels off and the scaly crystals are formed. It is thought that it forms and exhibits the effectiveness as a dry lubricant.
  • Example 26 Using a ceramic container with a koge and anti-adhesion effect made by Daikei Co., Ltd. Using the ceramic container “double pot (A)”, “cooking rice drop lid (B)”, and “tea pot (C)”, the sample of Example 14 was prepared. Using, brushing, air-drying and brushing three times, put it in an oven toaster at 200 ° C and heat-treat it for 1 hour. (A) contains raw soy milk and hot water in the lower pan.
  • Example 27 Ceramic polishing and evaluation of abrasion resistance
  • a sample equivalent to 2% of Example 6 was applied to an alumina ceramic ball 20 mm ⁇ manufactured by Daqing Co., Ltd., and air drying was repeated three times to obtain room temperature, 100 ° C, 200 ° C, 400 ° C, Put in a furnace at 800 ° C. and evaluate the brightness when heated for 1 hour (Luminance: ⁇ , Yes: ⁇ , No: ⁇ ) and put the resulting balls (filling rate 50%) into 1 liter of test ball mill 100 g of talc 100-mesh powder was put, rotated at a rotation speed of 60 r / m, and checked for radiance (abrasion) every hour. Table 20 shows the time in [].
  • Example 28 Decomposition of carbon dioxide A glass fiber of 0.1 mm ⁇ (manufactured by Asahi Glass Co., Ltd.) impregnated with TIPT-HC 2 P6, TIPT-MC 2 PM20 2% equivalent solution, and dried by ventilation three times. Put the sample heated in an oven at 200 ° C for 1 hour into a JIS tetra bag and measure the carbon dioxide concentration when the carbon dioxide gas is replaced five times to confirm that the purity is 99.9% or higher.
  • FIG. 4 shows the results of measuring the amount of CO (carbon monoxide) produced with irradiation of black light 500 W over time.
  • Example 29 Decomposition of water 150 g of the same sample as obtained in Example 28 was uniformly filled into a 2 liter glass graduated cylinder, charged with pure water, fitted with a rubber stopper at the top, and a cock at the top. Attached nozzle is attached, the tip of the nozzle is connected to a JIS tetra bag with a rubber hose, nitrogen is substituted from the tetra bag to the cock, 5 g of magnesium metal wire is put into the tetra bag, and the oxygen content is 0.1 ppm or less FIG.
  • FIG. 5 shows the result of measuring the concentration of hydrogen accumulated in the tetra bag after irradiating with a black light 500 W along the graduated cylinder and irradiating the tetra bag space to 1/5 or less and exhausting the gas.
  • the measuring instrument used is Shimadzu GC-MS-QP2010). The results are shown in FIG.
  • Example 30 Peeling due to affinity, white flower, omission prevention Example 13 showed the molecular design from hydrophilic (polar) to oleophilic (nonpolar), but it was used to test the method of selecting affinity for the substrate surface. The results are shown.
  • Example 31 When a urethane fluorine coating plate (fine 4F ceramic Nippon Paint) was brushed, the sample affinity of Example 14 was as shown in Table 21.
  • Example 32 Undercoat simulation test for glass compatibility and prevention of substrate erosion The affinity for glass was opposite to that in Example 31, and was A / ⁇ , B / ⁇ , C / ⁇ , D / x, and E / xx opposite to the affinity shown in the table of Example 31. .
  • methylsodium silicate obtained by reacting 2% trimethylphosphate (trimethyl phosphate) and 2% sodium silicate instead of phosphoric acid was designated as “PMS”.
  • the affinity of this material for glass was PS / ⁇ and PMS / ⁇ .
  • the ratio of trimethyl phosphate is increased, the polarity of PMS decreases and can provide lipophilicity.
  • Example 33 Antistatic (conductivity) test 40 cm square of polyester cloth was drained with a cotton towel that had been impregnated with 2% equivalent of the sample of Example 6 and dried, and dried under direct sunlight for 2 days. Hold it with two fingers, rotate it 10 times, and then place a 1-inch steel pipe with a steel ruler attached at a right angle close to the vertical tip, and repeat the adsorption distance 3 times in units of 0.5 cm. It was measured. The average value of the results is shown in Table 23. Compared to the comparative example, the antistatic effect was extremely high.
  • Example 34 Superconductivity test Equivalent to 10% of TMT-MC 2 -10-P14.3N and TIPT-MC 2 -10-P15.6N desalted by ion exchange after chain transfer polymerization with phosphoric acid synthesized in Example 8
  • a commercially available titanium nitride powder (particle size: 1.5 ⁇ m, manufactured by Nippon Shin Metal Co., Ltd.) is used as a comparative example.
  • a solid content of 50% by weight kneaded in a mortar, repeatedly applied and dried on a PET film, adjusted to 30 ⁇ m, and dried in a ventilated dryer at 130 ° C. for 24 hours.
  • Table 24 shows the results of measurement of the surface resistance value of the heat-treated sample using “High Lester IP” manufactured by Mitsubishi Chemical Corporation.
  • the content analysis as titanium phosphate is a value obtained by putting into a petri dish and scraping a material that has been air-dried at 130 ° C for 24 hours, and conducting elemental analysis.
  • Example 35 Starch saccharification test
  • the glass wool prepared in Examples 28 and 29 was joined in multiple stages with a glass U tube with an inner diameter of 25 mm ⁇ and a length of 300 mm. A total of 2000 mm was filled with 500 g, and a 200 W black light was attached to each tube stage.
  • the beta (beta reduction) and 10% starch solution (90 ° C. ⁇ 5 ° C.) the result was flowed at a rate 5 liter / Hr from the bottom by a metering pump, saccharification rate 95% TIPT-MC 2 -P6, TIPT -MC 2 -PM20 and 98%.
  • Example 36 Fish Farming Survival Test Using the plant of Example 35, the survival rate was measured using juvenile carp (6 months) harvested from the hatching pond and selected. As a comparative example, “Tropical Gold Treatment Zone” (manufactured by Tsuji Pharmaceutical Co., Ltd.) and “Untreated Zone” were used. The food provided 10g a day for each test section manufactured by Smack Co., Ltd.
  • Example 37 The structure is compared with known granular titania using the IR spectrum. As a comparison with TIPT-MC 2 P6 (FIG. 7) and TIPT-MC 2 PM20 (FIG. 8), the IR spectra of the suspension of Ishihara type STS-01 (FIG. 10) and YO type comparative example 1 (FIG. 9) are shown. The polymerization structure was estimated. The horizontal axis of each IR spectrum indicates the wave number, and the vertical axis indicates the transmittance.
  • the sample was taken in a petri dish, confirmed to have reached a constant weight by aeration drying at room temperature for 40 hours, the attached crystals were scraped with a spatula, mixed with KBr and molded, and the measurement results are shown in Table 26.
  • the titania of the comparative example is an aggregate of titanium hydroxide and has a low polymerization / crosslinking rate.
  • the titania of the present invention is titanium. Is apparently crosslinked and has a molecular structure completely different from that of Iohara type as well as YOO type titania, which supports the presumed molecular structure. Especially 1650 cm -1 titanate This is proof that the absorption that we think is differentiated from the comparative example. IR charts are attached as FIGS.
  • Example 38 Ultraviolet ray / heat ray protection test A 2% equivalent sample synthesized in Example 8 and a Saga type titania TA 2% as a comparative example were spray-coated on a 30 cm ⁇ 30 cm glass and left for 1 week in outdoor sunlight for 20 mm. Attached to one side of polystyrene foam box 30cm x 30cm x 30cm, sealed with gummed tape, attached thermometer, kept in a room at 20 ° C ⁇ 1 ° C for 1 hour, and placed in direct sunlight at an outdoor temperature of 30 ° C ⁇ 1 ° C The rate of temperature rise was measured. At the same time, unprocessed values are also added.
  • Example 39 Antibacterial, deodorant, rain removal, ground removal clothing test Using the sample used in Example 6 and a titanic acid group added with 1 ⁇ 2 mol of hydrogen peroxide, antibacterial and antibacterial Table 28 shows the results of odor, rain erasure and lichen erasure tests.
  • Table 28 shows the number of days when it was determined that the erasing was completed by observing the gray lichen that inhabited one leaf (firewood) with a cloth impregnated with the above-mentioned 2% solution and impregnating it, and observing it every 5 days.
  • Example 40 The product obtained in Example 7 was dissolved in a solvent of methanol 50: xylene 50 to make 10%, to which was added 7% of the dye Unilite High Conk Red (manufactured by Unilite), and Campehapio Co., Ltd.
  • Made of water-soluble acrylic silicon paint Happioselect red diluted with 50% water, as a comparative example, paints a surface of roof concrete water-based acrylic silicon paint after 1 year and Nippon Paint test piece NA-9903 flat (steel finish) Table 29 shows the results of observing the situation in which the brightness declines.
  • the radiance of the slate test piece that was stored indoors and stored was set to 10, and the attenuation of the radiance was measured every month to give a score.
  • the brightness was inferior to that of the example from the start, and the brightness declined rapidly with time.
  • Example 41 TIPT-MC synthesized under the same conditions as in Example 1, with (A) being a liquid in which 1 mol of barium chloride (reagent primary Wako product) was dispersed (partially dissolved) to a methanol weight percent of 10%. 2 One mole of 10% equivalent liquid was defined as (B).
  • the obtained sample was prepared to correspond to 2%, 0.2%, and 0.02%, and this solution was impregnated into gauze, applied to a preparation, and dried at room temperature. Although it seemed cloudy, a transparent film was formed.
  • barium alkoxytitanate it is assumed that when the water evaporates, the protecting group is destroyed, dealkylation proceeds, and pure barium titanate at the molecular level is sequentially formed. Barium is bonded to the protective group site of alkoxy titanate polymer, or the shape is a collection of several nano particles, which is the size of the barium acid unit, forming a barium titanate bond with the adjacent chain, making it less than 50 nano It is thought that it has become.
  • solution (B) tetraisopropyl titanic acid was dissolved in isopropyl alcohol to obtain a 10% solution, which was designated as solution (B).
  • the formed particles are assumed to be aggregates of barium titanate particles having an average particle diameter of several hundred nanometers.
  • Example 42 ⁇ Immobilization test of water-soluble chelating agent> Reagent liquid (A)
  • A [Experiment 1: Titania phosphate chelating agent] Methanol hydrochloric acid solution with 0.05 mol of 36.5% hydrochloric acid added to 50 g of methanol is placed in a flask and stirred with a three-month type peller while flowing water in a water bath so that the internal temperature becomes 40 ° C. or lower. Then, 0.1 mol of tetraisopropoxytitanate reagent was added dropwise, the reaction was completed over 60 minutes, and then a solution in which 0.05 mol of phosphoric acid was dissolved in 50 g of methanol was adjusted to an internal temperature of 40 ° C.
  • This powder 20 g of titania phosphate reticulate, was put into 100 cc of pure water, stirred with a stirrer in a beaker for 30 minutes, filtered with filter paper, washed with 300 cc of pure water, and then integrated with filter paper at 50 ° C / 1.
  • the weight after subtracting the filter paper at the point where the constant weight was reached in the stage of air-drying for 1 hour and further drying for 1 hour was 19.5 g.
  • Example 43 ⁇ Contrast of dilute concentration vs. time-dependent change of “exfoliated white flower” and “brightness”> Monomer “TIPT-MC 2 ” synthesized under the same conditions as in Example 1, polymer “TIPT-MC 2 PM20” synthesized in Example 6 using this monomer, and dehydrochlorinated polymer “TIPT-MC” synthesized in Example 8 2- P-15.6N "and a solution diluted with 2%, 0.2% and 0.02% using” Saga type TA "as a comparative example. Outer wall material Nippon Paint Test Piece" Fine Silicon UV, ND- A spray gun was applied to No.

Abstract

Cette invention concerne un monomère d'acide titanique et un polymère à base de celui-ci, qui sont chimiquement liés à un matériau de base, et permettent la formation d'un film ayant une stabilité à la contrainte permanente, une activité à l'abri de la lumière et sous un rayonnement lumineux permanente, et un éclat/des propriétés antitaches/des propriétés auto-nettoyantes, des fonctions électromagnétiques/électriques/ des fonctions anti-corrosion et autres permanentes. Plus spécifiquement, cette invention concerne un nouveau monomère d'acide titanique, un polymère, et un procédé de production du monomère d'acide titanique et du polymère, qui comprend : (1) une étape d'ajout d'un monomère d'acide alcoxytitanique pur ou de tétrachlorure de titane à un système dans lequel un alcool ne contenant pas d'eau en excédent et un acide minéral coexistent ou à un système dans lequel un peroxyde d'hydrogène ne contenant pas d'eau en excédent ou un peroxyde d'hydrogène et un alcool coexistent, pour synthétiser ainsi un monomère d'acide alcoxytitanique ou un monomère d'acide peroxytitanique ayant chacun une fonction protectrice ; (2) une étape d'utilisation du monomère d'acide alcoxytitanique ou du monomère d'acide peroxytitanique tel quel, ou une étape de dilution consistant à diluer le monomère d'acide alcoxytitanique ou le monomère d'acide peroxytitanique par ajout d'eau ou d'un alcool au monomère d'acide alcoxytitanique ou au monomère d'acide peroxytitanique pour provoquer une réaction d'hydratation ou autre réaction similaire ; (3) une étape de polymérisation consistant à polymériser le monomère d'acide alcoxytitanique ou le monomère d'acide peroxytitanique utilisé tel quel ou le monomère d'acide alcoxytitanique ou le monomère d'acide peroxytitanique préparé dans l'étape de dilution avec un catalyseur de polymérisation par transfert de chaîne à l'aide d'une résine échangeuse d'ions ou un agent de chélation, pour obtenir ainsi un polymère ; (4) une étape de formation d'un complexe ; et (5) une étape de dissolution consistant à diluer complètement le polymère obtenu avec de l'eau dans une réaction d'hydratation ou avec un solvant organique à des fins d'application à titre de revêtement. L'utilisation du monomère d'acide titanique et du polymère est également spécifiquement décrite.
PCT/JP2010/058759 2009-06-02 2010-05-24 Nouveau monomère d'acide titanique et polymère à base de celui-ci, procédé de production du monomère et du polymère, et utilisation du monomère et du polymère WO2010140501A1 (fr)

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JP5588088B1 (ja) * 2013-12-11 2014-09-10 賢次郎 牧野 線状のアルコキシチタン酸・リン酸重合体の製造方法
CN104059420A (zh) * 2014-05-22 2014-09-24 张扬 纳米浆料，自清洁、隔热涂膜液及其透明基材及制备方法
CN104294583A (zh) * 2014-10-20 2015-01-21 南通大学 抗菌抗紫外消臭自洁复合功能面料的制备方法
WO2015087694A1 (fr) * 2013-12-11 2015-06-18 賢次郎 牧野 Matériau générant un potentiel d'oxydo-réduction produit au moyen d'un composé acide alcoxytitanique-acide phosphorique
JP2015113463A (ja) * 2014-07-24 2015-06-22 賢次郎 牧野 線状のアルコキシチタン酸・リン酸重合体の製造方法
CN109174160A (zh) * 2018-10-12 2019-01-11 辽宁大学 一种g-C3N4光催化剂涂层及其制备方法和应用
CN112979349A (zh) * 2021-03-24 2021-06-18 江西金唯冠建材有限公司 一种耐磨防污陶瓷星光抛釉砖及其制备方法

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JP5588088B1 (ja) * 2013-12-11 2014-09-10 賢次郎 牧野 線状のアルコキシチタン酸・リン酸重合体の製造方法
WO2015087412A1 (fr) * 2013-12-11 2015-06-18 賢次郎 牧野 Procédé de production de polymère d'acide alcoxytitanique-acide phosphorique
WO2015087694A1 (fr) * 2013-12-11 2015-06-18 賢次郎 牧野 Matériau générant un potentiel d'oxydo-réduction produit au moyen d'un composé acide alcoxytitanique-acide phosphorique
JPWO2015087694A1 (ja) * 2013-12-11 2017-03-16 健一 牧野 アルコキシチタン酸・リン酸化合物を用いた酸化還元電位発生材
CN104059420A (zh) * 2014-05-22 2014-09-24 张扬 纳米浆料，自清洁、隔热涂膜液及其透明基材及制备方法
JP2015113463A (ja) * 2014-07-24 2015-06-22 賢次郎 牧野 線状のアルコキシチタン酸・リン酸重合体の製造方法
CN104294583A (zh) * 2014-10-20 2015-01-21 南通大学 抗菌抗紫外消臭自洁复合功能面料的制备方法
CN106087391A (zh) * 2014-10-20 2016-11-09 南通大学 抗皱柔软透气、无污染的复合功能面料的制备方法
CN106087391B (zh) * 2014-10-20 2018-03-20 江苏欣捷衬布有限公司 抗皱柔软透气、无污染的复合功能面料的制备方法
CN109174160A (zh) * 2018-10-12 2019-01-11 辽宁大学 一种g-C3N4光催化剂涂层及其制备方法和应用
CN109174160B (zh) * 2018-10-12 2021-11-30 辽宁大学 一种g-C3N4光催化剂涂层及其制备方法和应用
CN112979349A (zh) * 2021-03-24 2021-06-18 江西金唯冠建材有限公司 一种耐磨防污陶瓷星光抛釉砖及其制备方法

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