WO2004050560A1 - 変性された酸化第二スズゾル、酸化第二スズ−酸化ジルコニウム複合体ゾル、コーティング組成物及び光学部材 - Google Patents
変性された酸化第二スズゾル、酸化第二スズ−酸化ジルコニウム複合体ゾル、コーティング組成物及び光学部材 Download PDFInfo
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- WO2004050560A1 WO2004050560A1 PCT/JP2003/015486 JP0315486W WO2004050560A1 WO 2004050560 A1 WO2004050560 A1 WO 2004050560A1 JP 0315486 W JP0315486 W JP 0315486W WO 2004050560 A1 WO2004050560 A1 WO 2004050560A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/002—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/928—Mixing combined with non-mixing operation or step, successively or simultaneously, e.g. heating, cooling, ph change, ageing, milling
Definitions
- the present invention the surface of the tin oxide colloid or stannic oxide monoxide zirconium composite colloidal, formed by coating with composite colloid particles of the alkylamine containing S b 2 ⁇ 5 Koroido particles or antimony pentoxide and silica
- the present invention relates to a sol of colloidal particles of modified stannic oxide or modified stannic oxide having a particle diameter of 4.5 to 60 nm and a method for producing the same.
- the formed coating has excellent warm water resistance, and even when an inorganic oxide vapor-deposited film (such as an anti-reflection film) is formed on the coating, the weather resistance and light resistance of the coating are reduced.
- the present invention relates to a coating composition and an optical member which are not used. Background art
- a metal oxide sol having a high refractive index is used as a component of a hard coating agent applied to the surface.
- a hard coat agent containing 1 to 300 nm particles of metal oxides such as Ti, Zr, Sn, and Sb is described (for example, see Japanese Patent Publication No. 63-37142).
- a caustic acid-stannate composite sol in which the molar ratio of S 1: Sn is 2 to 1000: 1 has been proposed (see, for example, Japanese Patent Publication No. 50-40119).
- Colloidal particles of metal oxides having a valence of 3, 4 or 5 having a particle diameter of 4 to 50 nm are used as nuclei, and the surface has a W ⁇ 3 / SnO 2 weight ratio of 0.5 to 100 and a particle diameter of 0.5 to 100. It is composed of a modified metal oxide colloid having a particle diameter of 4.5 to 60 nm formed by being coated with colloidal particles of tungsten oxide monoxide complex of 2 to 7 nm, and these all metal oxides A stable sol containing 2 to 50% by weight has been proposed (see, for example, JP-A-3-217230).
- the metal oxide nuclei S N_ ⁇ 2 particles, S N_ ⁇ 2 - Z r 0 2 composite colloidal particles, the coating alkylene Ruamin containing S b 2 0 5 particles (M / S b 2 0 5 molar A sol having a ratio of 0.02 to 4.00) has been disclosed (for example, see JP-A-2001-122621).
- An aqueous alkali silicate solution or sol silicate solution and an aqueous alkali antimonate solution or an aqueous alkali stannate solution are mixed such that the molar ratio of Si: Sb or Si: Sn is 2 to 1000: 1.
- a method for producing a silicate solution of monocarboxylic acid-monic acid or a complex sol solution of maleic acid and monostannic acid, wherein the mixed solution is de-ionized with an acid-type ion exchanger after the mixing, is described (for example, And Japanese Patent Publication No. 50-410 19).
- a silica-antimony oxide composite sol is described in which antimony oxide colloid particles containing 0.1 to 50% by weight of an inorganic silicic acid compound as Si ⁇ 2 are dispersed in a dispersion medium (for example, Japanese Patent Application Laid-Open No. H11-163873). (See Fair Publication 7-255549).
- Plastic molded products are used in large quantities because of their advantages such as light weight, easy processability and impact resistance, but on the other hand, they have insufficient hardness, are easily scratched, are easily eroded by solvents, and are charged with dust. It has drawbacks such as adsorption of heat and insufficient heat resistance, and is practically insufficient compared to inorganic glass molded articles for use as eyeglass lenses, window materials, and the like. Therefore, it has been proposed to apply a protective coat to the plastic molded body. Numerous types of coating compositions for use in coatings have been proposed.
- Coating compositions containing an organic gay compound or its hydrolyzate as a main component are used for eyeglass lenses.
- refin component or film-forming component are used for eyeglass lenses.
- a silane coupling agent and metal oxide colloid particles (A) having a primary particle diameter of 2 to 60 nm as nuclei, and the surface thereof is coated with acidic oxide colloid particles (B). It contains particles (C) obtained by coating, and contains (C) in a proportion of 2 to 50% by weight in terms of metal oxide, and has a primary particle diameter of 2 to 100 nm. Coating compositions comprising stable modified metal oxide sols having the same are disclosed.
- the metal oxide nuclei S n 0 2 particles, S N_ ⁇ 2 - Z r 0 2 composite colloidal particles, Arukiruamin containing S b 2 O 5 particles coating (MZS b 2 0 5 molar ratio of 0 0.24 to 4.00) is disclosed (for example, see Japanese Patent Application Laid-Open No. 2001-123210). Disclosure of the invention
- the coating composition to which the conventional silica sol is added has a problem that interference fringes are visible in the coating film and the appearance of the lens is poor.
- an antireflection film (consisting of a multilayer structure of inorganic oxide thin films based on optical interference theory) is often formed on the coating film.
- the anti-reflection film exhibits, for example, an extremely light green reflection color, but this reflection color changes according to the position of the lens surface, and there is a problem that there is unevenness.
- the coating layer formed from this coating composition is resistant to water. Poor properties, blue by UV irradiation There was a drawback that it was colored.
- the hard coat and S b 2 0 5 sol -. When used as Bok component, the refractive index of the S b 2 0 5 1 6 5 to 7 0 about a is either et al, refraction of the plastic substrate of the lens when the rate is 1. 6 or more, the S b 2 0 5 zone refractive index of the cured coating was Le does not sufficiently improved anymore.
- the sol of tungsten oxide described in JP-A-54-52686 is prepared by adding a silicate to an aqueous solution of tungstic acid obtained by decationizing an aqueous solution of tungstate. Although it is obtained, it is stable only in strong acidity, and when used as a component of a hard coating agent, the effect of improving the refractive index of the coating film is small.
- the citric acid-stannic acid composite sol described in Japanese Patent Publication No. 50-41019 is obtained by deionizing a mixed aqueous solution of alkaline silicate and alkaline stannate.
- the effect of improving the refractive index of the coating film is small.
- the modified metal oxide sol described in Japanese Patent Application Laid-Open No. 3-217230 is stable with a refractive index of 1.7 or more, and can be used as a component of a hard coating agent for plastic lenses.
- the required performance of the hard coat film such as scratch resistance, transparency, adhesion, water resistance, and weather resistance, can be almost satisfied.
- the modified stannic oxide-zirconium oxide sol described in the above-mentioned Japanese Patent Application Laid-Open No. 6-24746 is stable as having a refractive index of 1.7 or more, and is used as a component of a hard coating agent for plastic lenses. It can almost satisfy the required performance of the hard coat film, such as scratch resistance, transparency, and adhesion.
- the present invention relates to a modified metal oxide described in Japanese Patent Application Laid-Open No. 3-217720 / 1994 It is a stable sol of modified varnish oxide or modified stannic oxide zirconium oxide that further improves transparency, adhesion, water resistance, weather resistance, etc., and is stable over a wide pH range. At the same time, it is an object of the present invention to provide a metal oxide sol that can be used as a component for improving the performance of a hard coat film formed on the surface of a plastic lens, which can be mixed with a paint for hard coat.
- An object of the present invention is to provide a composition and an optical member.
- the present invention is for a plastics molded article having excellent scratch resistance, surface hardness, abrasion resistance, flexibility, transparency, antistatic property, coloring property, heat resistance, water resistance, chemical resistance and the like.
- An object of the present invention is to provide a coating composition and an optical member.
- the gist of the present invention is as follows.
- . 1 is a composite particle with stannic oxide particles or stannic oxide particles and zirconium oxide particles, these oxides based on the weight Z r 0 2: S N_ ⁇ 2 0: 1-0.
- Colloidal particles (A) having a ratio of 50: 1 and a particle diameter of 4 to 50 nm are used as nuclei, and the surface of the colloidal particles has a particle diameter of 0.1 ⁇ m.
- colloid particles (A) are 0.05 ::! ⁇ 0.50: 1 Z r 0 2: S n0 2 weight ratio of composite sol of placing serial above 1 are colloidal particles of stannic oxide particles and zirconium oxide particles that Yusuke.
- (a) is a core, antimony pentoxide and silica whose surface has a molar ratio of S I_ ⁇ 2 ZS b 2 0 5 of from 0.55 to 55 of
- the composite colloid particles, the oligomer thereof, or a mixture thereof are coated with (B2), and the weight ratio of (B2) Z (A) is 0.01 to 0.50 based on the weight ratio of the metal oxides.
- Colloidal particles (A) is 0.05:. 1-0 50: 1 Z r 0 2: is a composite colloidal particles of the S n0 2 stannic oxide particles that have a weight ratio between oxide Jirukoniumu particles The sol described in 4 above.
- Step (c1) a step of aging the aqueous medium obtained in step (b1) at 20 to 300 for 0.1 to 50 hours.
- the method for producing a sol according to the above 1 or 3, comprising the following steps (a2), (b2), (c2) and (d2).
- Step 2 4 to 50 and the stannic oxide aqueous sol having a S n 0 2 concentration of the particle size from 0.5 to 50 wt% of nm, Z R_ ⁇ 0.5 to 50 in terms of 2 and an aqueous solution of Okishijirukoniu beam salts wt% concentration, and mixed to 0.05 to 0 50 weight ratio of the Z r 0 2 ZS N_ ⁇ 2, 10 60 and the resulting mixture Ot:. a, 0.
- an aqueous sol of stannic oxide and zirconium monoxide composite having a particle size of 4 to 50 nm is prepared.
- (b 2) Step:. (a 2) and stannic oxide monoxide zirconium composite aqueous sol obtained in the step, 0. 02 ⁇ 4 00 MZS b 2 0 5 molar ratio of (wherein M is Amin molecule alkylamine containing having a.) indicating the S b 2 ⁇ 5 colloidal particles, an oligomer thereof, or an aqueous medium containing their mixed compounds, S b 2 0 5 in terms of the metal oxide (Sn0 2 + 0. in a weight ratio of Z r 0 2) 01 ⁇ 0. mixing 50,
- Step (c2) a step of aging the aqueous medium obtained in step (b2) at 20 to 300 for 0.1 to 50 hours,
- Step (d2) The modified stannic oxide-zirconium oxide composite aqueous sol obtained in step (c2) is brought into contact with an anion exchanger to form anion present in the sol. Removing.
- Step (c3) a step of aging the aqueous medium obtained in step (b3) at 20 to 300 at 0:! to 50 hours.
- (b 4) Step:. (a 4) and stannic oxide monoxide zirconium composite aqueous sol obtained in the step, from 0.02 to 4 00 M / S b 2 ⁇ 5 molar ratio (wherein M is shows the Amin molecule.) alkylamine containing S b 2 ⁇ 5 colloidal particles having, an oligomer, or an aqueous medium containing their mixed compounds, S b 2 0 5 Z in terms of the metal oxides ( Sn0 2 + Z r 0 2) mixing the 0.01 to 0.50 by weight ratio,
- Step (c4) a step of aging the aqueous medium obtained in step (b4) at 20 to 300 for 0:! to 50 hours,
- Step (d4) The modified stannic oxide zirconium oxide composite aqueous sol obtained in step (c4) is brought into contact with an anion exchanger to remove anions present in the sol. Removing.
- (b 5) Step: The above (a 5) and a stannic oxide aqueous sol obtained in the step of 0. 55 ⁇ 55 S i 0 diantimony pentaoxide and silica having a 2 / S b 2 0 5 molar ratio of the composite colloidal particles child, and an aqueous medium containing the oligomer, or a mixture thereof, at a weight ratio of the metal oxides in terms of (S b 2 ⁇ 5 + S i 0 2) ( S N_ ⁇ 2) Mixing from 0.01 to 0.50, and
- Step (c5) a step of aging the aqueous medium obtained in step (b5) at 20 to 300 at 0 :! to 50 hours.
- Step (c6) a step of aging the aqueous medium obtained in step (b6) at 20 to 300 for 0.1 to 50 hours,
- Step (d6) The modified stannic oxide zirconium monoxide composite aqueous sol obtained in step (c6) is brought into contact with an anion exchanger to form anion present in the sol. Removing.
- Step 7 a hydrothermal treatment at a temperature of at 100-300, and to prepare a stannic oxide aqueous sol having a S N_ ⁇ 2 concentration of the particle diameter and 0.5 to 50 wt% of 4 to 50 nm Process,
- (b 7) Step: The above (a 7) and stannic oxide aqueous sol obtained in step, of 0. 55 ⁇ 55 S I_ ⁇ antimony pentoxide and silica having 2 ZS b 2 ⁇ 5 molar ratio of composite colloidal particles child, an oligomer, or an aqueous medium containing a mixture thereof, in a weight ratio of the calculated as metal oxides (S b 2 ⁇ 5 + S i 0 2) / (S N_ ⁇ 2) Mixing step from 0.01 to 0.50,
- the method for producing a sol according to the above 4 or 6, comprising the following (a8) step, (b8) step, (c8) step and (d8) step.
- Step 8 An aqueous stannic oxide sol hydrothermally treated at a temperature of 100 to 300 and having a particle size of 4 to 50 nm and a Sn ⁇ 2 concentration of 0.5 to 50% by weight; and an aqueous solution of O carboxymethyl zirconium salt of 0.5 to 50% strength by weight in terms of R_ ⁇ 2, were mixed in a weight ratio of 0.05 to 0.50 as Z r0 2 / SnO 2, resulting mixture Preparing the aqueous sol of stannic oxide and zirconium monoxide composite having a particle diameter of 4 to 50 nm by heating the liquid at 60 to 100 for 0.1 to 50 hours,
- Step (c8) The aqueous medium obtained in step (b8) is subjected to the reaction in 20 to 300 at 0 :! Aging process for ⁇ 50 hours,
- Step (d8) The modified stannic oxide zirconium oxide composite aqueous sol obtained in step (c8) is brought into contact with an anion exchanger to form anion present in the sol. Removing.
- a coating composition containing the following component (S) and component (T1).
- R 1 and R 3 represent an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methylacryloyl group, a mercapto group, and an amino group, respectively.
- an organic group having a cyano group and S i _C R is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group, and a and b are integers of 0, 1, or 2, respectively.
- a and b are integers of 0, 1, or 2, respectively.
- 3 +1) is an integer of 0, 1, or 2.
- R 4 represents an alkyl group having 1 to 5 carbon atoms
- X represents an alkyl group having 1 to 4 carbon atoms or an acyl group
- Y represents a methylene group or an alkylene group having 2 to 20 carbon atoms
- T 1 component a multi-coalesced particles of stannic oxide particles or stannic oxide particles and zirconium oxide particles, these oxides based on the weight Z r0 2: Sn_ ⁇ 2 0: 1 0.50:. the surface 1 of the ratio between 4 to colloidal particles having a particle size of 50 nm to (a) as nuclei, from 0.02 to 4 mole ratio of 00 M / S b 2 ⁇ 5 (where M denotes the Amin molecule.
- colloidal particles (A) is 0.05::! ⁇ 0.50: 1 Z r 0 2: composite colloidal particles of the S N_ ⁇ 2 have a weight ratio stannic oxide particles and zirconium oxide particles 16.
- a coating composition containing the following component (S) and component (T2).
- R and R represent an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacrylyl group, a mercapto group, an amino group, or a cyano group, respectively.
- R is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group, and a and b are An integer of 0, 1, or 2; a + b is an integer of 0, 1, or 2); and a general formula (I 1):
- R 4 represents an alkyl group having 1 to 5 carbon atoms
- X represents an alkyl group having 1 to 4 carbon atoms or an acyl group
- Y represents a methylene group or an alkylene group having 2 to 20 carbon atoms
- c is an integer of 0 or 1.
- (T2) component a multi-coalesced particles and stannic oxide particles or stannic oxide particles of zirconium oxide particles, these oxides based on the weight Z r 0 2: S n0 2 0: 1 0.50: 1 ratio and 4 colloidal particles having a particle size of 50 nm to (a) as nuclei, its surface has a molar ratio of S I_ ⁇ 2 / S b 2 ⁇ 5 of 0.55 to 55 It is coated with composite colloidal particles of antimony pentoxide and silica, its oligomer, or a mixture thereof (B2), and the weight ratio of (B2) / (A) is 0.01 based on the weight ratio of the metal oxides.
- colloidal particles (A) are stannic oxide.
- colloidal particles (A) is 0 0 5:.. 1-0 5 0: 1 Z R_ ⁇ 2: complex with S N_ ⁇ to have a 2 weight ratio of stannic oxide particles and zirconium oxide particles 21.
- component (A) is at least one silicon-containing substance selected from the group consisting of an organic silicon compound represented by the general formula (I) and a hydrolyzate thereof. Any of 2
- the coating composition according to any one of the above 15 to 23, comprising one or more curing catalysts selected from the group consisting of metal salts, metal alkoxides and metal chelate compounds.
- the present invention provides an antimony acid alkali salt, an alkali component-containing antimony pentoxide colloid and an oligomer thereof, a coating obtained by further adding a silica component thereto, and an antimony pentoxide-silicone composite colloid, an oligomer thereof, or a mixture thereof.
- the modified stannic oxide and / or stannic oxide zirconium monoxide composite colloid of the present invention is used as a hard coat agent component, yellowing due to ultraviolet irradiation observed when using a conventional metal oxide sol is used.
- a stable sol of modified metal oxide colloid particles having good water resistance and weather resistance is provided, and the hard coat is used as a component for improving the performance of a hard coat film formed on a plastic lens surface.
- the present invention provides a sol that can be used by being mixed with a paint for use.
- the sol of the surface-modified metal oxide colloid particles obtained by the present invention is colorless and transparent, the refractive index calculated from the dried coating film thereof is about 1.75-1.92, and the bond strength is High hardness and hardness, and good weather resistance, antistatic properties, heat resistance, abrasion resistance, etc. In particular, weather resistance and moisture resistance are significantly improved compared to conventional ones.
- the sol of the present invention is stable at a pH of 1 to 11, preferably 1.5 to 10, and can also provide sufficient stability to be supplied as an industrial product.
- the sol of the present invention has good miscibility with sols composed of other negatively charged colloidal particles since the colloidal particles are negatively charged.
- the cured film obtained by the coating composition of the present invention is a coating layer having improved scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, light resistance, weather resistance, and especially water resistance. In addition, it has good adhesion to antireflection films (such as inorganic oxides and fluorides) and metal vapor deposition films formed on this coating layer.
- antireflection films such as inorganic oxides and fluorides
- the optical member of the present invention has abrasion resistance, surface hardness, abrasion resistance, transparency, heat resistance, light resistance, and weather resistance. Highly transparent and excellent appearance with no interference fringes even when coated on a high refractive index member with a refractive index of 1.54 or more. .
- the present invention is a composite particle with stannic oxide particles or stannic oxide particles and zirconium oxide particles, these oxides based on the weight Z R_ ⁇ 2: S n0 2 0: 1-0 . 5 0:. its surface a ratio of colloidal particles having a particle size of 4 to 50 nm (a) as nuclei, 0. 02 ⁇ 4 00 MZSb 2 ⁇ 5 molar ratio of (wherein M is Amin molecule It is shown.
- the stannic oxide colloidal particles as the core particles (A) used in the production of the sol of the present invention can be prepared by a known method, for example, a method called an ion exchange method, a peptization method, a hydrolysis method or a reaction method. It can be easily prepared in the form of a sol of colloidal particles having a particle size of about 50 nm.
- Examples of the ion exchange method include a method in which a stannate such as sodium stannate is treated with a hydrogen-type cation exchange resin, or a method in which a stannic salt such as stannic chloride or stannic nitrate is converted to a hydroxyl-type cation exchange resin.
- a method of treating with an anion exchange resin may be used.
- Examples of the deflocculation method include neutralizing a stannic salt with a base, or washing a stannic hydroxide gel obtained by neutralizing stannic acid with hydrochloric acid and then peptizing with an acid or a base. Method.
- Examples of the above hydrolysis method include a method of hydrolyzing a tin alkoxide, and a method of hydrolyzing a basic stannic chloride basic salt under heating and then removing an unnecessary acid.
- Examples of the above reaction method include a method of reacting a metal tin powder with an acid.
- the aqueous stannic oxide sol produced by the above method can be used as it is, but can also be used after hydrothermal treatment at a temperature of 100 to 300 t.
- the above-mentioned aqueous stannic oxide sol is placed in a photoclave and subjected to a treatment at a temperature of 100 to 30 Ot: for 0.1 to 200 hours.
- the medium of these oxidized varnish sols may be either water or a hydrophilic organic solvent, but is preferably an aqueous sol in which the medium is water.
- the pH of the sol is preferably a value that stabilizes the sol, and is generally about 0.2 to 11.5.
- the oxidized varnish may contain optional components, for example, an alkaline substance for stabilizing the sol, an acidic substance, oxycarboxylic acid, and the like.
- concentration of the oxidized varnish to be used is about 0.5 to 50% by weight as the oxidized varnish, but the lower the concentration, the better, and preferably 1 to 30% by weight.
- Stannic oxide as the core particles used in the production of the sol of the present invention (A) - oxide Jirukoniu beam composite sol, the O carboxymethyl zirconium salt to the oxide first Nisuzuzoru Z R_ ⁇ 2 ZSn0 2 weight ratio 0.05 It can be obtained by mixing at 5 to 100 for 0.5 to 3 hours and then heating it to 60 to 100: for 0.1 to 50 hours so as to become 0.5.
- the oxidized varnish sol used here may be either a sol that has been subjected to a hydrothermal treatment or a sol that has not been subjected to a hydrothermal treatment.
- the oxyzirconium salt used includes zirconium oxyorganic acid such as zirconium oxychloride, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxyacetate, and zirconium oxycarbonate.
- These O carboxymethyl zirconium salt can be used as solids or aqueous solutions, as Z R_ ⁇ 2 0.5 to 5 0% by weight, preferably 0.
- Even salts insoluble in water, such as zirconyl oxycarbonate, can be used when stannic oxide is an acidic sol.
- an alkaline sol stabilized with an organic base such as amine is particularly preferable to use as the oxidized varnish sol.
- Mixing with an oxyzirconium salt is 5 to 100, preferably room temperature (20 V). 60 is preferred. This mixing may be carried out by adding an oxyzirconium salt to the oxidized varnish under stirring or by adding the oxidized varnish to an aqueous solution of the oxyzirconium salt, the latter being preferred. This mixing must be performed sufficiently, preferably for 0.5 to 3 hours.
- the alkylamine-containing antimony pentoxide colloid, its oligomer, or a mixture thereof (B 1) used as the coating sol of the present invention can be obtained by the following methods (oxidation method, acid decomposition method, etc.).
- Examples of the acid decomposition method include a method in which an alkali antimonate is reacted with an inorganic acid and then peptized with an amine (Japanese Patent Application Laid-Open (JP-A) No. 60-41536, and Japanese Patent Application Laid-Open No. 61-22791). No. 8, Japanese Patent Publication No. 2000-1—1 2 3 11 5), Example of oxidation method and method of oxidizing antimony trioxide with hydrogen peroxide in the coexistence of amine and alkali metal No. 118488, JP-A-59-23291) or the method of oxidizing antimony trioxide with hydrogen peroxide and then adding an amine-alkali metal.
- Examples of the amine of the above-mentioned amine-containing antimony pentoxide colloid, its oligomer, or a mixture thereof include ammonium, quaternary ammonium and water-soluble amine.
- Preferred examples thereof include alkylamines such as isopropylamine, diisopropylamine, n-propylamine and diisobutylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, monoethanolamine and triethanolamine.
- quaternary ammonium such as tetramethylammonium hydroxide. Particularly, diisopropylamine and diisobutylamine are preferred.
- the molar ratio of Al force re ingredient ⁇ Min-containing diantimony pentaoxide colloid and antimony pentoxide MZ S b 2 ⁇ 5 to zero. 0 2 to 4.0 0 are preferred, obtained with less than this colloid If the sol is too large, the water resistance of the dried coating film obtained by using such a sol becomes low, which is not preferable in practical use.
- the amine-containing antimony pentoxide colloid particles, oligomers thereof, or a mixture thereof are minute colloidal particles of antimony pentoxide, oligomers thereof, or a mixture thereof. Electron microscopic observation of the colloidal particles revealed particles of 20 nm or less. Oligomers are polymers and cannot be observed with an electron microscope.
- the colloid particles (A) have a particle diameter of 4 to 5 nm
- the metal oxide particles modified by coating (B 1) have a particle diameter of 4.5 to 60 nm. This increase in particle size causes the negatively charged (B 1) colloidal particles, their oligomers, or mixtures thereof to form chemical bonds on the surface of the positively charged colloidal particles (A), thereby It is coated.
- an alkyl amine salts such as Jie isopropyl amine as the amine component
- the molar ratio of amine S b 2 ⁇ 5 is 0. 0 2 to 4.0 0.
- alkylamine-containing silica particles can be further added to the amine-containing antimony pentoxide colloid particles, their oligomers, or a mixture thereof.
- the composite colloid of antimony pentoxide and silica used as the coating sol of the present invention, an oligomer thereof, or a mixture thereof (B 2) can be prepared by a known method described below (for example, Japanese Patent Publication No. Sho 501-41019). ). That is, an aqueous solution of an alkali silicate or a sol solution of silicate It can be obtained by mixing with an aqueous solution of an alkali thymonate, followed by dehydration cation with a cation exchange resin.
- an aqueous antimonic acid solution can be preferably used.
- silica raw material sodium silicate, potassium silicate, or active silicate obtained by subjecting these to cation exchange can be used.
- the molar ratio of S i 0 2 / S b 2 0 5 is zero. 5 5-5 5.
- the composite colloid of antimony pentoxide and silica, an oligomer thereof, or a mixture thereof is a fine composite colloid of antimony pentoxide and silica, an oligomer thereof, or a mixture thereof.
- the colloid particles were found to be 5 nm or less by electron microscopy. Oligomers are polymers and cannot be observed with an electron microscope.
- the colloid particles (A) have a particle diameter of 4 to 50 nm
- the metal oxide particles modified by coating (B 2) have a particle diameter of 4.5 to 60 nm.
- This increase in particle size is due to the negatively charged (B 2) colloidal particles of antimony pentoxide and silica, their oligomers, or a mixture thereof, being chemically treated on the surface of the positively charged colloidal particles (A). It forms a strong bond and is covered by it.
- the stannic oxide - zirconium oxide composite colloids particles are positively charged, S b 2 ⁇ 5 colloid is negatively charged. Therefore, stannic oxide is charged to the positive by mixing - colloids S b 2 ⁇ 5 which are negatively around the zirconium oxide composite colloidal particles are attracted electrically, and colloidal particles of positively charged Sb 2 ⁇ 5 was bound by chemical bonding on the surface, and the surface was modified by the negatively charged S b 2 ⁇ 5 covering the positively charged particles as nuclei. It is considered that stannic oxide and zirconium monoxide composite colloid particles were formed.
- zirconium oxide composite colloidal particles nuclei becomes insufficient coverage of the front surface to, easily caused aggregation of generating colloidal particles, it is considered that makes it unstable generation sol.
- the amount of S b 2 ⁇ 5 colloidal particles and an oligomer thereof to be mixed Is stannic oxide-acid
- the amount may be less than the amount covering the entire surface of the zirconium composite colloid particles, but is not less than the minimum amount required to generate a sol of stable modified stannic oxide zirconium monoxide composite colloid particles.
- the resulting sol contain S b 2 ⁇ 5 colloid, an oligomer thereof or a mixture thereof It is only a stable mixed sol of an aqueous medium and a sol of the resulting modified stannic oxide zirconium monoxide composite colloidal particles.
- Modified stannic oxide or modified stannic oxide-zirconium oxide composite the surface of which is coated with the composite colloid of antimony pentoxide and silica, an oligomer thereof, or a mixture thereof (B 2) according to the present invention
- the colloid particles are negatively charged in the sol.
- the stannic oxide zirconium monoxide composite colloid particles are positively charged, and the composite colloid of antimony pentoxide and silica is negatively charged. Therefore, the negatively charged composite colloid of antimony pentoxide and silica is electrically attracted around the positively charged stannic oxide-zirconium oxide composite colloid particles by mixing.
- the composite colloid of antimony pentoxide and silica is bonded to the surface of the positively charged colloidal particles by chemical bonding, and the composite colloid of antimony pentoxide and silica whose surface is negatively charged with the positively charged particles as nuclei. It is considered that the modified stannic oxide zirconium monoxide composite colloidal particles were formed by covering.
- the amount of the composite colloid of antimony pentoxide and silica is insufficient, the coating of the surface of the core of the composite stannic oxide-zirconium oxide composite colloid particles with the colloid particles of the composite is insufficient. It is considered that the formed colloid particles are likely to aggregate, which makes the formed sol unstable. Therefore, the amount of the antimony pentoxide and silica composite colloid particles, the oligomer thereof, or a mixture thereof to be mixed may be smaller than the amount covering the entire surface of the stannic oxide zirconium monoxide composite colloid particles. The amount is at least the minimum amount necessary to generate a sol of stable modified stannic oxide zirconium monoxide composite colloidal particles.
- the resulting sol will contain antimony pentoxide and silica. It is merely a stable mixed sol of an aqueous medium containing the composite colloid, its oligomer, or a mixture thereof, and the resulting sol of modified stannic oxide zirconium monoxide composite colloid particles.
- the amount of the antimony pentoxide and silica composite colloid, the oligomer thereof, or the mixture thereof (B 2) is determined by the amount of metal in the nuclear sol. to oxide (S N_ ⁇ 2 or Z r 0 2 + S n0 2 ) 100 by weight parts, preferably 50 parts by weight as the metal oxide in the coating sol.
- step: (b 1) is at 20 to 300 and the aqueous medium obtained in step, 0.1 Step of aging for 1 to 50 hours to obtain a stable sol of modified stannic oxide colloid particles.
- the step (d1) can be added when the oxidized varnish sol in the step (al) contains anion.
- step (d1) the modified stannic oxide aqueous sol obtained in step (c1) is brought into contact with an anion exchanger to remove anions present in the sol; Thereafter, a step of aging at 20 to 300 at 0.1 to 50 hours is added to obtain a stable sol of modified stannic oxide colloid particles. Aging at 100 or more can be performed using an autoclave.
- This sol is a sol surface oxidation secondary tin colloid particles having a particle Cai. 4 to 50 nm and (A) as nuclei, 0. 02 ⁇ 4.
- step (a2) a particle diameter of 4 to 50 nm and 0.5 to 50% by weight of SnO 2 a stannic oxide aqueous sol having a concentration, and an aqueous solution of Okishijirukoniu beam salts of from 0.5 to 50% strength by weight in terms of Z r0 2, 0. as Z r 0 2 ZS N_ ⁇ 2 05-0.
- the mixture was mixed at a weight ratio of 50, and the resulting mixture was heated at 60 to 100 for 0.1 to 50 hours to obtain a stannic oxide zirconium oxide composite having a particle size of 4 to 50 nm.
- step: (a 2) stannic oxide obtained in step - zirconium oxide composite aqueous sol, 0.0 2-4 00 moles of MZS b 2 ⁇ 5 ratio (where M is. showing the Amin molecules) water containing alkyl Amin containing S b 2 ⁇ 5 colloidal particles having, oligomers thereof, or mixtures thereof Step of mixing the media, to the S b 2 as calculated as metal oxides ⁇ 5 (Sn0 2 + Z r 0 2) 0. by weight ratio of 01 ⁇ 0 50, (c 2) Step:.
- the aqueous sol of the composite is brought into contact with an anion exchanger, and then aged at 20 to 30 Ot: for 0.1 to 50 hours to obtain a stable sol of modified stannic oxide-zirconium oxide composite colloid particles.
- Can be Aging above 100 can be done using autoclaves.
- the sol is a sol containing a composite colloidal particle of modified oxidized varnish particles and zirconium oxide particles having a particle size of 0.01 to 0.50 and a particle size of 4.5 to 60 nm.
- the above production method can also be performed under pressure using an autoclave.
- step (a3) a hydrothermal treatment at a temperature of 100 to 300, and a particle diameter of 4 to 5011111 and 0.5 to 50% by weight of preparing a stannic oxide aqueous sol having Sn_ ⁇ 2 concentration
- step (c 3) showing the Amin molecule) alkylamines containing Sb 2 ⁇ 5 colloidal particles having, and an aqueous medium containing the O Rigoma one, or mixtures thereof, mixing the 0.01 to 0 50 in a weight ratio of S b 2 OsZS N_ ⁇ 2 as calculated as metal oxides, (c 3) step:. 20 a (b 3) an aqueous medium obtained in about E
- the modified stannic oxide aqueous sol is obtained from the step of aging at 300 for 0.1 to 50 hours.
- step (d3) can be added if the oxidized varnish sol in step (a3) contains anion.
- step (d3) the modified stannic oxide aqueous sol obtained in step (c3) is brought into contact with an anion exchanger to remove anions present in the sol.
- a stable sol of modified stannic oxide colloidal particles is obtained by adding a step of aging at ⁇ 300 for 0.1-50 hours. Aging above 100 can be done using autoclaves.
- This sol is a sol surface oxidation secondary tin colloid particles having a particle size of. 4 to 50 nm and (A) as nuclei, 0. 02 ⁇ 4.
- step hydrothermal treatment at a temperature of 100 to 300 Is processed, and the oxide first Nisuzu aqueous pull with S N_ ⁇ 2 concentration and particle size 0.5 -50 wt% of 4 to 50 nm, Z R_ ⁇ 2 in terms of 0.5 50 wt% concentration of the and an aqueous solution of O alkoxy zirconium salts, mixed in a weight ratio of 0.05 0.50 as Z r0 2 ZSn0 2, 60 ⁇ the resulting mixed-solution 10 O: a heated 0.1 to 50 hours
- step stannic oxide and zirconium oxide composite obtained in step (a4) and body aqueous sol, 0.02 ⁇ 4.
- Step (c4) Aging the aqueous medium obtained in Step (b4) at 20 to 300 for 0.1 to 50 hours, and Step (d4): Modification obtained in Step (c4)
- the aqueous sol of stannic oxide-zirconium oxide composite is contacted with an anion exchanger, and then aged at 20-300 for 0.1-50 hours to transform stannic oxide monoxide.
- a stable sol of zirconium composite colloid particles is obtained.
- the sol oxide based on the weight Z 1 " ⁇ 2:51 0 2 as 0.05:.
- stannic oxide that have a particle diameter of 1 ratio and 4 to 50 nm is its surface composite colloidal particles (a) as nuclei for the particles and the zirconium oxide particles, 0. 02 ⁇ 4.
- the step (d5) can be added if the varnish oxidized in the step (a5) contains anion. That is, the step (d5): the modified stannic oxide aqueous sol obtained in the step (c5) is brought into contact with an anion exchanger to remove anions present in the sol. Then, a step of aging at 20 to 300 for 0.1 to 50 hours is added to obtain a stable sol of the modified stannic oxide colloid particles. 10 ot: The above aging can be performed using an autoclave.
- step (a6) particle diameter of 4 to 50 nm and 0.5 to 50% by weight of SnO 2 a stannic oxide aqueous sol having a concentration, and an aqueous solution of Okishijirukoniu beam salts of 0. 5 to 50 wt% concentration in terms of Z R_ ⁇ 2, 0.1 as Z r 0 2 ZS N_ ⁇ 2 05-0
- the mixture was mixed at a weight ratio of 50 and the resulting mixture was heated at 60-100 for 0.1-50 hours to obtain a stannic oxide-zirconium oxide composite having a particle size of 4-50 nm.
- Step 6 (a 6) stannic oxide obtained in step - zirconium oxide composite aqueous sol, antimony pentoxide with a molar ratio of S I_ ⁇ 2 / S b 2 0 5 of 0.5 5 to 55 composite colloids particles of silica, and an aqueous medium containing the oligomer, or a mixture thereof, in terms of the metal oxide (Sb 2 ⁇ 5 + S I_ ⁇ 2) / (Sn0 2 + Z r0 2) (C6) step: aging the aqueous medium obtained in the step (b6) at 20 to 300 for 0.1 to 50 hours, and Step (d6): The aqueous sol of the modified varnish oxide-zirconium oxide complex obtained in step (c6) is brought into contact with an anion exchanger, and then aged at 20 to 30 for 0.1 to 50 hours.
- a stable sol of the modified stannic oxide-zirconium oxide composite colloid particles is obtained. Aging at 100 or more can be performed using an autoclave.
- the above-mentioned production method can be carried out under pressure using a autoclave.
- step a hydrothermal treatment at a temperature of 100 to 30 Ot: and a particle diameter of 4 to 501111 and a 0.5 to 50 weight % of preparing a stannic oxide aqueous sol having Sn_ ⁇ 2 concentration
- step step: the above (a 7) and stannic oxide aqueous sol obtained in step, of 0.
- step (c 7) step:.
- a modified stannic oxide aqueous sol is obtained from the step of aging for 0.1 to 50 hours.
- the step (d7) can be added when the stannic oxide in the step (a7) contains anion.
- step (d7) the modified stannic oxide aqueous sol obtained in step (c7) is brought into contact with an anion exchanger to remove anions present in the sol; Thereafter, a step of aging at 20 to 300 at 0.1 to 50 hours is added to obtain a stable sol of modified stannic oxide colloid particles.
- This sol is a sol surface oxidation secondary tin colloid particles having a particle size of.
- nuclei pentoxide having a molar ratio of S i C ⁇ ZS b 2 ⁇ 5 of 0.55 to 55 It is coated with composite colloidal particles of antimony and silica, its oligomer, or a mixture thereof (B2), and the weight ratio of (B2) / (A) is 0.01 based on the weight ratio of the metal oxides. It is a sol containing modified stannic oxide particles having a ratio of ⁇ 0.50 and a particle size of 4.5-60 nm.
- step (a8) hydrothermal treatment at a temperature of 100 to 300 oxide first Nisuzu aqueous sol having a S n 0 2 concentration of the particle diameter and 0.5 to 50 wt.% of to 50 nm, the O alkoxy zirconium salt of 0.5 to 50% strength by weight in terms of Z r0 2 an aqueous solution, mixed with 0.05 to 0 50 weight ratio of the Z r 0 2 ZS N_ ⁇ 2, 10 60 and the resulting mixed-solution Ot:.
- step (b8) stannic oxide and zirconium monoxide composite obtained in step (a8) an aqueous sol of 0.
- the composite aqueous sol is brought into contact with an anion exchanger and then aged at 20 to 300 T for 0.1 to 50 hours to obtain a stable sol of modified stannic oxide zirconium monoxide composite particles.
- SnO 2 05:. 1 ⁇ 0 50 zirconium oxide particles with stannic oxide particles having a particle diameter ratio of 1. 4 to 50 nm composite colloidal particles (a) is the surface as a nucleus, ⁇ of 0.
- the particles used for the nucleus are stannic oxide
- a sol of composite varnish and zirconium oxide is used.
- the former has a rutile-type crystal structure, and those obtained by applying these sols as a coating composition to a substrate and firing them have a high refractive index (the refractive index calculated from the coating film is 1.7 to 1.8) And excellent transparency.
- the latter has excellent weather resistance (light) performance by combining zirconium oxide in addition to the performance of the former.
- Each of the above sols may be either autoclave-treated or not autoclaved with stannic oxide.
- the latter has the excellent performance of the former, and the coating film obtained by applying these sols as a coating composition to a substrate and baking it has a high refractive index (the refractive index calculated from the coating film is 1.8 to: 1). . 9)
- the above-mentioned modified stannic oxide zirconium monoxide composite colloid particles can be observed by an electron microscope and have a particle size of approximately 4.5 to 60 nm.
- the sol obtained by the mixing has a pH approximately 1-9, but from Okishijirukoniu beam salt used for the modification CI-, N0 3 -, Anion such CH 3 C_ ⁇ _ ⁇ - Due to the high content of colloids, the colloid particles undergo micro-aggregation and the sol has low transparency.
- a stable, transparent, modified stannic oxide-zirconium oxide having a pH of 3 to 11 and good transparency is obtained.
- a sol of the nickel composite colloid particles can be obtained.
- the removal of the ion in the step is obtained by treating the sol obtained by the above-mentioned mixing with a hydroxyl-type ion-exchange resin at a temperature of 100 or less, preferably room temperature (at 20) to a temperature of about 60 to 60.
- a hydroxyl-type ion-exchange resin at a temperature of 100 or less, preferably room temperature (at 20) to a temperature of about 60 to 60.
- a hydroxyl group type anion exchange resin a commercially available product can be used, but a strong base type such as Amberlite 410 is preferable.
- the treatment with the hydroxyl group type anion exchange resin in the step (d) is performed at a metal oxide concentration of 1 to 10% by weight of the sol obtained by the mixing in the step (c).
- aging for 0.1 to 200 hours at a temperature of 20 to 100 can be performed in the step (c). It can be applied for 1 to 200 hours.
- the method for producing (a3 to d3), the method for producing (a4 to d4), the method for producing (a7 to d7), and the method for producing the raw material using the oxidized varnish sol subjected to hydrothermal treatment In the production method of (a8 to d8), aging for 0.1 to 200 hours at a temperature of 20 to 100 in those (c) steps is possible, but hydrothermal treatment of 100 to 30 Ot: For 0.1 to 200 hours. Both are possible.
- a preferred aqueous composite sol of the modified aqueous varnish varnish according to the present invention and the modified stannic oxide zirconia has a pH of 1.5 to 11.5, wherein pH is 1 to 1.5. . 1 exceeds 5, modified oxidized second tin colloid, and modified stannic oxide - easy S b 2 ⁇ 5 Koroido covering the oxide di Rukoniumu composite colloidal particles dissolved in the liquid. Further, when the total concentration of all the metal oxides in the sol of the modified stannic oxide colloid and the modified stannic oxide zirconium monoxide composite particles exceeds 60% by weight, Sols tend to be unstable. The preferred concentration as an industrial product is about 10 to 50% by weight.
- the modified metal oxide sol of the present invention can contain other optional components as long as the object of the present invention is achieved.
- oxycarboxylic acids are contained in an amount of about 30% by weight or less based on the total amount of all metal oxides, a colloid having further improved properties such as dispersibility can be obtained.
- the pH of the silane coupling agent or the hydrolyzate thereof is weakly acidic.
- An acid can be added to the modified metal oxide sol of the present invention to lower the pH in advance.
- the modified metal oxide sol has a pH of about 4 to 6.
- Examples of the oxycarboxylic acid used include lactic acid, tartaric acid, citric acid, dalconic acid, lingic acid, glycolic acid and the like. Further, it is possible to contain an alkali component, for example, L i, N a, K , R b, alkali metal hydroxides such as C s, NH 4, Echiruamin, Toriedji Ruamin, isopropyl ⁇ Min, n- propylamine Alkylamines such as benzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine. These can be used as a mixture of two or more. It can be used in combination with the above acidic components. These can be contained in about 30% by weight or less based on the total amount of all metal oxides.
- an alkali component for example, L i, N a, K , R b, alkali metal hydroxides such as C s, NH 4, E
- the sol concentration can be concentrated to a maximum of about 50% by weight by a conventional method, for example, an evaporation method or an ultrafiltration method.
- the concentration can be adjusted by adding the alkali metal, organic base (amine), oxycarboxylic acid or the like to the sol after concentration.
- a sol having a total metal oxide concentration of 10 to 40% by weight is practically preferable.
- the ultrafiltration method is used as the concentration method, polyanion, ultra-fine particles, etc., which coexist in the sol, pass through the ultrafiltration membrane together with water, and this causes the sol to become unstable. Polyanion, ultrafine particles, etc. can be removed from the sol.
- an organosol can be obtained by replacing the aqueous medium of the aqueous sol with a hydrophilic organic solvent.
- This substitution can be performed by a usual method such as a distillation method and an ultrafiltration method.
- the hydrophilic organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; linear amides such as dimethylformamide and N, N'-dimethylacetamide; N-methyl-2-pyrrolidone Cyclic amides, etc .; glycols such as ethyl acetate sorb, ethylene glycol and the like.
- R 2 and R 3 are the same organic group or different organic groups, and organic silicon compounds where a and b are the same integer or different integers.
- the organosilicon compound represented by the general formula (I) in the component (A) includes, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraphenylsilane Sethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, Cyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamicoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane , Dalicidoxymethyltriethoxysi
- the hydrolyzate of the organic silicon compound of the general formula (I) in the component (S) used in the coating composition of the present invention is obtained by hydrolyzing the organic silicon compound of the general formula (I). As a result, a compound in which part or all of R 2 is substituted with a hydrogen atom is obtained.
- These hydrolysates of the organic silicon compound of the general formula (I) can be used alone or in combination of two or more.
- the hydrolysis is performed by adding an acidic aqueous solution such as an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of acetic acid to the above-mentioned organic silicon compound and stirring the mixture.
- Organic Kei-containing compound represented by the 2 Y (II) is, for example, methylene bis methyldimethoxysilane, Echire emissions bis E chill dimethoxysilane, propylene bis E chill GETS Toxysilane, butylenebismethyljetoxysilane and the like can be mentioned. These can be used alone or in combination of two or more.
- the hydrolyzate of the organic silicon compound represented by the general formula (II) in the component (S) used in the coating composition of the present invention is obtained by hydrolyzing the organic silicon compound represented by the general formula (II). As a result, a compound in which part or all of X is substituted with a hydrogen atom is obtained.
- These hydrolysates of the organic silicon compound represented by the general formula (II) can be used alone or in combination of two or more.
- the hydrolysis is performed by adding an acidic aqueous solution such as an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of acetic acid to the above organic silicon compound, followed by stirring.
- the component (S) used in the coating composition of the present invention is at least one selected from the group consisting of the organic silicon compounds represented by the general formulas (I) and (II), and a hydrolyzate thereof.
- One type of silicon-containing substance is selected from the group consisting of the organic silicon compounds represented by the general formulas (I) and (II), and a hydrolyzate thereof.
- the component (S) used in the coating composition of the present invention is preferably at least one silicon selected from the group consisting of an organic silicon compound represented by the general formula (I) and a hydrolyzate thereof. It is a contained substance.
- one of R 1 and R 3 is an organic group having an epoxy group
- R 2 is an alkyl group
- a and b are each 0 or 1
- 3+ is 1 or 2.
- the organosilicon compound represented by the general formula (I) and a hydrolyzate thereof are preferred.
- Examples of the preferred organosilicon compounds include glycidoxymethyltrimethoxysilane, dalicydoxymethyltriethoxysilane, ⁇ -glycidoxyshethyltrimethoxysilane, a-dalicydoxyshethyltriethoxysilane, and 3-Dalicidoxyshethyltrimethoxysilane,) 3-Glycidoxyshethyltriethoxysilane, a-Dalicidoxypropyltrimethoxysilane, a-Glycidoxypropyltriethoxysilane,
- aglycidoxypropyl trimethoxysilane aglycidoxypropyl pyrmethyljetoxysilane, aglycidoxypropylmethyldimethoxysilane and hydrolysates thereof, and these are used alone or It can be used as a mixture.
- tetrafunctional compounds include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetran-propoxysilane, tetra-n-butoxysilane, tetra-tert-butoxysilane, and tetrasec-butoxy. Silane and the like.
- the modified metal oxide particles used for the component (T1) and the component (T2) of the coating composition of the present invention the modified sols described in the above 1 to 6 can be used.
- the coating composition of the present invention comprises the component (T1) or the component (T2) in an amount of preferably 1 to 500 parts by weight, particularly preferably 50 to 250 parts by weight, per 100 parts by weight of the component (S). It is to be combined. That is, (T1) component: a composite particle of stannic oxide particles or stannic oxide particles and zirconium oxide particles with respect to 100 parts by weight of the (S) component: the organic silicon compound. object based on the weight Z R_ ⁇ 2: S n0 2 0:. 1-0 50: 1 ratio and 4 colloidal particles having a particle size of 50 nm (a) is its surface as a nucleus, 0. 02-4. the 00 of MZS b 2 0 5 molar ratio (wherein M is.
- the coating composition of the present invention comprises the component (T1) or the component (T2) in an amount of preferably 1 to 500 parts by weight, particularly preferably 50 to 250 parts by weight, per 100 parts by weight of the component (S). It is to be combined. That is, based on 100 parts by weight of the component (S): 100 parts by weight of the organic silicon compound, the component (T2) is stannic oxide particles or composite particles of stannic oxide particles and zirconium oxide particles. object based on the weight Z R_ ⁇ 2: S N_ ⁇ 2 0:. 1-0 50: 1 ratio and 4 colloidal particles having a particle size of 50 nm to (a) as nuclei, its surface 0 .
- S i 0 2 ZS b 2 ⁇ 5 molar ratio composite roller i de particles of antimony pentoxide and silica having a 55 to 55, an oligomer thereof or a mixture thereof (B 2), and (B 2 ) / (A) is a ratio of 0.01 to 0.50 based on the weight ratio of the metal oxides, and a modified metal oxide having a particle size of 4.5 to 60 nm. It is appropriate to contain 1 to 500 parts by weight of the particles. If the modified metal oxide sol is less than 1 part by weight, the cured film will be refracted The rate of application is low, and the range of application to the substrate is significantly limited. On the other hand, if it exceeds 500 parts by weight, cracks and the like are likely to occur between the hardened film and the substrate, and the possibility of lowering the transparency is further increased.
- the coating composition of the present invention includes a curing agent for accelerating the reaction, a particulate metal oxide for adjusting the refractive index of the lens to be various substrates, and improving the wettability at the time of application.
- Various surfactants can be contained for the purpose of improving the smoothness of the cured film.
- an ultraviolet absorber, an antioxidant and the like can be added as long as they do not affect the physical properties of the cured film.
- the curing agent examples include amines such as arylamine and ethylamine, and various acids and bases including Lewis acids and Lewis bases, for example, organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, perchloric acid, and bromic acid.
- Lewis acids and Lewis bases for example, organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, perchloric acid, and bromic acid.
- a salt or metal salt having selenious acid, thiosulfuric acid, orthogeic acid, thiocyanic acid, nitrous acid, aluminic acid, carbonic acid, etc., and a metal alkoxide having aluminum, zirconium, titanium, or a metal chelate compound thereof. can give.
- Examples of the fine metal oxide include fine particles of aluminum oxide, titanium oxide, antimony oxide, zirconium oxide, silicon oxide, cerium oxide, and the like.
- the coating composition of the present invention can be applied to a substrate and cured to form a cured film. Curing of the coating composition is performed by hot air drying or active energy ray irradiation, and the curing is preferably performed in hot air of 70 to 200, particularly preferably 90 to 150. . Active energy rays include far-infrared rays, which can reduce damage due to heat.
- the coating composition of the present invention can be applied and cured on a substrate to form a cured film. Further, according to the present invention, an optical member having on its surface a film formed by laminating a cured film, an impact absorbing film, and an antireflection film made of the above coating composition can be obtained.
- Examples of a method for forming a cured film comprising the coating composition of the present invention on a substrate include a method of applying the above-described coating composition to a substrate.
- a coating method a commonly used method such as a dipping method, a spin method, and a spray method can be applied, but a diving method and a spin method are particularly preferable in terms of area.
- a chemical treatment with an acid, an alkali, or various organic solvents, a physical treatment with plasma, ultraviolet light, or the like, a detergent treatment with various detergents, and further using various resins Before applying the above-mentioned coating composition to a base material, a chemical treatment with an acid, an alkali, or various organic solvents, a physical treatment with plasma, ultraviolet light, or the like, a detergent treatment with various detergents, and further using various resins.
- the primer treatment the adhesion between the base material and the cured film can be improved.
- modified metal oxide particles described in the component (T 1) and the component (T 2) as a refractive index adjusting agent to the various resins for the primer.
- the antireflection film composed of a vapor-deposited inorganic oxide film provided on the cured film composed of the coating composition of the present invention is not particularly limited, and may be any of known inorganic oxide vapor-deposited films.
- a single-layer or multilayer antireflection film can be used.
- the anti-reflection film include, for example, anti-reflection films disclosed in Japanese Unexamined Patent Application Publication No. Hei 2-262104 and Japanese Patent Application Laid-Open No. 56-116003. .
- the shock absorbing film improves impact resistance.
- This shock absorbing film is made of a polyacrylic resin, a polyvinyl acetate resin, a polyvinyl alcohol resin, or the like.
- the cured film made of the coating composition of the present invention can be used as a high refractive index film for a reflective film, and can be used as a multifunctional film by adding a functional component such as antifogging, photochromic, and antifouling. You can also.
- the optical member having a cured film made of the coating composition of the present invention can be used for eyeglass lenses, camera lenses, window glasses of automobiles, optical filters attached to liquid crystal displays, plasma displays, and the like.
- the ratio of hydrogen peroxide to metallic tin was H 2 ⁇ 2 ZS n molar ratio was 2.5 .
- the time required for the addition of the aqueous hydrogen peroxide and metallic tin was 4.5 hours. After completion of the addition, the mixture was aged for 0.5 hours while maintaining the liquid temperature at 90 to 95.
- the Sn / C 1 equivalent ratio during the reaction was 1.92.
- the obtained tin oxide sol was 340 kg. This sol was a pale yellow transparent sol. The particle size of the tin oxide colloid was less than 10 nm under an electron microscope. It was stable even if left at room temperature for more than one year.
- the time required for the addition was 2.5 hours. After the addition was completed, the reaction was terminated by heating for 1 hour while maintaining the liquid temperature at 90.
- the ratio of hydrogen peroxide to metallic tin was H 2 O 2 / Sn molar ratio was 2.44.
- Specific gravity yield 352 kg of the obtained tin oxide sol 1. 22, pH 1. 49, Sn_ ⁇ 2 2 6.1 wt%, oxalic acid concentration from the charged 7.6 wt%, (COOH) 2 / Sn_ ⁇ 2 molar ratio was 0.47.
- the obtained sol had thixotropic properties, but had lower thixotropic properties than when an aqueous hydrochloric acid solution was used.
- the particle size of the tin oxide colloid was 10 to 15 nm under an electron microscope, and was spherical and had good dispersibility. This sol showed a tendency to slightly increase in viscosity upon standing, but was stable with no gelling observed at room temperature for 6 months.
- A—2300 g of the aqueous stannic oxide aqueous sol obtained in Step 1-1 was heated and aged at 140 ⁇ for 5 hours in an autoclave.
- the solution After diluting the obtained mixed aqueous solution of potassium hydroxide and potassium antimonate with pure water to a concentration of 5% by weight, the solution is passed through a column filled with a cation-type ion-exchange resin to form antimony pentoxide-silica. An aqueous medium containing the composite colloid and its oligomer was obtained.
- the obtained composite colloid was colorless and transparent, had a pH of 1.8, and had particles of 5 nm or less observed by a transmission electron microscope.
- the resulting modified aqueous stannic oxide sol (dilute solution) is concentrated at room temperature using a filtration device of an ultrafiltration membrane having a molecular weight cut-off of 50,000, and a high-concentration modified aqueous sol of stannic oxide is added to the aqueous solution. g obtained.
- This sol was stable at a specific gravity of 1.220, a pH of 7.90, a viscosity of 2.3 c.p., and a concentration in terms of metal oxide of 20.3% by weight.
- the alkali metal-containing antimony pentoxide colloid and its oligomer of B-111 component of Production Example 1 were mixed so that the weight ratio of (B) / (A) in terms of metal oxide was mixed to 0.1.
- the procedure was performed in the same manner as in Production Example 1 except that the aqueous medium having 51 g was changed to 277.8 g of an aqueous medium containing antimony pentoxide colloid containing B-1-2 component and its oligomer.
- the resulting modified high-concentration aqueous stannic oxide sol was stable at a specific gravity of 1.218, a pH of 8.80, a viscosity of 2.8 cp, and a concentration in terms of metal oxide of 20.4% by weight.
- the above-mentioned high-concentration modified stannic oxide aqueous sol (245 g) was distilled off at a rotary evaporator under reduced pressure at a liquid temperature of 30 at a temperature below, while adding 10 liters of methanol little by little to remove water. 162 g of modified stannic oxide sol obtained by replacing water of the sol with methanol was obtained.
- This sol has a specific gravity of 1.093, pH 8.34 (equivalent mixture with water), viscosity of 1.8 cp, and a concentration of 30.5% by weight in terms of metal oxide, a water content of 0.81% by weight, and an electronic component. Microscopic observation showed a particle size of 5 to 15 nm.
- the sol had a colloidal color, was highly transparent, and was stable without any formation of sediment, turbidity, thickening, etc., even after standing at room temperature for 3 months.
- the dried product of this sol had a refractive index of 1.76.
- the stannic oxide colloid of A—1-1—component of Production Example 1 was mixed with the A—1—3 component of A—1—3 so that the weight ratio of (B) / (A) in terms of metal oxide was mixed to 0.1.
- Aqueous medium containing B-1-1 component alkali component-containing antimony pentoxide and its oligomer is added to B07-1-2 colloid stannic oxide 127.07 g.
- the procedure was performed in the same manner as in Production Example 1 except that the amount of the aqueous medium containing the colloid and its oligomer was changed to 277.8 g.
- the resulting modified high-concentration aqueous stannic oxide sol was stable at a specific gravity of 1.220, a pH of 8.51, a viscosity of 2.4 c.p., and a concentration in terms of metal oxide of 21.2% by weight.
- the resulting modified high-concentration aqueous stannic oxide sol was stable at a specific gravity of 1 ⁇ 226, pH 7.92, viscosity of 3.1 cp. And a concentration of 22.0% by weight in terms of metal oxide.
- Step: B- in terms of the aqueous medium 68. 83 kg (S b 2 0 5 containing colloids and its cage Goma of Amin containing antimony pentoxide obtained in 1- 2 containing 1. 24 kg . to), the stirring (a) stannic oxide obtained in the step - the composite sol 779. 2 kg of zirconium oxide, S b 2 0 5 Roh (S N_ ⁇ 2 + Z R_ ⁇ 2) 0.1 was gradually added and mixed.
- the modified stannic oxide zirconium monoxide composite sol was obtained by heating and aging at 90-95 for 2-3 hours.This sol has a specific gravity of 1.011 and a viscosity of 2.9 c. ⁇ ⁇ , ⁇ 10.58, indicating that the sol had good transparency.
- the resulting modified stannic oxide zirconium monoxide complex aqueous sol (dilute solution) is fractionated by a filtration device of an ultrafiltration membrane having a molecular weight of 100,000 to obtain a high-concentration modified stannic oxide. 64.7 kg of an aqueous sol of the zirconium oxide composite was obtained. This sol was stable at a specific gravity of 1.233, a viscosity of 4.8 cp, a pH of 9.75, and a total metal oxide concentration of 22.1% by weight.
- the above-mentioned high-concentration modified stannic oxide zirconium monoxide composite aqueous sol (50 kg) was depressurized at a rotary evaporator overnight, and at a liquid temperature of 30 or less, water was distilled while gradually adding 1200 kg of methanol.
- 30.8 kg of a modified methanol oxide-zirconium oxide composite sol in which the aqueous sol was replaced with methanol was obtained.
- the methanol sol of the modified stannic oxide-zirconium oxide complex obtained by filtering this sol and adjusting the concentration has a particle diameter of 12 nm as observed by electron microscope, a specific gravity of 086, and a viscosity of 3.2 cp.
- This sol had a colloidal color, was highly transparent, and was stable without any formation of sediment, turbidity, thickening, etc., even after 3 months at room temperature.
- the refractive index of this sol was 1.87.
- the prepared mixture was subjected to a heat treatment at 95 under stirring for 5 hours to obtain 910.2 kg of a stannic oxide-zirconium oxide composite sol.
- the sol 1.75% by weight Sn0 2, 0. 26% by weight Z R_ ⁇ 2, was 2.01% by weight Sn0 2 + Z r0 2.
- the mixed sol-like slurry obtained in the step (c) is passed through a column filled with a hydroxyl-type anion exchange resin in the step (d) to remove anions (C 1-) contained in the sol. Removed. Then, a modified stannic oxide zirconium oxide composite sol was obtained by heating and aging at 90 to 95 for 2 to 3 hours. This sol was a highly transparent sol having a specific gravity of 1.012, a viscosity of 3.0 cp. And an H of 10.78.
- the resulting modified stannic oxide zirconium monoxide composite aqueous sol (dilute solution) is fractionated by a filtration device of an ultrafiltration membrane having a molecular weight of 100,000 to obtain a high-concentration modified stannic oxide-oxidized solution. 69.5 kg of a zirconium composite aqueous sol was obtained. This sol was stable at a specific gravity of 1.284, a viscosity of 5.0 c ⁇ ., ⁇ ⁇ .19, and a total metal oxide concentration of 26.1% by weight. Water of 50 kg of the above-mentioned high-concentration modified stannic oxide / zirconium monoxide composite aqueous sol was taken out under reduced pressure at a temperature of 30 ° C.
- the modified stannic oxide zirconium monoxide composite methanol sol obtained by filtering and adjusting the concentration of this sol has a particle size of 13 nm as determined by electron microscope observation, a specific gravity of 1.086, and a viscosity of 4.2. c p., pH 8.92 (equivalent mixture with water), the concentration in terms of metal oxide was 30.3% by weight, and the water content was 0.33% by weight.
- This sol has a colloidal color, high transparency, and 3 No abnormalities such as sedimentation, turbidity, and thickening were observed even after standing for a month.
- the refractive index of this sol was 1.92.
- the resulting modified aqueous stannic oxide sol (dilute solution) is concentrated at room temperature by a filtration device of an ultrafiltration membrane having a molecular weight cut-off of 50,000, and a high-concentration aqueous sol of modified stannic oxide is added to the solution.
- This sol was stable with a pH of 87, a viscosity of 2.3 c.p. and a concentration of 12.7% by weight in terms of metal oxide.
- the above-mentioned high-concentration modified stannic oxide aqueous sol (472 g) was distilled under reduced pressure at the mouth of a tally evaporator at a liquid temperature of 3 O: the water was distilled off while adding 9 liters of methanol little by little. 190 g of a modified stannic oxide yellow sol obtained by replacing the water of the sol with methanol was obtained.
- This sol has a specific gravity of 1.009, pH of 2.06 (equiweight mixture with water), viscosity of 1.6 cp., A concentration converted to metal oxide of 30.3% by weight, transmittance of 68%, and moisture of 0%. 9% by weight, particle size was 10 to 15 nm observed by electron microscopy.
- This sol had a colloidal color, was highly transparent, and remained stable without any formation of sediment, turbidity, thickening, etc. even after standing at room temperature for 3 months.
- the dried product of this sol had a refractive index of 1.8.
- the prepared mixed solution was subjected to a heat treatment at 95 with stirring for 5 hours to obtain 799.2 kg of a stannic oxide / zirconium oxide composite sol.
- step (b) B- 2 - in aqueous medium 1050 containing colloid and an oligomer thereof of the silica complex g (S b 2 O s + S I_ ⁇ 2 as 10 g containing) - antimony pentoxide obtained in 1 Then, with stirring, the complex sol of stannic oxide and zirconium monoxide obtained in step (b) was
- the modified stannic oxide-zirconium oxide composite sol was obtained by heating and aging at 90 to 95 tons for 2 to 3 hours. This sol was PH 8.00 with good transparency. .
- the above high-concentration modified stannic oxide / zirconium oxide composite aqueous sol (517 g) was distilled under reduced pressure at a low evaporator at a liquid temperature of 30 at a temperature of 30 or less while gradually adding 8 L of methanol.
- 190 g of a modified stannic oxide zirconium monoxide composite methanol sol in which the aqueous sol was replaced with methanol was obtained.
- the modified stannic oxide zirconium oxide composite sol obtained by filtering and adjusting the concentration of this sol has a particle size of 10 to 15 nm as observed by electron microscopy. 1.
- Glycolic acid (5.9 g) was added to 1.3 kg of the modified stannic oxide / zirconium monoxide complex methanol sol obtained in Production Example 11, dissolved, and allowed to stand still.
- the obtained sol was stable at a specific gravity of 1.094, a viscosity of 1.6 cp, a pH of 5.2, and a total metal oxide concentration of 30.3% by weight.
- the resulting modified high concentration aqueous stannic oxide sol had a pH of 11.1, a viscosity of 2.5 cp, and a stable concentration of 13.5% by weight in terms of metal oxide.
- the above high-concentration modified stannic oxide aqueous sol (392 g) was distilled off by distilling water while gradually adding 9 liters of methanol at a liquid temperature of 3 Ot or less under reduced pressure at the mouth of the evaporator. 173 g of a modified stannic oxide sol obtained by replacing water in the aqueous sol with methanol was obtained.
- This sol has a specific gravity of 1.091, pH 8.7 (mixed mixture with water), viscosity of 1.0 cp, concentration in terms of metal oxide is 30% by weight, moisture is 1.9% by weight, electron microscopic observation Was 10 to 15 nm.
- This sol had a colloidal color, was highly transparent, and was stable without any formation of sediment, turbidity, thickening, etc. after standing at room temperature for 3 months.
- the dried product of this sol had a refractive index of 1.95.
- the stannic oxide colloid of A—1-1—component of Production Example 1 was mixed with the A—1—5 component of A—1—5 so that the weight ratio of (B) / (A) converted to metal oxide was
- An aqueous medium containing an antimony pentoxide colloid containing an alkali component of B-1-1 and its oligomer was added to 53 73 g of stannic oxide colloid, and an antimony pentoxide containing an alkali component of B-2-1 component-silicone composite
- the procedure was performed in the same manner as in Production Example 1 except that the amount of the aqueous medium containing the colloid and its oligomer was changed to 503 g.
- the resulting modified high-concentration aqueous stannic oxide sol has a specific gravity of 1.222, pH 3.2, viscosity of 2.1 cp., And a stable concentration of 19.8% by weight in terms of metal oxide. there were.
- the water of the aqueous sol was replaced with methanol by distilling water while slightly adding 21 liters of methanol to the above-mentioned high-concentration modified stannic oxide aqueous sol 2160 g with a rotary evaporator under slightly reduced pressure. 1360 g of the modified modified stannic oxide methanol sol was obtained.
- This sol has a specific gravity of 1.083, pH 6.8 (equivalent weight mixture with water), viscosity of 1.2 c.P., concentration in terms of metal oxide is 30% by weight, water is 2.0% by weight, electron microscope Observed particle size was 10-15 nm.
- This sol had a colloidal color, was highly transparent, and was stable without any formation of sediment, turbidity, thickening, etc. after standing at room temperature for 3 months.
- the dried product of this sol had a refractive index of 1.95.
- a titanium oxide methanol sol used in a comparative example of the present invention was prepared.
- Titanium tetrachloride (to 2% by weight 27. As T i 0 2. C 1 content 32. 0% by weight. Sumitomo Sitix (Ltd.)) 587. 5 g (T i 0 2 as 159. 8 g containing.) and a water 2608. 5 g was taken up in 3 L jacketed glass separable flask of titanium water solution chloride 3196 g (T I_ ⁇ 2 5. containing 0 wt%.) was created. After adding 50 g of 28% aqueous ammonia to this aqueous solution while stirring with a glass stirring rod, the aqueous solution is hydrolyzed with 95 at room temperature for 10 hours. An assembly was obtained.
- This titanium oxide colloid aggregate slurry was subjected to suction filtration using 5 B filter paper, and then washed with about 40 liters of water to remove excess electrolyte to obtain 620 g of titanium oxide wet cake. .
- an anion exchange resin (Amberlite IRA-410, manufactured by Organo Corporation) 200 m 1
- This sol was concentrated under reduced pressure on a rotary evaporator to obtain 1070 g of an aqueous concentrated sol of alkaline titanium oxide.
- aqueous medium was replaced with methanol by a distillation method to prepare 775.2 g of a titanium oxide methanol sol.
- the resulting methanol sol had a specific gravity of 0.970, a viscosity of 4.5 mPa ⁇ s, PH (1 + 1) 8.98, an electrical conductivity of 1600 s / cm, a Ti 0 2 of 20.2% by weight, and a water content of 3 4% by weight.
- a modified stannic oxide composite methanol sol coated with the alkylamine-containing antimony pentoxide obtained in Production Example 1 described above (containing 30.5% by weight in terms of total metal oxides) 397.8% by weight Parts, 65 parts by weight of butyric ester, and 4.2 parts by weight of aluminum acetylacetonate as a curing agent 142.1 parts by weight of a partial hydrolyzate of the above-mentioned 7 "-glycidoxypropyl trimethoxysilane
- the mixture was filtered to prepare a coating liquid.
- Table 1 shows the evaluation results.
- Example 6 Instead of ⁇ -glycidoxypropyltrimethoxysilane corresponding to the component A, 74.2 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane corresponding to the component A and ⁇ -glycidoxypropylmethyldimethoxysilane 3 1 The procedure was the same as in Example 3 except that 1 part by weight was used. Table 1 shows the evaluation results.
- the modified oxide coated with the alkylamine-containing antimony pentoxide of Production Example 5 was used instead of the modified oxidized nitrous oxide sol coated with the alkylamine-containing antimony pentoxide of Production Example 1 used in Example 1.
- Complex methanol sol of tin tin zirconium monoxide (containing 30.5% by weight in terms of total metal oxides) The same procedure as in Example 1 was carried out except that 39.77.8 parts by weight were used. .
- Example 7 instead of the modified oxyhydrazine sol coated with an alkylamine-containing antimony pentoxide of Production Example 1 used in Example 1, coated with a complex colloid of antimony pentoxide-silica of Production Example 7 The same procedure was performed as in Example 1 except that 40.3 parts by weight of the modified stannic oxide methanol sol (containing 30.3% by weight in terms of total metal oxides) was used.
- Modified stannic oxide zirconium monoxide composite methanol sol (containing 25.0% by weight in terms of total metal oxide) Performed in the same manner as in Example 1 except that 45.2 parts by weight was used.
- Example 1 modified stannic oxide sol coated with alkylamine-containing antimony pentoxide of Production Example 1 used in Example 1, it was coated with a complex colloid of antimony pentoxide-silicone force of Production Example 8.
- Modified stannic oxide zirconium monoxide composite methanol sol (containing 25.0% by weight in terms of total metal oxide) Performed in the same manner as in Example 1 except that 45.2 parts by weight was used.
- Example 1 was coated with a complex colloid of antimony pentoxide-silicone force of Production Example 8.
- Example 9 The modified oxide coated with the alkylamine-containing antimony pentoxide of Production Example 9 instead of the modified stannic oxide sol coated with the alkylamine-containing antimony pentoxide of Production Example 1 used in Example 1 was used.
- Complex methanol sol of tin tin zirconium oxide (contains 30.1% by weight in terms of total metal oxide) The same procedure as in Example 1 was carried out except that 403.1 parts by weight was used. .
- the modified stannic oxide methanol sol coated with the alkylamine-containing antimony pentoxide of Production Example 1 used in Example 1 instead of the modified stannic oxide methanol sol of Production Example 15 used in Example 1 was used.
- Ditin methanol sol (containing 30.1% by weight in terms of total metal oxides) was carried out in the same manner as in Example 1 except that 403.1 parts by weight was used.
- Example 16 Modified stannic oxide methanol sol (containing 30.1% by weight in terms of total metal oxides) The same procedure as in Example 1 was carried out except that 403.1 parts by weight was used.
- Example 1 instead of the sol used in Example 1, except for using (2 0. 2 containing wt%. As T i 0 2) 6 4 3. 6 parts oxidized Chitanmetano one Ruzoru produced in Comparative Production Example 1 Were performed in the same manner as in Example 1. Table 1 shows the evaluation results.
- Example 1 a tin oxide methanol sol (Sn) coated with tungsten oxide / stannic oxide composite fine particles disclosed in 0 2 + W0 3 as 3 0. containing 0 wt%.) was carried out in the same manner as the 4 3 3. 3 parts by weight of all the actual Example 1, except that the catalyst.
- the evaluation results are shown in Table 1.
- Example 1 a colloidal methanol sol (T i 0 2 + S N_ ⁇ 2 + Z r 0 2 as 3 0. containing 0 wt%.) was carried out in the same manner as the 4 3 3. 3 parts by weight in example 1 except the using. Table 1 shows the evaluation results.
- Comparative Example 4 The same procedure was performed as in Example 1 except that 650.0 parts by weight of colloidal silica (methanol sol, solid content 20%, average particle size 15 nm) was used instead of the sol used in Example 1. The evaluation results are shown in Table 1.
- the physical properties of the optical members having a cured film obtained in the present example and comparative example were measured by the following measurement methods.
- the surface of the cured film was rubbed with steel wool # 0000 to determine the difficulty of scratching.
- Judgment criteria were evaluated as A> B> C in order of difficulty of scratching.
- the optical member having the cured film was visually judged under a fluorescent lamp.
- the criteria are as follows. A has almost no interference fringes, and B and C are more likely to occur in the following order.
- the optical member was immersed in warm water at 80 for 2 hours and subjected to the same adhesion test as described above.
- the film was visually inspected under a fluorescent lamp indoors for cloudiness.
- the criteria are as follows. A has almost no cloudiness, and B and C are more likely to occur in this order.
- the obtained optical member was exposed outdoors for one month, and the appearance change of the optical member after the exposure was visually judged.
- Example 1 AA ⁇ && A A ⁇ ⁇ Example 2 AA 3 ⁇ 4 3 ⁇ 4 3 ⁇ 4 A A A ⁇ Example 3 A r r & 3 ⁇ 4 A A A ⁇ ⁇ ⁇ 4 A r ⁇ A Without a temple
- Example 5 AAA
- Example 6 A r A ⁇ Abnormal None
- Example 7 A Electricity Ari None
- Example 8 A ⁇ ⁇ r r ⁇ e
- Example 1 3 A ⁇ A A ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4
- Example 1 4 A A A None Example 1 7 AA Good Good A No abnormality
- Example 18 AA Good Good A No abnormality
- Example 19 AA Good Good A No abnormality Comparative Example 1 BA Good Peeling B
- Comparative example 2 BA good Partial peeling A Slight yellowing Comparative example 3 A-BA good good A-B No abnormality Comparative example 4 AC good Good A No abnormality Examples 1 to 19 of the present invention showed scratch resistance and interference It was excellent in stripes, adhesion, warm water resistance, transparency, and weather resistance. However, Comparative Examples 1 and 2 were not satisfactory in abrasion resistance, hot water resistance, transparency, and weather resistance, and Comparative Example 4 was not preferable because interference fringes were observed. Further, Comparative Example 3 had practically no inferior results, but was slightly smaller than Examples 1 to 19. Industrial applicability
- the sol of the present invention is particularly useful as a component for improving the refractive index, dyeing property, chemical resistance, water resistance, moisture resistance, light resistance, weather resistance, abrasion resistance, etc. for forming a hard coat film on a plastic lens. Although effective, it can be used for various other purposes.
- sols of the present invention By applying the sol of the present invention to the surface of organic fibers, textiles, paper, and the like, the flame retardancy, surface slip resistance, antistatic property, dyeing property, and the like of these materials can be improved.
- These sols can be used as a binder for ceramic fibers, glass fibers, ceramics and the like. Furthermore, by mixing and using in various paints and various adhesives, the water resistance, chemical resistance, light resistance, weather resistance, abrasion resistance, flame resistance, etc. of these cured coatings are improved. be able to.
- these sols can be generally used as surface treatment agents for metal materials, ceramic materials, glass materials, plastic materials, and the like. It is also useful as a catalyst component.
- Optical member having a cured film comprising the coating composition of the present invention in addition to the eyeglass lens, It can be used for camera lenses, automotive window glass, optical filters attached to liquid crystal displays and plasma displays, and so on.
- Japanese Patent Application No. 2002-350762 (filed on December 3, 2002) and Japanese Patent Application No. 2002-350763 (2002 Japanese Patent Application 2003-097786 (filed on April 1, 2003), Japanese Patent Application 2003-097789 (filed on April 1, 2003) Japanese Patent Application 2003-161080 (filed on June 2003)
- the entire contents of the specifications of Japanese Patent Application No. 2003-161087 (filed on June 5, 2003) are incorporated herein by reference.
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US10/537,438 US7563827B2 (en) | 2002-12-03 | 2003-12-03 | Modified stannic oxide sol, stannic oxide-zirconium oxide composite sol, coating composition and optical element |
AU2003289144A AU2003289144A1 (en) | 2002-12-03 | 2003-12-03 | Modified stannic oxide sol, stannic oxide-zirconium oxide composite sol, coating composition and optical member |
EP03777209.2A EP1568659B1 (en) | 2002-12-03 | 2003-12-03 | Modified stannic oxide sol, stannic oxide-zirconium oxide composite sol, coating composition and optical member |
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JP2002350762 | 2002-12-03 | ||
JP2002350763 | 2002-12-03 | ||
JP2002-350763 | 2002-12-03 | ||
JP2002-350762 | 2002-12-03 | ||
JP2003-97789 | 2003-04-01 | ||
JP2003-97786 | 2003-04-01 | ||
JP2003097789 | 2003-04-01 | ||
JP2003097786 | 2003-04-01 | ||
JP2003-161080 | 2003-06-05 | ||
JP2003-161087 | 2003-06-05 | ||
JP2003161080 | 2003-06-05 | ||
JP2003161087 | 2003-06-05 |
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US (1) | US7563827B2 (ja) |
EP (2) | EP1568659B1 (ja) |
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EP1661861A1 (en) * | 2004-11-29 | 2006-05-31 | Nissan Chemical Industries, Limited | Process for producing modified stannic oxide sol and stannic oxide/zirconium composite sol |
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US6626987B1 (en) * | 1999-08-16 | 2003-09-30 | Nissan Chemical Industries, Ltd. | Modified metal oxide sol, coating composition and optical element |
DE60330921D1 (de) | 2002-12-03 | 2010-02-25 | Nissan Chemical Ind Ltd | Verfahren zur Herstellung von modifiziertem Zinnoxidsol und Zinnoxid-Zirkonoxid-Mischsol. |
US7556682B2 (en) * | 2005-08-09 | 2009-07-07 | Nissan Chemical Industries, Ltd. | Zirconium oxide-tin oxide composite sol, coating composition and optical member |
JP5146683B2 (ja) * | 2006-07-14 | 2013-02-20 | 日産化学工業株式会社 | 変性された酸化ジルコニウム−酸化第二スズ複合体ゾルの製造方法 |
US8697757B2 (en) * | 2008-07-17 | 2014-04-15 | Nissan Chemical Industries, Ltd. | Hydrophobic organic solvent-dispersed sol of anhydrous zinc antimonate colloidal particles and method for producing the same |
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US11583389B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing |
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US11529230B2 (en) | 2019-04-05 | 2022-12-20 | Amo Groningen B.V. | Systems and methods for correcting power of an intraocular lens using refractive index writing |
US11564839B2 (en) | 2019-04-05 | 2023-01-31 | Amo Groningen B.V. | Systems and methods for vergence matching of an intraocular lens with refractive index writing |
US11583388B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for spectacle independence using refractive index writing with an intraocular lens |
US11944574B2 (en) | 2019-04-05 | 2024-04-02 | Amo Groningen B.V. | Systems and methods for multiple layer intraocular lens and using refractive index writing |
CN112978788B (zh) * | 2021-02-07 | 2022-04-22 | 武汉大学 | 二氧化锡溶胶制备方法、无退火效应的二氧化锡平面结构钙钛矿光伏电池及制备方法 |
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- 2003-12-03 DE DE60330921T patent/DE60330921D1/de not_active Expired - Lifetime
- 2003-12-03 EP EP03777209.2A patent/EP1568659B1/en not_active Expired - Lifetime
- 2003-12-03 US US10/537,438 patent/US7563827B2/en active Active
- 2003-12-03 WO PCT/JP2003/015486 patent/WO2004050560A1/ja active Application Filing
- 2003-12-03 AU AU2003289144A patent/AU2003289144A1/en not_active Abandoned
- 2003-12-03 EP EP07013820A patent/EP1847511B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
AU2003289144A1 (en) | 2004-06-23 |
US20060025518A1 (en) | 2006-02-02 |
EP1568659A1 (en) | 2005-08-31 |
EP1847511B1 (en) | 2010-01-06 |
EP1568659A4 (en) | 2006-07-05 |
EP1847511A1 (en) | 2007-10-24 |
US7563827B2 (en) | 2009-07-21 |
DE60330921D1 (de) | 2010-02-25 |
EP1568659B1 (en) | 2015-09-02 |
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