WO2010140501A1 - Novel titanic acid monomer and polymer thereof, process for production of the monomer and the polymer, and use of the mobnomer and the polymer - Google Patents

Abstract

Disclosed are a titanic acid monomer and a polymer thereof, which have a chemical bond to a base material, and enables the formation of a film having permanently retained strength stability, permanently retained activity in dark places and under irradiation with light, and permanently retained brightness/stain-proof properties/self-cleaning properties, electromagnetic/electrical functions/corrosion-resistant functions and the like. Specifically disclosed are a novel titanic acid monomer, a polymer, and a process for producing the titanic acid monomer and the polymer, which comprises: (1) a step of adding a pure alkoxytitanic acid monomer or titanium tetrachloride to a system in which an excess water-uncontaining alcohol and a mineral acid coexist or a system in which excess water-uncontaining hydrogen peroxide or hydrogen peroxide and an alcohol coexist, thereby synthesizing an alkoxytitanic acid monomer or a peroxytitanic acid monomer each having a protective function; (2) a step of using the alkoxytitanic acid monomer or the peroxytitanic acid monomer without any modification, or a dilution step of diluting the alkoxytitanic acid monomer or the peroxytitanic acid monomer by adding water or an alcohol to the alkoxytitanic acid monomer or the peroxytitanic acid monomer to cause a hydration reaction or the like; (3) a polymerization step of polymerizing the alkoxytitanic acid monomer or the peroxytitanic acid monomer without any modification or the alkoxytitanic acid monomer or the peroxytitanic acid monomer prepared in the dilution step with a chain transfer polymerization catalyst using an ion exchange resin or a chelating agent, thereby producing a polymer; (4) a step of forming a complex; and (5) a dissolution step of completely diluting the resulting polymer with water through a hydration reaction or with an organic solvent for the purpose of the application to coating. Also specifically disclosed is use of the titanic acid monomer and the polymer.

Description

Novel titanic acid monomer and polymer thereof, and production method and use thereof

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. , 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. In contrast, 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. As a result, it is possible to freely design a catalyst that increases photoactivity, and can freely design high lipophilicity and high hydrophilicity, and there is no need to use a different undercoat agent or adhesive. In the bag method), it becomes a value that does not show activity, but it is a novel titania that expresses the activity in a short time due to light or self-intramolecular activity, and heat, and the condition of contact with the chelating agent and hydrogen peroxide, Non-light-to-ultraviolet catalyst, phosphoric acid titania 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 resistance Titanium film forming agent, electromagnetic wave protection agent, superconducting agent, antistatic agent for fibers, yarns and plastics, antiwear agent, heat resistance, glittering agent, dry lubricant, rust inhibitor, heat resistance glitter Surface treatment agent, lipophilic paint film forming agent, hydrophilic paint film forming agent, surface treatment agent imparting high lipophilicity / hydrophilicity, moss remover, moss preventive, bactericides, antibacterial agents, fungicides, anti Mold 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 (immobilizing) agent, chelating agent, Water-based transesterification catalyst, CO ₂ , H ₂ O decomposition catalyst, particulate titania bonding adhesive, polysaccharide hydrolysis catalyst, rust preventive, wood preservative ant, pesticide, fish farming, antifouling / defouling It can be used for (self-cleaning) agents, UV heat ray protection agents, restoration agents for deteriorated / white flowers, etc., and can be formed into spinning and film forms as well as coating methods. New titanic acid monomers and The present invention relates to a polymer and a production method and use thereof.

In the present invention, “titania” is a term indicating “a titanic acid monomer having a protecting group and a polymer obtained by chain transfer polymerization”.

In known and publicly used titania, 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.

As these improved technologies, Saga-type titania / peroxytitanic acid (a 1 to 2% transparent liquid obtained by peroxylating the surface of a hydroxide titanate sol with hydrogen peroxide) has been developed. 9-124865, Patent Document 3: Japanese Patent Laid-Open No. 9-71418) A possible reason that the photocatalytic antifouling activity cannot be maintained for a long time is that the reducing group contains a peroxide group contained in atmospheric gas, sandfall, etc. 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).

There are further improved patent applications for titania phosphate (Patent Document 4: Japanese Patent Application Laid-Open No. 2004-130195, Patent Document 5: Japanese Patent Application No. 2001-111097) of Osaka City, Kogyo, Ken and YOO Corporation. In this method, 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 (titanate group and IPA are molecularly bonded) 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). 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. Further, although 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.

Further, in the claim, “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. In addition, it has not yet invented 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 Synthesize 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. When further added, 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.

Thereafter, in order to solve these drawbacks, YOO Corporation has disclosed an amorphous-metal composite in Patent Document 6 (Japanese Patent Laid-Open No. 2005-82863), but 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. 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. In addition, 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. When coated with a silane film, 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. (This is the same technology as the paint that can be freely designed for adhesion, and in contrast to Patent Document 1 (Japanese Patent Laid-Open No. 10-314598) that provides a hydrophilic surface with titania, Asahi Kasei (Hebel wall material) and others are external wall materials. It has the same spirit as the developed acrylic (hydrophilic self-cleaning wall material technology), and its self-cleaning effect is excellent for oil-based dirt such as exhaust gas, but it is good for hydrophilic dirt such as sewage and sandfall. Has the disadvantage that the dirt adhesion effect is more remarkable than the antifouling effect, and it is not catalytic effect.Transparent, high concentration, deodorizing, antibacterial, It does not solve the problem of permanently imparting and maintaining dirt and activity, and similarly, as a method of coating the surface of titania with a porous inorganic substance, Patent Document 7 (Japanese Patent Laid-Open No. 9-16418). In contrast, there is 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.

A product similar to this (Osaka Titanium Technology) apatite and coated with particulate titania has been developed. As a related patent, Patent Document 9 (Patent No. 9 of the National Institute of Advanced Industrial Science and Technology) No. 3837517: Application No. 20011.9), which is also encompassed in the patents of JP-A-2008-72003, the Japan Sheet Technology Research Laboratory, and exhibits 100% titania activity. Not a thing, 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 Honda 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.

However, the exposure of titania particles to the surface has changed to the gathering place of ultrafine contaminants brought about by attenuation of brightness due to dirt / dropping, reduced activity, and atmospheric precipitation, and the paint is once a few years. The same problems are likely to arise as they need to be renewed, have not been tracked for years in maintaining stable membranes, and do not solve the disadvantages of particulate titania.

Focusing on these disadvantages, titania (Patent Document 11: Japanese Patent Laid-Open No. 2002-104876) that forms a plate-like crystal developed by Otsuka Chemical is attracting attention. I can't. 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. Even if 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.

¡If peeling occurs, it cannot be denied that it leads to the same claims as particulate titania.

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.

According to the technology of the University of Tokyo's Solid State Chemistry Laboratory and Associate Professor Hiroshi Hatakeyama, who developed plate-like crystal iron, trivalent and pentavalent iron was made into plate-like crystals, and it was registered with Nature as the first technology in the world. Although it is a wonderful technology, it has not yet reached the technology to freely convert titania and other metals into plate crystals.

However, if this technology is used, it is regarded as an epoch-making technology used for power generation elements and electromagnetic wave protection by superconductivity, but it does not cause problems that cannot solve the drawbacks of Otsuka Chemical's plate titania. Absent.

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.

In addition, it is a titanic acid compound such as alkoxy titanic acid, peroxytitanic acid, titanium phosphate, etc., and it is a transparent aqueous solution. The synthesis technique and its polymerization mucus with 2% or more monomer (2% for Saga type) As a result, there is no titanium or titanium phosphate that becomes viscous from a syrupy form and eventually gels into a transparent jelly form, which returns to a transparent solution when added and dissolved in water or an organic solvent.

Conventionally, 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.

On the other hand, in YOO et al. Patent, 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. However, it has been found that the performance of the white flower is lost in 3 to 6 months, and 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.

In addition, there is a company that sells titania that uses a mixture of highly active granular titania and Saga type as a high light activity titania using a product (product name IS) developed by the inventor in cooperation with Saga University in 2002 and a similar product. Its activity is higher than that of Ishihara type, but it cannot prevent white flower and omission after 0.5 to 1 year. In addition, although three patents have already been published for those similar to this technology, the highly active granular titania composition using the monomer or polymer of the present invention as an adhesive does not fall off and has been active for more than 5 years. It cannot be compared with existing technology.

While paying attention to these, many patents related to amorphous titania have been filed in addition to YOO and others. However, white flower and omission cannot be prevented, and the performance cannot be maintained permanently.

In addition, as a technique that is very similar to the present invention, Patent Document 16 (Japanese Patent Laid-Open No. 2006-206855), Patent Document 17 (Japanese Patent Laid-Open No. 2006-56866), and Patent Document 18 (Japanese Patent Laid-Open No. 2005-15497) are added. As described in Japanese Patent Laid-Open Publication No. 2000-2001), 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. Water-soluble resol resin (varnish) of 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. There, near the mechanism for crosslinking gelation step to promote the polymerization, neither intended to suit the application proposed by the present invention, nor deserve conflict.

Next, 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) with a solvent to be dissolved has been proposed. 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.

Next, Patent Document 20 (Japanese Patent Application Laid-Open No. 3-126463) 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.

Next, 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.

Furthermore, in the present invention, when a chelating agent or a phosphoric acid compound is used, 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.

Furthermore, as an effect that the product of the present invention manifests, it 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.

Japanese Patent Laid-Open No. 10-314598 Japanese Patent Laid-Open No. 9-124865 JP-A-9-71418 JP 2004-130195 A Japanese Patent Application No. 2001-111097 JP 2005-82863 A JP-A-9-164188 JP 2005-104817 A Japanese Patent No. 3837517 JP 2008-72003 A JP 2002-104876 A Japanese Patent Laid-Open No. 11-228140 JP 2005-97395 A JP-A-6-55075 Japanese Patent Laid-Open No. 2001-111097 JP 2006-206855 A JP 2006-56866 A JP 2005-15497 A JP 2008-156280 A Japanese Patent Laid-Open No. 3-126663 JP 2004-182960 A

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. It is possible to freely design underactive / darkness inactive / light-active, and the activity and polarity can be freely selected simply by modifying the same basic molecule and modifying it. By the action of UV rays, heat, chelating agents, and hydrogen peroxide, dehydration and solidification and demethylation at the same time become titanium oxide bonds or titanium phosphate bonds, which can add activity and increase the strength and hardness of the film. , Novel titanic acid monomer, polymer capable of chemically bonding with active groups exposed on the surface of the base, and capable of permanently maintaining from white light to dark place activity, preventing deterioration of the substrate, and It is to provide their manufacturing methods and uses.

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. , Following the step of synthesizing the methoxy titanic acid monomer (2) 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 ½ molar value or less to 1 mol of titanic acid to the hydrated monomer or polymer to form a peroxyalkyl titanic acid monomer or polymer;
(7) In order to be applied after the polymerization step, it is diluted and dissolved in excess water and completely hydrated, or a hydrophilic organic solvent such as xylene and other hydrophilic organic solvents such as alcohols and ketones, or a mixed solvent. A dissolution process using
It is a novel titanic acid monomer and polymer and a method for producing the same.

Further, the present invention is an alkoxy titanic acid monomer or a peroxy titanic acid monomer obtained by the steps (1) to (2).

Further, the present invention is a novel titanic acid polymer obtained by the steps (1) to (4).

It is preferable that the excess alcohol is methanol or ethanol and the mineral acid is hydrochloric acid.

It is preferable that the excess alcohol is methanol.

In addition, immediately after coating, 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. This is a method for producing a titanic acid monomer and a polymer obtained by treatment.

It is preferable that the chelating agent is a phosphate compound or an anion exchange resin.

It is preferable that the excess alcohol and the mineral acid coexist with the alkoxy titanic acid monomer from a half-valence mole to an equivalent or less.

As 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.

It is preferable that 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. Of 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.

Using the alkoxytitanic acid monomer or polymer or peroxytitanic acid polymer formed by the above production method and having a protective function, 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, water-based transesterification catalysts, CO _2, H ₂ O decomposition catalyst, binding adhesive particulate titania, polysaccharides hydrolysis catalyst, rust, wood preservative termiticide, pesticides, fish drugs, antifouling It is preferably used for a decontamination (self-cleaning) agent, an ultraviolet ray heat protection agent, a repairing agent for a deteriorated / whitened surface, a water-soluble chelating agent insolubilizing (fixing) agent, a chelating agent, and the like.

Further, using the alkoxytitanic acid monomer or polymer or peroxy titanic acid polymer formed by the above-described production method, 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, C _2, H ₂ O decomposition catalyst, binding adhesive particulate titania, polysaccharides hydrolysis catalyst, rust, wood preservative termiticide, pesticides, fish drugs, antifouling dividing fouling (self-cleaning) agents, It is an application that is used for ultraviolet heat ray protective agents, repair agents for deteriorated / whitened surfaces, water-soluble chelating agent insolubilizing (fixing) agents, chelating agents, and the like.

Forming a chelate with the phosphoric acid compound, alkoxytitanic acid, titanic acid or titanium ion selected from the group consisting of water-soluble phosphoric acid, phosphate, and phosphoric acid alkyl ester on the chain transfer polymerization catalyst, at room temperature It is preferable that these become a linear transfer catalyst through a protective group that does not form a chelate bond or a chemical bond even when a reagent such as an organic or inorganic compound to be evaporated alone or a mixture or an anion exchange resin is used.

It is preferable that the water-soluble alkyl phosphate ester is methyl phosphate, ethyl phosphate, isopropyl phosphate, butyl phosphate and volatile phosphate compounds.

According to the novel titanic acid monomer and polymer production method of the present invention, a monomer that has excellent adhesion to all substrates, is synthesized at a high concentration, is infinitely transparent in water, and is also soluble in organic solvents. 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. 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.

It is a graph which shows the decomposition rate of gas at the time of irradiating with an ultraviolet lamp. In 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. Using the polymers TIPT-MC4-PM518 and TMT-MC2-10PM27.4 obtained in Example 2, 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. It is a graph which shows the result of having test-dried 100 ppm of acetaldehyde by the tetrabag method after hold | maintaining and drying for 7 hours to +/- 1 degreeC and 50% or less of humidity. In Example 28, it is a graph which shows the result of having measured the production amount of CO (carbon monoxide) for every time. In Example 29, it is a graph which shows the result of having measured the density | concentration of the hydrogen accumulate | stored in a tetrabag. In 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. In particular, when a titanium oxide bond and a titanium phosphate bond are formed, 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), For example, when trimethyl phosphate and sodium silicate (nonpolar) are used, 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. By forming a strong bond by intermolecular reaction and forming a network structure of several nanometers from angstrom, 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. Withstand and friction and stress, such as shock and provides a permanent titania film. In addition, 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. Nevertheless, it can provide the same or better activity than known titania from dark to ultraviolet, and has the same self-cleaning property as hydrophilic antifouling type titania (contact angle of 5 ° or less) that has no photoactivity. Provides a product with excellent catalytic activity, and allows the technology to be compared with known hydrophilic titania that cannot prevent hydrophilic soiling, while the known highly active titania is opaque and milky white emulsion, It is an epoch-making material that can form a transparent network film, so that the metal can be converted into a flat-plate network crystal. In addition to solving the disadvantages of the known titania catalyst, spinning is performed using a linear polymer. Can provide titania yarns, 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) agents, UV / heat ray protection agents, repair agents for deteriorated and whitened surfaces, water-soluble chelating agent insolubilization (immobilization) agents, chelating agents and other versatile functional metal materials Can do.

This technology is considered to be consistent with the technical theory that has both “non-conductive and conductive properties” discovered by RIKEN, using strontium titania. It is a novel titania and its manufacturing technology that are extremely excellent in remarkableness, inventive step, and novelty that express and provide a novel substance, function, and activity of a novel inorganic polymer that has “major properties”.

Further, in order to explain in detail the novelty, saliency, and inventive step of the present technology, the concept that became the starting point of the present invention and the details of the progress of the completed technology will be described in the order of the claims.

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. At first, focusing on the corrosion theory of pure titanium steel, 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. "In the presence of the oxidant" (Source: Sumitomo Metal Technical Report 5, 95 '(1964)) and "Coexistence of methanol (alcohol) and hydrochloric acid described on page 122" (God In laboratories reported No1491 (1962)), by noting significant corrosion occurs.

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) In addition, (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.

When the 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.

In addition, 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) + α, that is, α is an evaporation decomposition loss of methanol or hydrogen peroxide. Only about 1 mole value), and others can be synthesized up to the concentration using alkoxy titanic acid or titanium tetrachloride), and polymerized by chain transfer polymerization without diluting with water or an organic solvent and causing precipitation. Even a polymerized and gelatinized polymer can be diluted and dissolved to provide a transparent aqueous solution or organic solvent solution.

As a result of FT-IR analysis, 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. Monomers mainly composed of I, dimethyldiperoxytitanic acid (b) III, diperoxy, dichlorotitanic acid (a) II, forming a protecting group structure having the following molecular structure when hydrated. To infer.

[Estimation formula]

As shown in the above chemical formula, the corrosion of titanium metal is stabilized by the dissolution of titanium ions, which are dissolved in water indefinitely. Diluting the monomer synthesized with water at a high concentration close to the equimolar value of methanol to titanic acid from 2% or less because it is possible to use 2% or less because transparent titania is 2% or less) Since it does not advance to titanium oxide, it forms the most immobile effect against corrosion, it is thought that the titanium oxide film is not formed, and it is thought that it is eroded one after another. 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).

When water is added to the monomer having the protecting group (a), (b), or (c) obtained by the above method, it becomes a transparent diluted aqueous solution no matter how the monomer concentration becomes thin, and is used for paints. Chelating agents and ion exchanges that form strong chelates with water-soluble phosphoric acid or titanate ions typified by phosphoric acid compounds, including monomers that are soluble in organic solvents alone or in mixtures and do not hydrate When the resin is added, the known technique immediately produces titania phosphate or titanium chelate precipitate with a chelating agent, resulting in a sol that can be 100% precipitated by filtration. In the technique of the present invention, the monomer concentration is increased. Depending on the addition of chelating agents and ion exchange resins that form chelates with titanic acid, the viscosity of the monomer gradually increases to several cP / 20 ° C (B-type viscometer) and becomes a water tank. Before long it became clear Naru Nikawaka point (diesel, jelly-like). As hydrochloric acid approaches 4 molar values, it does not gel and thickens, and eventually the viscosity decreases.

When this polymerized polymer is dissolved in a large amount of water, a uniform transparent aqueous solution is obtained, and a polymer formed from a monomer that is not hydrated is set to the maximum value, depending on the water content. It dissolves infinitely and neither cloudiness nor precipitation occurs.

From the above, 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. However, it is considered that while 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.

In addition, when the above reaction is illustrated, it is estimated that the 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.

[Estimated reaction formula]
The estimation formula for the chain transfer polymerization of the reaction system (c) I is shown in [Chemical Formula 4], the end group of which is considered to be [Chemical Formula 5], and the molecular nodes forming the linear polymer chain The structure of is considered to conform to [Chemical 29].

Next, 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, For the purpose of showing strong intramolecular and self-activity in the dark (under no light) due to the phenomenon of anode and cathode and the compatibility of yellow phosphorus and red phosphorus, the examples were limited to phosphate compounds However, if 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. There is a possibility of creating a new functional material in a new application field not described. For example, if the chain transfer catalyst having a large organic property is used and the ratio to the titanium ratio is increased, 100% silicone Polymer It is estimated from this definition theory that 100% titanium-based plastics or paints similar to the examples in the table can be designed freely, and that linear polymers of other polyvalent metals can be created. Is done.

Next, 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.

Next, a monomer that does not use a chain transfer catalyst and is infinitely soluble in water having a protecting group, and a polymer polymerized using this monomer while desalting with an ion exchange resin show little activity in the absence of light. Under the light, demethylated by solar heat or ultraviolet rays, forming a titanium oxide condensation in a network, showing high activity, outstanding brightness and transparency, hardly affected by the polarity of the coated surface, a wide undercoat agent It is also effective for repairing the surface of synthetic paints where the coating surface has deteriorated due to deterioration such as ultraviolet rays (considered by chemical bonding with terminal groups on the deteriorated surface of the paint), When phosphoric acid or phosphoric acid ester is used to be equivalent to titanic acid, after application, it is dried and, after aging, almost all become titania phosphate bonds, and in the dark (under no light) Maximum intramolecular self-activity Are shown, because under light activity is small, the surface to be coated under ultraviolet is effective to decompose efflorescence easily surface as an undercoat material.

In order to produce white flower by applying titania and titanic acid compound (1) When the phenomenon of “self-white flower” that titanium compound becomes coarse particles of titanium oxide and (2) polarity of coated surface do not match It can be invented that there is a phenomenon "peeling white flower" that peels off due to a high coating concentration and (3) a phenomenon "erosion white flower" that occurs when the coated surface deteriorates due to photocatalytic activity. It was. Since the product of the present invention is not a crystalline particle titanium compound, “self-whiteness” does not occur except those that include a portion of the titanium oxide bond that imparts intense activity. Next, “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. Of course, depending on the chemical composition of the coated surface (the surface of the coating film that is susceptible to oxidative degradation), “erosion whiteness” may occur. In that case, 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.

Next, after applying this titania, apply a temperature higher than the boiling point of the alcohol, apply ultraviolet light, receive natural ultraviolet light, or use a chelating agent such as phosphoric acid or a phosphoric acid compound for the undercoat or overcoat. When overcoating the dried titania film with hydrogen oxide, the alkyl group remaining in the linear polymer undergoes a desorption reaction to form a titanium oxide bond, a titanium phosphate bond, or a peroxytitanium bond. It is possible to increase the activity rapidly.

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.

That is, when applied, 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.

Next, 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) (This technology is also attributed to the technology of the present invention) and those obtained by chain transfer polymerization using the monomer of the present invention, as in the Saga-type patent method, can be photoactive even without heat treatment. However, 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). 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. However, 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.

On the other hand, 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.

Next, 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.

Hereinafter, the novel titanic acid monomer and polymer of the present invention and the production method and use thereof will be described in more detail.

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. Following the process of synthesizing peroxytitanic acid monomer and peroxyalkoxytitanic acid monomer with protective function by adding excess hydrogen peroxide without adding water and adding pure alkoxytitanic acid monomer to alcohol system (2) After the protective function formation step (or peroxytitanate monomer synthesis step), dilute with water according to the polymerization concentration The hydration reaction while, and alkoxy titanate monomers completely dissolved, a synthesis step of synthesizing peroxy titanate monomer, a peroxy alkoxy titanate monomers,
(3) Water can be added to the alkoxytitanic acid monomer, peroxytitanic acid monomer, or peroxyalkoxytitanic acid monomer depending on the polymerization concentration, or the monomer can be mixed with alcohol or alcohol instead of water or alone. 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.

First, the process (1) will be described. (C) 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. And (a) II hydrogen peroxide and titanium tetrachloride, (b) III or hydrogen peroxide, methanol and alkoxytitanic acid coexist to form a protective function.

[Estimation formula]

As 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. Further, 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. Further, it is preferable that the alkenyl titanic acid monomer has a valence of at least ½ valence to the equivalent. In the case of less than ½ valence mole, 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. There is a problem that 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.

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 ½ molar equivalent and equimolar relative to tetravalent molar titanic acid, most preferably hydrochloric acid. In addition, excess alcohol, at least an equimolar or higher alcohol, and most preferably, when alkoxytitanic acid is added without adding water in the presence of methanol, alkoxytitanic acid is hydrolyzed to form hydroxytitanic acid, As shown in the formula ((a) (b) (c)), 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.

Next, the process (2) will be described. 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) will be described. The step (3) is a step of diluting by adding water according to the polymerization concentration of the alkoxytitanic acid monomer. Here, 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. In addition, 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) will be described. The step (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. Therefore, compounds that volatilize at room temperature and pressure are preferable.Inorganic compounds may interfere with catalyst activity or use against the main purpose of this technology. In consideration of the point that 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. And 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. In addition, 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.

Next, the present invention will be specifically described with reference to examples.

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)”.

Next, 190 g of tetrachlor was added to 272 g of 50% hydrogen peroxide (2 times excess (2 mol of H ₂ O ₂ contributed to the formation of protective groups with respect to 1 mol of titanium tetrachloride)). Titanium was added, and the reaction was carried out with appropriate cooling in a large-scale synthesis so that the temperature was 50 ° C. or lower. Further, 172 g of tetramethoxy titanic acid was reacted at 50 ° C. or lower with a solution of 272 g of 50% hydrogen peroxide and 1 kg of methanol, and the obtained product was designated as “POT-OM ₂ ” (b).

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.

Next, 1 kg of water was added to TIPT-MC4, and a hydration reaction was performed at 40 ° C. or lower. As a result, a transparent monomer was obtained, which was designated as “TIPT-MC4-10”. Similarly, 1 kg of water was added to TIPT-2MC2 and reacted in the same manner. As a result, a transparent monomer was obtained, which was designated as “TIPT-MC2 10”. Similarly, 1 kg of water was added to TMT-MC4 and reacted in the same manner. As a result, a transparent monomer was obtained, which was designated as “TMT-MC4 10” (3). Further, 1 kg of water was added to TMT-MC2 and hydrated to obtain “TMT-MC2 10” (4). Similarly, 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”.

When each of the obtained monomers corresponding to 10% was diluted in water, it was dissolved infinitely, no white precipitate was formed, and even when stored for 3 years, it was transparent and no precipitate was formed.

The absorption of 700 cm ^-1 to 1200 cm ^-1 is very small,

2800 ~ 3000 cm ^-1, in order to absorb the methoxy titanate 1350 ~ 1450 cm ^-1 was found to be mainly in TIPT starting material, mostly becomes methoxy titanate, peroxy titanate system,

1800 cm ^-1 in mostly longitudinal and 1000 cm ^-1 before and after the absorption of the monomer synthesized in this method is transparent, causing white turbidity

Absorption of 1000-1400 cm ⁻¹ , 3000-3400 cm ⁻¹ ,

Of 1000 ~ 1200 cm ^-1, since the absorption of titanium oxide of 1700 cm ^-1 was detected almost monomer is purely bulk polymerization course is estimated to linear oligomers are pure monomers are not formed The

As described above, 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.

That is, 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.

[Estimation formula]

The 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.

However, in an excessive solvent system, methanol and hydrochloric acid, hydrogen peroxide, and hydrogen peroxide and methanol may form protective groups in the form of titanic acid and complex.

Normally, 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.

This is considered to exist as fine crystals of 50 nanometers or less that appear as a transparent liquid having a titanium oxide bond and a hydroxyl group (titanate group) on the surface (terminal) even at 10% or more.

Chemical Industry Journal, Vol. 23, No. 1 (1997) p129-131.

In addition, as the 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. In addition, there is no technology that can be dissolved in an organic solvent in the world, but other metals are considered to be water-soluble or solubilized in an organic solvent by this method.

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.

Comparative Example 1
When 1 mol of tetrachlorotitanium was added to 2 kg of a mixed solution of water and isopropyl alcohol 1: 1 based on the synthesis method of YO type titania, white precipitation occurred and precipitation occurred.

When the precipitate having a hydroxyl group (titanic acid) on the surface of the titanium oxide crystal was filtered and the transparent liquid portion was analyzed, the titanium content was 0.5% by weight. It was considered as a protective colloid solution with titanic acid isopropyl and was designated as “Y-TIP”.

Next, when 190 g of titanium tetrachloride was added to 2 kg of water based on a method for synthesizing Saga-type titania, white precipitation immediately occurred and a titanium oxide (titanium hydroxide) sol was formed.

A large excess of 4 mol (272 g) of 50% hydrogen peroxide was added to this product, and the content of peroxytitanic acid in the aqueous solution obtained by filtration was 1%. Considered to be the saturated concentration of peroxytitanic acid, this was defined as (S-POT).

In addition,

Is tetravalent, so 1 mole is 4 molar.

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). Acid trimethyl ester) and polymerize, gradually become viscous, transparent gelation point or highest viscosity point (viscosity increases and becomes thicker, does not gel, and when added further, viscosity decreases As a result of measuring the concentration of the catalyst reaching the gelation point, the concentration of the catalyst reaching the gelation point was measured in the same manner by chain transfer polymerization of 2 mol hydrochloric acid (1/2 mole of titanium) monomer. Met. In addition, the rotation speed at the time of reaction was performed at 10 m / min or more, and the rotation speed was adjusted by the dropping speed and the cooling efficiency.

When 1 mol of titanium has 4 mol of HCl (equal molar number), the polymerization does not reach high molecular weight, terminates at low molecular weight, does not reach the point of gelation, and phosphoric acid and trimethyl phosphate are used as solvents. It is thought that the viscosity decreases as it goes on. The addition of a large excess of the phosphoric acid compound does not produce a cloudy chelate precipitate, demonstrating the stability of the protecting group.

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.

On the other hand, when phosphoric acid and trimethyl phosphate were added to the 1% solution of “S-POT”, the viscosity increased, milky whitening was reached and the gelation point was reached.

When stopped just before gelatinization, it became cloudy dissolved in water, but the gelatinized material did not dissolve even when dissolved by adding water. As described above, 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 ¾ molar ratio to methoxytitanic acid 10% equivalent of TMT-MC ₃ 2% equivalent and TMT-MC ₄ 10% equivalent and 2% equivalent As a result of adding 8.5% phosphoric acid to 200 g each (4/4 molar value with respect to methoxy titanic acid) and measuring the addition limit of the phosphoric acid catalyst reaching the gelation point (or peak of thickening), It became as shown in Table 2. Further, hydrochloric acid was added to TIPT-MC ₂ (hydrochloric acid 2/4 molar value) equivalent to 10% and 2%, and TIPT-MC ₄ (hydrochloric acid 4/4 molar value) equivalent to 10% and equivalent to 2%, and TIPT-MC ₂ The number of grams as a result of conducting the same test using TIPT-MC ₃ (hydrochloric acid 3/4 molar value) equivalent to 10% and equivalent to 2% is shown in parentheses.

Below 2/4 molar value of hydrochloric acid, it becomes cloudy when phosphoric acid is added, and when it becomes 1.8 / 4 molar value or less, it forms a cloudiness with precipitation, but when it is above 2/4 molar value, it gradually polymerizes without becoming cloudy. Occurs, thickens, and eventually reaches a transparent glue point. When the phosphoric acid is further added while forcibly stirring until reaching the gelation point, it is considered that the solvent (dissolution) effect returns to the viscous liquid because 8.5% phosphoric acid is used. Even if a large amount of phosphoric acid is added, white precipitation does not occur, thus demonstrating the presence of protecting groups. Since the agitation becomes uneven at the time of gelation, further dilution of the polymer sample after the gelation point causes the white orinic polymer to suspend without precipitation. This is a heterogeneous system with some cross-linking of polyacrylamide. This is the same phenomenon that occurs when linking, and it is apparent that the linear polymer was formed until the stirring stopped, and it was thought that chain transfer polymerization was performed.

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.

Furthermore, it is presumed from the approximation with the data in () that it has been converted to the TMT type even if it starts from TIPT.

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.

In 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. As a result of the ultraviolet irradiation methylene blue test method, the following values were obtained.

Experiments were conducted on the behavior of peroxytitanate polymer.

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.

"Test of adhesive effect of known granular titania"
The results of the above test using a mixture of 2% product of Titania STS-01 manufactured by Ishihara Sangyo Co., Ltd. and 2% product of Saga-type titania TA (Teo-Techno) are shown in Table 5 as AB and C. As a binder, the product of the present invention is more effective than the Saga type because the hydroxyl group (titanic acid), which is a terminal group of commercially available particulate titania, and the ester group on the base surface are transesterified with a water-soluble alkoxytitanic acid protecting group. In order to form a strong chemical bond through a substitution reaction, it is considered stable for a long period of time to prevent cracking, peeling and dropping.

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.

According to the theory of polymerization, when polymerizing in 2 kg including 1 kg of methanol and 1 kg of water, and when polymerizing in 1 kg of methanol, the monomer concentration before the polymerization is approximately doubled, the polymerization rate is increased, and the gelation is increased. The point will be faster and the amount of catalyst should be less, but the opposite is that the polymer based on methoxytitanic acid is greater in methanol than in water / methanol Therefore, the gelation point is slow and the polymerization in the water-free system is only water contained in phosphoric acid, hydrochloric acid and hydrogen peroxide water, and the water of the monomer in which hydrochloric acid and methoxytitanic acid form a protecting group. This is probably because the activity of the chain transfer catalyst is suppressed because the sum rate is extremely low, and the reaction proceeds slowly. The order of chain transfer is thought to be due to the chain transfer of hydrated methoxy titanate groups and phosphoric acid formed at the end, with HCl replacing H ₂ O and further HCl replacing the catalyst (eg phosphoric acid). . This theory is similar to the oxalic acid method used in the synthesis of barium titanate, that is, when barium chloride and titanium tetrachloride are reacted, if oxalic acid is present together, dehydrochlorination will result in barium oxalate titanate. Yes.

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 mmφ 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 results are shown in Table 7.

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.

On the other hand, polymers that have undergone chain transfer polymerization with a chelating agent do not cause white precipitation even after dehydrochlorination and do not thicken. 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.

Chemical formula 5a

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.

The polymer after removal of monomeric hydrochloric acid and the dehydrochloric acid solution of phosphorylated polymer proved to be a strong rust preventive and are expected to be effective for non-chromium plating of automotive steel sheets. Not only as a rust inhibitor, but also expected is that methyl titanate and water or phosphoric acid and methyl titanate form a protective group like a complex (Chemical Formula 5b). There are acrylic and urethane types of body paints, but it is thought that methyl, OH, isocyanate, carboxyl, amino groups, etc. are left exposed on the surface. It can be inferred that the acid complex reacts strongly from the fact that the alkoxytitanic acid used as a raw material becomes a strong ester conversion and catalyst, and it can be considered that the paint peel strength and adhesiveness can be greatly improved.

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. for 1 hour, 2 hours and 3 hours (heat treatment activated (X)) and 10 ± 20 days in a dark place at 20 ± 1 ° C., 30 days Hold the sample (self-intramolecular activation (Y)) and unprocessed (ultraviolet activation (Z)) into the bag by JIS tetrabag B method, inject 100 ppm acetaldehyde, 500 W black light (ultraviolet The decomposition rate of the gas was plotted. The results are shown in FIG.

(X) Heat treatment activated sample increased to a maximum of 100 to 150 ppm, (Y) Dark place retention (self activation) increased to a maximum of 110 to 180 ppm, and (Z) Untreated (only UV activated) increased to a maximum of 250 ppm to 300 ppm. It was found by UV that the activity suddenly appears when the methyl group is eliminated. It is inferred that the heat treatment becomes active in a short time and is self-activated due to the redox effect of the anode, cathode and red phosphorus / yellow phosphorus generated between the phosphoric acid and titanium in the molecule when kept in the dark for a long time. (Provides proof of dark activity).

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)

110 ℃ / 3Hr Phosphate treatment Heat treatment
(A) TIPT-MC2-10-P15.6 (A)-(1) ○ A- (2)
(B) TIPT-MC2-10-PM29.4 (B)-(1) B- (2)
(C) STS-21 ×, (D) TA △

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.

Those treated with phosphoric acid further showed high activity even in the dark, and were found to exhibit immediate activity equivalent to or better than 110 ° C / 2Hr treatment. Known titania showed immediate activity in a tetrabag, but methoxytitanate polymer was The JIS method was demethylated gas, so it was limited to the disadvantages (blind spots) of the JIS method that did not show activity in several hours, but this method (A), (B), especially the method (B) It was proved that it is effective as a construction method for PVC cloth, indoor and new homes, or when it is required outdoors in winter, cold and cold, or cloudy weather.

(Discussion)
Compared to the treatment at 110 ° C./2Hr in Example 10, it is considered that demethylation occurs by self-activity even in the dark.

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.

When the sample TIPT-MC4-PM518, 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.

Furthermore, this high dark type titanic acid catalyst binds to and associates with the surface of the cloth to form a film. However, 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, Inside the cloth, especially inside the ester plasticizer, 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

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. .

(Discussion)
The glass test piece of Example 10 and the PVC sheet behave slightly differently. Methanol decomposed by self-activity in the dark does not gasify and moves to the plasticizer in the cloth. It is assumed that gas is generated.

Example 13
Polarity contrast test and self-cleaning test Samples with the highest hydrophilicity to the highest lipophilicity are arranged as shown below. As a comparative example, Saga-type peroxytitanate TA (Teo-Techno) is added, and each 2% solution. Was spray-coated on a slide and kept in a box at 20 ± 1 ° C and 50% humidity for 5 hours. As a comparative example, 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. Moreover, after apply | 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.

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). Under the conditions, impregnated with 2% solution of the alkoxy titanic acid polymer used in Example 6, and attached to the outdoor wall surface, contrasted with discoloration caused by mold and moss, tied 10 flooring, left under the floor and discolored Table 11 shows the results of comparison between peanuts and white ants.

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 ×.

In addition, the absence of phytotoxicity is indicated by () in parentheses, △ if there is a little, and × if there is a considerable amount. As a comparative example, Top Gin M ^* (Nippon Soda Co., Ltd.) and blank were compared.
* The degree to which the skin peels and falls, and the leaves turn and fall.
None ○: There is no change △: There is considerable disappearance of radiance on the peels and leaves ×: Fallen fruit, fallen leaves

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.

Apply the 2% solution of hydrophilicity (A) and lipophilicity (B) to the surface of the K ground I tunnel until the surface is evenly wetted, and after 10 months, the untreated surface is used as a comparative example. The soot adhering to the lower part is wiped with gauze of 20 cm x 40 cm and about 1 mm in thickness over an area of 100 cm x 200 cm, extracted in 500 cc of water, and the concentrations of sulfuric acid and nitric acid contained therein are ionized. The results measured with a chromatograph (manufactured by Toa DKK Co., Ltd.) are shown in Table 14 and the NOx and SOX resolution in exhaust gas were estimated and compared.

In addition, the soot was washed with tap water, and “Good for ○”, “Good for △”, and “No for good” was written in parentheses.

It is presumed from this result that 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.

Particularly, (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.

Considering, it was found that the type having a great affinity with Saran Wrap has a greater protection. A uniform network of several angstroms to several nanometers may be formed, and it is possible to cope with deformation and bending by including 40 ± several% plasticizer in Saran Wrap (registered trademark) It is considered that it is effective for a surface containing plastic, particularly ester or OH, because it is transesterified with a methoxytitanic acid group.

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.

[Estimated chemical formula]
One case

(Discussion)
Even if a chain transfer polymerized polymer is dehydrochlorinated, the end is blocked, and even if a chelating agent (chain transfer catalyst) is added to this, it does not thicken and white precipitation does not occur. It was discovered that the methoxy titanate group is extremely stable, and neither self-polymerization nor chelation occurs in a short time in an aqueous system.

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.

[Estimated chemical formula]

From this reaction route, it is considered that 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, In addition, even in the absence of hydrochloric acid, 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. In other words, the estimated chemical formula shown in the terminal formula

Estimated chemical formula
The following estimated chemical formula shown in the polymer chain equation

Is the estimated chemical formula by condensing two methoxy groups

It is estimated that it is stabilized in the form of

Next, when the polymer obtained by adding a chelating agent (for example, phosphoric acid) as a complex (complex salt) to the methoxytitanic acid hydration protecting group obtained above is applied and dried, the hydration protecting group becomes more dehydrated and concentrated. At the same time, 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.

The reasoning about the mechanism in which the monomer and polymer having the obtained protective group are applied and the protective group is destroyed and crosslinked is described below.

Estimation formula

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 0.5mmφ 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 mmφ 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 300mmφ, 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.

As a comparative example, in the test section that had been polished and then subjected to fluorine treatment (manufactured by Beebrand Medico Dental), the faint radiance disappeared from around 10th.

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.

By rotation, 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. Indirect heating for 30 minutes, with yuba koge on the water surface and wall, (B) put “Daikei ceramic drop lid” while cooking 3 rice in a rice cooker (ECJ-IHP18 Sanyo), sticking rice grains The state was contrasted. In (C), black tea was put in a Daqing black tea cup, evaporated to dryness in an oven, and the adhesion state of black tea tannin was compared. (D) burned rice with rice using a Daqing-style direct fire ceramic pan.

In addition, kogation and adhesion were evaluated by applying tap water pressure based on “can be taken well”, “can be taken”, “cannot be taken”, and “cannot be taken ×” and are shown in Table 19.

Note) It was found that protein, starch, and tannin can be self-cleaned.

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 mmφ 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 mmφ (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.

As a result of putting 5 g of magnesium metal wire in the tetra bag and absorbing the generated O ₂ , the CO production rate was accelerated to ○-○ and Δ- △ (the measuring machine was made by Shimadzu, GC-MS- QP2010 was used). The results are shown in FIG.

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. 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.

1) When the base is wiped with zet water or a compress and air-dried, a polar to non-polar material is applied using a brush, and the wet surface retains a stable film. When separation is performed, it is assumed that there is no affinity.

2) Next, in an environment where lipophilic substances such as dust and exhaust gas that cause dirt adhere, a hydrophilic grade may be applied thereon, and an environment where hydrophilic dirt such as dust will adhere. Then, the method of applying a lipophilic grade is selected. The results are shown in FIG.

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. .

2. As catalyst poison, sodium silicate 2% solution and phosphoric acid 2% solution were reacted to obtain “PS” as sodium silicate phosphate 2% solution.

Next, 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 / △. When the ratio of trimethyl phosphate is increased, the polarity of PMS decreases and can provide lipophilicity.

3. Apply methylene blue methanol solution to a glass preparation, dry, and apply PS to the undercoat agent, and spray apply A (TIPT-MC ₄ -P254) and B (TMT-MC ₂ P14) without applying. And left under the PVC corrugated roof (under weak UV light). Table 22 shows the results of measuring the time for decoloring after untreatment.

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 As a comparative example, a commercially available titanium nitride powder (particle size: 1.5 μm, manufactured by Nippon Shin Metal Co., Ltd.) is used as a comparative example. ) And blended to a solid content of 50% by weight, kneaded in a mortar, repeatedly applied and dried on a PET film, adjusted to 30 μm, 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.

Note: 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 mmφ 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%. When changing the flow rate of the starch, 10 l / Hr in TIPT-MC ₂ -P6 in 56%, 57% in TIPT-MC ₂ -PM20, in 15 l / Hr, 31% in the TIPT-MC ₂ -P6, TIPT -MC ₂ -PM20, 32%. As a result of continuous operation at 5 liters / hr, the catalyst efficiency has fallen from around 3.5 hours, so when the liquid is drained, washed with water and filled with 1% hydrochloric acid for 10 minutes, further washed with water and restarted, The activity could be restored. It is thought that it may be due to activity inhibition by a trace amount of Na ⁺ and K ⁺ ions contained in starch.
Analysis: HPLC method, sugar analyzer SU-300, manufactured by Toa DKK Co., Ltd.

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.

While aeration of 60 L / Hr in a 1 m ³ tank and adding 10 L / Hr of fresh water well through the plant of Example 35, 50 juvenile pupae were added and the survival rate for each day was measured (survival) number).

(Discussion) It is considered that water is decomposed to generate active oxygen, which shows a bactericidal effect and a BOD component decomposition effect produced from excrement.

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.

[Discussion]
From 1), 2), 3), 4), 5), 6) and 7), 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.

[Discussion]
Even when a transparent film is formed, Saga-type titania is in the form of particles of several nanometers to several tens of nanometers, and when coated and dried, peroxy groups are unlikely to form titanium oxide bonds and are reduced to titanium hydroxide, which binds to titanium oxide. Even so, peroxy is exposed on the surface due to bonding between particles, and this becomes a titanium hydroxide group, so the titanium oxide bonding nuclei are not uniformly arranged, so it seems that the ultraviolet ray and heat ray protection ability is small .

Example 39
Antibacterial, deodorant, rain removal, ground removal clothing test Using the sample used in Example 6 and a titanic acid group added with ½ mol of hydrogen peroxide, antibacterial and antibacterial Table 28 shows the results of odor, rain erasure and lichen erasure tests.

[Antimicrobial test]
Bulgarian yogurt (manufactured by Meiji Dairies) and milk (manufactured by Meiji Dairies) were mixed at a weight ratio of 3 to 7, and 20 g was dispensed into a 30 cc test tube. In addition, shake, leave at 20 ° C. ± 5 ° C. window, slowly tilt every hour to measure the point of thickening, and further stand at point where separation occurs () in Table 28 Shown in time.

[Deodorization test]
Absorbent cotton was impregnated with the above sample, drained with a thick towel, and dried for 1 hour with a ventilation dryer at 75 ° C. ± 1 ° C. to prepare. Wrapped in a tissue paper soaked with 3 g of paraformaldehyde, placed in the same tube as the above test tube, the treated cotton wool was divided into 10 g units, and this was plugged. Let stand for 5 minutes at the window of 20 ° C ± 1 ° C, and the five evaluators do not smell (5), smell a little (4), smell (3), quite smell (2), smell strongly (1 ), And the average value is shown in Table 28 by rounding off.

[Rain dripping elimination test]
Long-term field data on the elimination of green moss growing on the north-facing side with a slate on the roof fence is shown in Example 6 (Table 5). A black rain spilling stain was eluted from the bottom of the fence cover along the side seam. Table 28 shows the number of days when it was determined that the 2% solution was brushed, observed to disappear every 5 days, and completely erased.

[Lichen elimination test]
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.

In the comparative example, the brightness was inferior to that of the example from the start, and the brightness declined rapidly with time.

Example 41
1) 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).

2) Attach a stirrer (emulsifier, Kinematica PT-2000, Switzerland) to the flask containing the liquid of (A), allow cold water to overflow into the water bath, and place (B) liquid in the dropping funnel. When the mixture was added so as not to exceed 40 ° C., a slightly milky white uniform reaction solution was obtained. The obtained liquid was not separated and precipitated.

3) A 10% equivalent solution of barium alkoxytitanate chloride as a reaction solution was diluted to 2%. This liquid was passed through an exchange tower packed with a weak anion exchange resin through a 30 mmφ × 300 mmL column at a passing speed of 10 mmL / min, and fractions were collected every 50 mL, and fractions not clouded with silver nitrate were collected.

4) 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. In the obtained 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.

Comparative Example 41
By a known sol-gel method, 1 mol of diisopropoxybarium was dissolved in isopropyl alcohol to prepare a 10% solution, which was designated as solution (A).

Next, tetraisopropyl titanic acid was dissolved in isopropyl alcohol to obtain a 10% solution, which was designated as solution (B).

When (A) liquid equivalent to 1 mol was put in the apparatus which attached the emulsifier to the flask used in Example 41, and (B) liquid equivalent to 1 mol was dripped on the same conditions as Example 1, it became cloudy. When the dropping was completed, it became a sol.

Samples diluted with water to 2%, 0.2%, and 0.02% and samples diluted with isopropyl alcohol to 2%, 0.2%, and 0.02% were the same as in Example 41. As a result of applying to the preparation by the above method, all the samples became white opaque, and after drying, they were removed by wiping with gauze.

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) [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. or lower. As the solution was added dropwise, the viscosity increased and the mixture became glued at the time when 0.01 mol was added. While stirring the bottom of the flask while stirring with a moon-shaped peller, the remaining 0.09 mol of phosphoric acid methanol solution was added and reacted for a total of 60 minutes, and the bath temperature was kept at 80 ° C. ± 5 ° C. The solvent was distilled off to dryness and kept for another 30 minutes to obtain 29 g of powder. The rest was attached to the flask.

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.

(B) [Experiment 2: Titania citrate chelator]
When titania citrate was synthesized with the same apparatus, composition and conditions as in Experiment 1, the number of moles reaching the gelation point was 0.02 moles relative to 0.1 mole of tetraisopropyl titanate.

Similarly, the remaining 0.08 mol was added to the linear polymer for crosslinking, slurrying (reticulation), and drying to obtain 43 g of powder, which was slightly adhered to the flask.

As a result of conducting an extraction test in the same manner as in Experiment 1 using 20 g of the obtained powder, 19.4 g was obtained.

(C) [Experiment 3: Crust Titanate Chelating Agent]
Under the same conditions as those in Experiment 1, methanol and hydrochloric acid solution containing 0.1 mol of tetraisopropoxytitanic acid was crushed with astringent peel with the apparatus of Japanese Patent Application No. 2009-129419, and 20 g of powder was added to 100 cc of water. The slurry dispersed in this manner was reacted under the same apparatus and conditions as in Experiment 1 and dried to obtain 41 g (the rest adhered to the dose flask). 20 g of this powder was extracted under the same conditions as in Experiment 1 and dried to obtain 18.8 g of scabbard titanate chelating agent.

As a comparative example, 20 g of the same crushed crushed product was extracted under the same conditions as in Experiment 1 and the obtained crushed sole chelating agent was 11.5 g.

(D) [Discussion]
By immobilizing water-soluble titania, the column can be packed into the column and the target metal can be efficiently recovered using the target chelating agent. Of chelating agents using biomass proposed by Japanese Patent Application No. 2006-60150 and Japanese Patent Application No. 2006-280628, which were jointly researched by the inventor for many years in industry, government, and academia. It can be used as a low-cost fixing agent for cross-linking agents, particularly low-molecular water-soluble organic acids, saccharides and oligosaccharides.

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. 108, and “Brightness” and “Peeling white flower (Comparative example white flower)” were compared with time. Brightness was excellent and no peeling was assigned 5 points, and “disappearance of brightness” and “exfoliation white flower” were assigned 0 points (average values of 5 evaluation points were rounded down).

[Discussion]
(1) The coating concentration limit of particle-type titania (one-time application in which the spray surface gets wet) is 0.2% or higher, or 0.2% is not applied several times, and no glitter is produced.
(2) In the titania of the present invention, even when 0.02%, the brightness is remarkably 0.2 to 0.02% was found to be more effective for preventing the brightness and exfoliation whitening. The consumption of titania per 1 m ² corresponds to 1/10 to 1/50.
(3) It is considered that the effect of dehydrochlorination is more effective in preventing glitter and exfoliation whiteness because there is no gas negative effect due to dehydrochlorination.

1 TIPT-MC ₂ -10 P15.6 Measured by tetrabag method after 110 ℃ / 3Hr treatment X
2 TIPT-MC ₂ -10 PM29.4 Measured by tetrabag method after 110 ℃ / 3Hr treatment X
3 TIPT-MC ₂ -10 P15.6 Measured by Tetrabag method after 110 ℃ / 2Hr treatment X
4 TIPT-MC ₂ -10 PM29.4 Measured by Tetrabag method after 110 ℃ / 2Hr treatment X
5 TIPT-MC ₂ -10 P15.6 Measured by Tetrabag method after 110 ℃ / 1Hr treatment X
6 TIPT-MC ₂ -10 PM29.4 Measured by Tetrabag method after 110 ℃ / 1Hr treatment X
7 TIPT-MC ₂ -10 P15.6 Measured by Tetrabag method after standing in the dark for 30 days Y
8 TIPT-MC ₂ -10 PM29.4 Measured by Tetrabag method after standing in the dark for 30 days Y
9 TIPT-MC ₂ -10 P15.6 Measured by Tetrabag method after standing in the dark for 20 days Y
10 TIPT-MC ₂ -10 PM29.4 Measured by Tetrabag method after standing in the dark for 20 days Y
11 TIPT-MC ₂ -10 P15.6 Measured by Tetrabag method after standing in the dark for 10 days Y
12 TIPT-MC ₂ -10 PM29.4 Measured by Tetrabag method after standing in the dark for 10 days Y
13 TIPT-MC ₂ -10 P15.6 Untreated (measured by the Tetrabag method immediately after drying the coating) Z
14 TIPT-MC ₂ -10 PM29.4 Untreated (Measured by Tetrabag method immediately after coating is dried) Z
15 TIPT-MC ₂ -10 P15.6 Phosphoric acid treatment A- (2)
16 TIPT-MC ₂ -10 P15.6 110 ℃ / 2Hr heat treatment A- (1)
17 TIPT-MC ₂ -10 PM29.4 Phosphate treatment B- (2)
18 TIPT-MC ₂ -10 PM29.4 110 ℃ / 2Hr heat treatment B- (1)
19 TA (Saga-type Tio-Techno) 2% (D)
20 STS-21 (Ishihara Sangyo) 2% (C)
21 TMT-MC ₂ -10-PM27
22 TIPT-MC ₄ -10-PM518
23 TA (Saga type)
24 STS-01 (Ishihara type)
25 TIPT-MC ₂ -P6 With metal magnesium 26 TIPT-MC ₂ -PM20 With metal magnesium 27 TIPT-MC ₂ -P6 Without metal magnesium 28 TIPT-MC ₂ -PM20 With metal magnesium When not 29 TIPT-MC ₂ -P6
30 TIPT-MC ₂ -PM20

Claims (15)

1. (1) Pure alkoxy titanate monomer is added to a system in which excess alcohol without water and mineral acid coexist, or titanium tetrachloride without adding water to excess alcohol without water (hereinafter referred to as tetrachloride) Adding titanium tetrachloride to a step of synthesizing an alkoxy titanic acid monomer having a protective function added thereto, or industrial high-concentration hydrogen peroxide (hereinafter referred to as hydrogen peroxide), Following the process of synthesizing peroxytitanic acid monomer or peroxy, methoxytitanic acid monomer with a protective function by adding pure alkoxy titanic acid monomer to excess alcohol and hydrogen peroxide system without adding water (2) The alkoxy titanate monomer, peroxy titanate monomer or peroxy methoxy titanate monomer (hereinafter referred to as peroxy titanate monomer) Tan called acid monomer), an organic solvent or by adding water to the dilution hydration depending on the polymerization concentration, or without addition of water, in particular alcohols, and dilution step in which particular dilution adding methanol,
   (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 polymerization catalyst with an ion exchange resin;
   (5) after ion exchange polymerization, adding phosphoric acid or alkylphosphoric acid to form a complex;
   (6) adding hydrogen peroxide having a ½ molar value or less to 1 mol of titanic acid to the hydrated monomer or polymer to form a peroxyalkyl titanic acid monomer or polymer;
   (7) It consists of 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.
   Novel titanic acid monomer and polymer, production method thereof and use thereof.
2. 2. The alkoxytitanic acid monomer or peroxytitanic acid monomer obtained by the steps (1) to (2) in the production method according to claim 1.
3. The novel titanic acid monomer and polymer obtained by the steps (1) to (7) of the production method according to claim 1.
4. The novel titanic acid monomer and polymer, production method thereof and use thereof according to claim 1, wherein the excess alcohol is methanol or ethanol, and the mineral acid is hydrochloric acid.
5. 5. The novel titanic acid monomer and polymer, production method thereof and use thereof according to claim 1 or 4, wherein the excess alcohol is methanol.
6. Immediately after application, titanic acid obtained by contacting and treating a chelating agent represented by ultraviolet rays, heating and a phosphoric acid compound, and hydrogen peroxide in order to show immediate light activity under the measurement conditions (short time) according to JIS method. Monomer and polymer production methods and uses thereof.
7. The method for producing a titanic acid monomer and polymer and use thereof according to claim 6, wherein the chelating agent is a phosphoric acid compound.
8. The method for producing a novel titanic acid monomer and polymer according to claim 1 or 2, wherein the excess alcohol and the mineral acid coexist with the alkoxy titanic acid monomer from a half-valence mole to an equivalent or less. As well as its use.
9. As 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, The method for producing a novel titanic acid monomer and polymer according to claim 1, further comprising a coating step of undercoating an acid, an alkali phosphate compound, and a methyl silicate alkali phosphate compound and applying a titanic acid monomer or polymer thereon. As well as its use.
10. The novel titanic acid monomer and polymer according to claim 9, and a production method and use thereof, wherein the alkali contains sodium and potassium.
11. The alkoxytitanic acid monomer is added with water-free titanium tetrachloride in water-free alcohol, or alkoxytitanic acid is added with water-free alcohol with 2% or more, preferably 15% or more mineral acid. In particular, a method of adding in hydrochloric acid, or adding titanium tetrachloride without adding water to 30% or more, preferably 50% or more of hydrogen peroxide (hereinafter referred to as hydrogen peroxide) without adding water, or alkoxy titanium 2. The novel titanic acid monomer and polymer according to claim 1, which are synthesized by a method in which an acid is added to hydrogen peroxide and alcohol without adding water, and a production method and use thereof.
12. The alkoxytitanic acid monomer or polymer having a protective function produced by the production method according to claim 1 and a peroxytitanic acid monomer or polymer as they are or after dehydrochlorination are used from under non-light to ultraviolet Bottom catalyst, titania phosphate film-forming agent, titania peroxyphosphate film-forming agent, intramolecular self-activator, burnt and seizing release agent, PVC cross-linked titania, surface polarity conversion agent, acid-resistant titanium film-forming agent , Electromagnetic wave protective agent, superconducting agent, anti-static agent for fibers / threads and plastics, antiwear agent for wear / heat resistance / brightness, dry wetting agent, rust preventive agent, surface treatment for imparting highly hydrophilic / lipophilic surface Agent, hydrophilic / lipophilic coating film-forming agent, moss remover, moss preventive agent, bactericidal agent, antibacterial agent, fungicidal agent, antifungal agent, titanic acid thread or film molding, deodorant, NOX- SOX fixed Catalyst, barium titanate synthesized agents for ceramic capacitors, aqueous transesterification catalyst, CO _2, H ₂ O decomposition catalyst, binding adhesive particulate titania, polysaccharides hydrolysis catalyst, rust, wood preservative termiticide , Pesticides, fish farming agents, antifouling / defouling (self-cleaning) agents, UV heat protection agents, restoration agents for deteriorated / white flowers, water-soluble chelating agent insolubilizing (fixing) agents, chelating agents, etc. The method for producing a titanic acid monomer and polymer according to claims 1 to 4.
13. The alkoxytitanic acid monomer or polymer having a protective function produced by the production method according to claim 1 and a peroxytitanic acid monomer or polymer as they are or after dehydrochlorination are used from under non-light to ultraviolet Bottom catalyst, titania phosphate film forming agent, titania peroxyphosphate 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, anti-static agent for fibers / threads and plastics, antiwear agent for wear / heat resistance / brightness, dry wetting agent, rust preventive agent, surface treatment for imparting highly hydrophilic / lipophilic surface Agent, hydrophilic / lipophilic coating film-forming agent, moss remover, moss preventive agent, bactericidal agent, antibacterial agent, fungicidal agent, antifungal agent, titanic acid thread or film molding, deodorant, NOX- SOX fixed Catalyst, barium titanate synthesized agents for ceramic capacitors, aqueous transesterification catalyst, CO _2, H ₂ O decomposition catalyst, binding adhesive particulate titania, polysaccharides hydrolysis catalyst, rust, wood preservative termiticide , Pesticides, fish farming agents, antifouling / defouling (self-cleaning) agents, UV heat protection agents, restoration agents for deteriorated / white flowers, water-soluble chelating agent insolubilizing (fixing) agents, chelating agents, etc. Uses.
14. The chain transfer catalyst forms a chelate with a phosphoric acid compound selected from the group consisting of water-soluble phosphoric acid, phosphate, and alkyl phosphate ester, alkoxy titanic acid, titanic acid or titanium ion, and evaporates at room temperature. 10. The organic compound or inorganic compound to be used alone or a mixture thereof, or a reagent such as an anion exchange resin, which becomes a chain transfer catalyst through a protecting group that does not form a chelate bond or a chemical bond. 2. The novel titanic acid monomer and polymer according to claim 1 and a production method and use thereof.
15. 10. The novel titanic acid according to claim 1, wherein the water-soluble alkyl phosphate is methyl phosphate, ethyl phosphate, isopropyl phosphate, or butyl phosphate compound. Monomers and polymers and methods and uses thereof.

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