WO2007060884A1 - 中空シリカ微粒子、それを含む透明被膜形成用組成物、および透明被膜付基材 - Google Patents
中空シリカ微粒子、それを含む透明被膜形成用組成物、および透明被膜付基材 Download PDFInfo
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- WO2007060884A1 WO2007060884A1 PCT/JP2006/322961 JP2006322961W WO2007060884A1 WO 2007060884 A1 WO2007060884 A1 WO 2007060884A1 JP 2006322961 W JP2006322961 W JP 2006322961W WO 2007060884 A1 WO2007060884 A1 WO 2007060884A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
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- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/149—Coating
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- C01B33/113—Silicon oxides; Hydrates thereof
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- C01B33/126—Preparation of silica of undetermined type
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- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/60—Particles characterised by their size
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
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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
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2996—Glass particles or spheres
Definitions
- the present invention relates to hollow silica fine particles whose surface is treated with a silane compound, and a method for producing the same.
- the present invention also relates to a transparent film-forming composition containing the hollow silica fine particles, and a substrate having a transparent film on the surface thereof, which is obtained by curing the transparent film-forming composition.
- hollow silica particles having a particle diameter of about 0.1 to 380 ⁇ m are known (see Patent Document 1 and Patent Document 2).
- alkaline silica silicate aqueous solution active silica is precipitated on a core made of a material other than silica, and the material is removed without destroying the silica shell, thereby producing a hollow particle having a dense silica shell force. This method is known (see Patent Document 3).
- micron-sized spherical silica particles having a core-shell structure in which the outer peripheral portion is a shell and the central portion is hollow, and the shell is denser on the outer side and has a coarser concentration gradient structure on the inner side are known (Patent Document 4). reference).
- the applicant of the present application first obtains nanometer-sized composite oxide fine particles having a low refractive index by completely covering the surface of porous inorganic oxide fine particles with silica or the like. (See Patent Document 5), and further, a silica coating layer is formed on the core particles of the composite oxide composed of silica and an inorganic acid other than silica, so that an inorganic acid other than silica is formed. It is proposed that nanometer-sized silica-based fine particles with a low refractive index having cavities inside can be obtained by removing particles and coating silica if necessary (see Patent Document 6). ).
- Patent Document 8 (a) —general formula: RSi (OR 2) [R: hydrocarbon group having 1 to 6 carbon atoms, R: carbon
- trialkoxysilane is calculated as RSiO.
- the coating film can be whitened by limiting the amount of silica fine particles. There is a description about being suppressed.
- Patent Document 9 (A) acetyl cetatoate compound and (B) inorganic compound fine particles are uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent. Proposes a method of using an inorganic compound particle having an average particle size of 50 nm or less as an inorganic compound particle for preventing whitening of a transparent film obtained by applying a coating liquid for coating formation to a substrate and curing it. .
- Patent Document 10 as an antireflective film that does not cause the surface to be scratched by abrasion or the like and does not peel off the low refractive index layer, at least one on the transparent plastic film substrate has 2 per molecule.
- Inorganic fine particles with an average particle size of 0.5 to: LOOnm were added to a matrix composed of UV-cured resin, the main component of which is a polyfunctional monomer containing at least one (meth) ataryloxy group
- ⁇ An antireflection film characterized by having a low refractive index layer containing silica fine particles of LOOnm has been proposed.
- the use of inorganic fine particles of less than 20 Onm By scattering There is a description that the hard coat layer can suppress whitening.
- Patent Document 11 includes a base material and a transparent film provided on the surface of the base material.
- the bright film comprises (0 a matrix containing a fluorine-substituted alkyl group-containing silicone component and inorganic compound particles having a GO outer shell layer and porous or hollow inside, and in the transparent film Transparent, characterized by maintaining porosity or cavities
- An invention relating to a coated substrate is disclosed.
- a transparent coating comprising such hollow silica fine particles and a binder is a characteristic unique to hollow silica fine particles. 1.25 ⁇ : Low refractive index of about L 45 can be realized, but whitening of the coating occurs.
- Patent Document 1 Japanese Patent Laid-Open No. 6-330606
- Patent Document 2 Japanese Patent Laid-Open No. 7-0113137
- Patent Document 3 Japanese Translation of Special Publication 2000-500113
- Patent Document 4 Japanese Patent Application Laid-Open No. 11-0129318
- Patent Document 5 JP-A-7-133105
- Patent Document 6 Japanese Patent Laid-Open No. 2001-233611
- Patent Document 7 Japanese Patent Laid-Open No. 4-348147
- Patent Document 8 JP-A-1-306476
- Patent Document 9 Japanese Patent Laid-Open No. 4-247427
- Patent Document 10 Japanese Patent Application Laid-Open No. 2004-326100
- Patent Document 11 Japanese Unexamined Patent Application Publication No. 2002-79616
- a coating composition containing hollow silica fine particles and a binder is prepared and a transparent film is formed on a substrate
- a composition containing ordinary silica fine particles and a binder is prepared, and a transparent film is similarly formed.
- a transparent film having a low refractive index can be obtained as compared with the case where it is formed, when hollow silica fine particles are used, there is a problem that whitening (whitening) easily occurs in the transparent film.
- further improvements have been required for scratch resistance and adhesion.
- the present invention has been made to solve such a problem, and even when a coating composition containing hollow silica fine particles and a binder is prepared and a transparent film is formed on a substrate, it is transparent.
- An object of the present invention is to provide a hollow silica fine particle capable of suppressing whitening of a film and exhibiting excellent scratch resistance and adhesion, and a method for producing the same.
- the present invention also provides a transparent film-forming composition containing hollow silica fine particles capable of exhibiting such excellent effects, and a substrate with a transparent film obtained by curing the transparent film-forming composition. For the purpose.
- An object of the present invention is to further provide a substrate with a transparent film, in which hollow silica fine particles are unevenly distributed in a transparent film of the substrate with a transparent film, and a composition for forming a transparent film therefor. It is what.
- the present invention provides a substrate with a transparent film in which hollow silica fine particles and metal oxide fine particles are unevenly distributed in the transparent film of the substrate with a transparent film, and a composition for forming a transparent film therefor, respectively. It is intended to be provided.
- an average particle diameter measured by a dynamic light scattering method is 5 to 300 nm, a specific surface area is 50 to 1500 m 2 Zg, and a cavity is formed inside the outer shell.
- the hollow silica fine particles are characterized by exhibiting a weight loss of 1.0% by weight or more in a temperature range of 200 ° C. to 500 ° C. by thermogravimetry (TG). .
- the second invention of the present application is characterized in that the hollow silica fine particles have a positive DTA peak in a differential heat retention measurement (DTA) in a temperature range of 200 ° C. to 500 ° C.
- a third invention of the present application is characterized in that the hollow silica fine particles have an organic group bonded directly to a silicon atom on the surface thereof.
- the hollow silica fine particles have a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms or a halogen atom having 1 to 18 carbon atoms in which an organic group directly bonded to a silicon atom on the surface thereof is saturated. ⁇ It is characterized by one or more selected hydrocarbon bases.
- an organosol having a silica concentration of 1 to 70% by weight in which hollow silica fine particles are dispersed is prepared, and the organosol is mixed with a silane compound and a silane compound in a temperature range of 30 ° C to 300 ° C.
- the addition amount of the silane compound is in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the hollow silica fine particles, and the addition amount of the alkali catalyst is Above A method for producing hollow silica fine particles characterized by being in the range of 20 to 2, OOOppm with respect to the organosol.
- a seventh invention of the present application is a composition for forming a transparent film, comprising the hollow silica fine particles according to any one of the first to fourth inventions and a binder.
- the eighth invention of the present application is a substrate with a transparent film, characterized in that the transparent film-forming composition according to the seventh invention has a transparent film on the surface.
- the hollow silica fine particles according to the fourth aspect are represented by the following general formula:
- It has an organic group of (1) or general formula (2) and shows a weight loss of 1.5% by weight or more in a temperature range of 200 ° C to 500 ° C by thermogravimetry (TG). It is the hollow silica fine particle characterized.
- R is a divalent hydrocarbon group having 1 to 12 carbon atoms
- R is a divalent hydrocarbon group having 1 to 12 carbon atoms
- the hollow silica fine particles according to the fourth aspect of the present invention are represented by the following general formula:
- the eleventh aspect of the present invention relates to the seventh aspect of the present invention.
- the surface charge amount (Q) of the hollow silica fine particles contained in the composition for forming a transparent film is in the range of 5 to 20 / ⁇ / 8.
- composition for transparent film formation characterized.
- the concentration (C) of the hollow silica fine particles contained in the composition for forming a transparent film according to the eleventh aspect is 0.1 to 20% by weight, the solid content of the binder,
- composition for forming a transparent film is characterized in that the concentration (C) is in the range of 1 to 50% by weight and the solvent is a polar solvent.
- the composition for forming a transparent film according to the seventh invention has a surface charge amount (Q)
- A)] is a composition for forming a transparent film, wherein the value is in the range of ⁇ 95 ⁇ eqZg.
- the concentration (C) of the hollow silica fine particles contained in the composition for forming a transparent film according to the thirteenth aspect is 0.1 to 20% by weight, and the metal oxide Fine particles
- the concentration of the child (C) is in the range of 0.1 to 20% by weight
- the transparent film forming composition is in the range of 1 to 50% by weight, and the transparent film forming composition is characterized in that the solvent is a polar solvent.
- the fifteenth invention of the present application has a transparent coating (film thickness ⁇ ! To lOOOOnm) on the surface, which is a cured film of the transparent film-forming composition according to the eleventh invention or the twelfth invention.
- a sixteenth aspect of the present application is the substrate with a transparent coating according to the fifteenth aspect, wherein the hollow silica fine particles are unevenly distributed and the dispersed state is a single layer or a multilayer. It is.
- the seventeenth invention of the present application has a transparent film (film thickness ⁇ ! To lOOOOnm), on which the transparent film-forming composition according to the thirteenth invention or the fourteenth invention is cured, on the surface.
- a substrate with a coating wherein the hollow silica fine particles are unevenly distributed and dispersed on the outer surface side from the intermediate point in the thickness direction of the transparent coating, and are on the substrate side from the intermediate point in the thickness direction.
- a substrate with a transparent coating characterized in that the metal oxide fine particles are unevenly distributed and dispersed.
- the hollow silica fine particles are unevenly distributed and the dispersed state is a single layer or a multilayer, and the metal oxide fine particles are unevenly distributed.
- the substrate with a transparent coating is characterized in that the dispersed state is a single layer or a multilayer.
- the average particle diameter measured by a dynamic light scattering method is 5 to 300 nm
- the specific surface area is 50 to 1500 m 2 Zg
- a cavity is formed inside the outer shell.
- Hollow silica fine particles and measured by thermogravimetry (TG) in the temperature range of 200 ° C to 500 ° C. 1.
- TG thermogravimetry
- the surface charge (Q) is in the range of S SO / z eqZg
- an organosol having a silica concentration of 1 to 70% by weight in which hollow silica fine particles are dispersed is prepared, and a silane compound and a silane compound are added to the organosol in a temperature range of 30 ° C to 300 ° C.
- Z or a polyfunctional acrylate ester resin having a hydrophobic functional group and an alkali catalyst are added, and the water content is 0.1 to 50% by weight with respect to the amount of silica compound.
- a method for producing hollow silica fine particles comprising reacting the hollow silica fine particles.
- a transparent film obtained by applying the composition for forming a transparent film containing the hollow silica fine particles of the present invention and a binder to a substrate is a low refractive index film having a refractive index of 1.25 to L45.
- it is excellent in scratch resistance and adhesion, in which discoloration such as whitening of the film hardly occurs.
- the transparent film is excellent in chemical resistance and water resistance. For example, it is difficult to leave a drip mark after wiping off a water droplet or a condensed water droplet dripped on the transparent film according to the present invention. It has the effect of.
- the hollow silica fine particles can be produced efficiently.
- the transparent coating in which predetermined hollow silica fine particles are unevenly distributed in the transparent coating is characterized by the properties based on the hollow silica fine particles (antireflection properties, antistatic properties). Etc.) are strongly expressed.
- the transparent film-coated substrate of the present invention the transparent film in which the predetermined hollow silica fine particles and the predetermined metal oxide fine particles are unevenly distributed in the respective layers in the transparent film is described above based on the hollow silica fine particles. In addition to the characteristics, various characteristics based on the metal oxide fine particles are strongly expressed easily.
- the composition for forming a transparent film of the present invention which contains the predetermined hollow silica fine particles and the predetermined metal oxide fine particles, is obtained by performing the coating treatment once to form the hollow silica fine particles and the metal oxide particles in the transparent film. Soot fine particles are unevenly distributed in layers. A transparent coating or a substrate with a transparent coating can be obtained.
- the hollow silica fine particles of the present invention are hollow silica fine particles having an average particle diameter of 5 to 300 nm, a specific surface area of 50 to 1500 m 2 Zg, and having cavities formed inside the outer shell. ),
- the hollow silica fine particles are characterized by exhibiting a weight loss of 1.0% by weight or more in a temperature range of 200 ° C. to 500 ° C.
- such hollow silica fine particles are usually characterized by showing a positive DTA peak in differential heat retention measurement in a temperature range of 200 ° C to 500 ° C.
- the hollow silica fine particles of the present invention are usually produced by subjecting the surface of conventionally known hollow silica fine particles to a surface treatment with a silane compound. Specifically, an organosilyl group (monoganosilyl, diorganosilyl or triorganosilyl group) is bonded to the surface of the hollow silica fine particles by a hydrolysis reaction between silanol groups on the surface of the hollow silica particles and the silanic compound.
- the hollow silica fine particle of the present invention has an organic group directly bonded to a large number of silicon atoms on the surface thereof.
- Such an organic group directly bonded to a silicon atom has a structure such as Si-O-SiA (A is an organic group) due to the reaction between the silanic compound and the surface silanol group of the hollow silica fine particles.
- thermogravimetry analysis is a measurement of the change in the weight of the sample due to the rise (fall) in the sample's ambient temperature with respect to the temperature.
- the weight change curve for the change in temperature is TG. It is called a curve.
- the differential thermal analysis detects the temperature difference between the reference and the sample by the electromotive force of the thermocouple provided in the sample container, and measures the change in heat with respect to the temperature.
- the calorific value change curve with respect to temperature change is called DTA curve.
- the hollow silica fine particles of the present invention exhibit excellent effects not found in conventional silica fine particles or hollow silica fine particles. Regarding this excellent effect, specifically, when a composition for forming a transparent film obtained by blending the hollow silica fine particles of the present invention into a binder is cured on a substrate, for example, it has good properties. A substrate with a transparent coating can be obtained. In particular, compared with the case where a substrate with a transparent coating is prepared using a composition for forming a transparent coating composed of conventional silica fine particles or hollow silica fine particles, whitening (whitening) that occurs in the transparent coating is suppressed. It has succeeded in improving the scratch resistance and adhesion.
- the transparent coating is whitened, resulting in insufficient scratch resistance and adhesion.
- the organosilyl group is a substituent that is firmly bonded to the surface of the hollow silica fine particles, and suppresses aggregation of the silica fine particles in the transparent film, which causes whitening of the transparent film. It is guessed that it contributes to doing.
- the presence of the organosilyl group contributes to the improvement of the dispersibility of the silica fine particles in the organosol and the transparent coating, and the densification of the transparent coating by chemical bonding with the binder resin. It is presumed to impart scratch resistance and adhesion.
- the surface treatment is performed by a method not corresponding to the method for producing hollow silica fine particles of the present invention.
- the hollow silica fine particles a decrease in mature weight of 1.0% by weight or higher at 200 ° C or higher is not observed, so that the surface-treated step force and the strong bond are not formed.
- the effect as seen in the hollow silica fine particles of the present invention is hardly exhibited as in the case of the conventional hollow silica fine particles.
- the hollow silica fine particles of the present invention in addition to the thermogravimetric characteristics, also in the differential heat retention characteristics, a specific peak is observed at 200 ° C to 500 ° C. In the case of hollow silica fine particles that have been surface-treated by a method that does not correspond to the method for producing silica fine particles or the hollow silica fine particles of the present invention, such a peak cannot be seen.
- the peak of the DTA curve represents an exothermic reaction accompanying the elimination of an organic group.
- the peak of the DTA curve usually appears in the temperature range (200 ° C. to 500 ° C.) where the thermogravimetric characteristics appear.
- the average particle size of the hollow silica fine particles of the present invention is preferably in the range of 5 to 300 nm. Hollow silica fine particles having an average particle diameter in this range are preferred for obtaining a transparent film. Hollow silica fine particles with an average particle diameter of less than 5 nm are difficult to obtain! On the other hand, when the thickness exceeds 300 nm, light scattering increases, and the reflection becomes large in the thin film, so that the antireflection function cannot be exhibited. As a more preferable average particle size range of the hollow silica fine particles of the present invention, a range of 10 to 200 nm is recommended, and a range of 10 to LO Onm is more preferable.
- the specific surface area of the hollow silica fine particles of the present invention is preferably in the range of 50 to 1500 m 2 / g in order to obtain the dispersibility and stability of the hollow silica fine particles in the solvent or in the film formation.
- it is less than 5 Om 2 / g, it is difficult to obtain hollow silica fine particles having a low refractive index.
- it exceeds 1500 m 2 / g, the dispersion stability of the hollow silica fine particles is lowered, which is not desirable.
- a range of 50 to 200 m 2 / g is recommended.
- the hollow silica fine particles of the present invention are required to exhibit a weight loss of 1.0% by weight or more in thermogravimetry in a temperature range of 200 ° C to 500 ° C.
- a substrate with a transparent coating formed by blending hollow silica fine particles with a thermal weight loss of less than 1.0% by weight whitening occurs, resulting in insufficient scratch resistance and adhesion.
- thermogravimetric reduction temperature Those having a thermal weight loss of 1.05% by weight or more are preferred in the range of 200 to 500 ° C. 1. Those showing a decrease in mature weight of 5% by weight or more are more preferred.
- the hollow silica fine particles of the present invention preferably exhibit a peak in the differential heat retention measurement in the temperature range of 200 ° C to 500 ° C in the differential heat retention measurement. Yes. Usually, when the thermogravimetric decrease is shown in the same temperature range, at least one peak is also confirmed in the differential heat retention measurement.
- the hollow silica fine particle of the present invention has an organic group directly bonded to a silicon atom on the surface thereof.
- the type of organic group it has an affinity with a binder for preparing a transparent film-forming composition, particularly an organic resin, and is obtained by curing the transparent film-forming composition on a substrate.
- the substrate is not limited as long as it does not cause whitening of the transparent film and does not impair scratch resistance and adhesion.
- a hydrocarbon group or a carbon atom or a different atom other than a hydrogen atom is not limited. It may be a hydrocarbon group containing an atom.
- the hydrocarbon group may be aliphatic, aromatic, saturated hydrocarbon group, or unsaturated hydrocarbon group. Further, it may contain a double bond or a triple bond or may have an ether bond.
- hetero atom examples include an oxygen atom, a nitrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a sulfur atom, a silicon atom, a boron atom, an aluminum atom, a magnesium atom, a sodium atom, a lithium atom, a calcium atom, Examples include potassium atom, but are not limited thereto.
- Preferable examples of the organic group directly bonded to the silicon atom include an organic group having a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms and a halogenated hydrocarbon group having 1 to 18 carbon atoms. The group can be mentioned.
- the hollow silica fine particles of the present invention are usually dispersed in an organic solvent.
- Silica thick The degree is preferably 1 to 70% by weight, more preferably 3 to 40% by weight, more preferably 3 to 40% by weight.
- the hollow silica fine particles of the present invention have the following general formula (1) from the viewpoints of adhesion to the substrate of the transparent coating containing the hollow silica fine particles of the present invention, prevention of whitening of the coating, and scratch resistance.
- R is a divalent hydrocarbon group having 1 to 12 carbon atoms
- R is a divalent hydrocarbon group having 1 to 12 carbon atoms
- the hollow silica fine particles of the present invention preferably have an organic group represented by the following general formula (3).
- the hollow silica fine particles of the present invention have an average particle diameter of 5 to 300 nm and a specific surface area of 50 to 1500 m 2 Zg measured by a dynamic light scattering method, and cavities are formed inside the outer shell.
- Hollow silica fine particles, and thermogravimetry (TG) shows a weight loss of 1.0% or more in the temperature range of 200 ° C to 500 ° C, and retains differential heat in the same temperature range.
- DTA it is a hollow silica fine particle having a positive DTA peak and having an organic group directly bonded to a silicon atom on the surface thereof.
- hollow silica fine particles of the present invention use known hollow silica fine particles as a raw material. It is. Generally, hollow silica fine particles have pores in the outer shell. In the hollow silica fine particles of the present invention, pores in the outer shell may be present, or the pores may disappear due to heating during the process of the production method as described below. .
- hollow silica fine particles used as the raw material of the present invention those having an average particle diameter of 5 to 300 nm and a specific surface area of 50 to 1500 m 2 Zg are used.
- the raw material hollow silica fine particles include, for example, an aqueous solution of silicate and Z or acidic silicic acid solution, and an alkali-soluble inorganic compound aqueous solution, an alkaline aqueous solution of pHIO or higher, or pHIO in which seed particles are dispersed as required.
- a core particle dispersion in which the molar ratio of silica and an inorganic compound other than silica is in the range of 0.3 to 1.0 is prepared by adding to the above alkaline aqueous solution at the same time.
- the first silica coating layer is formed on the particles, and then an acid is added to the dispersion to remove part or all of the elements constituting the core particles (Patent Document 6).
- an organosol of hollow silica fine particles having a silica solid content in the range of 1 to 70% by weight is prepared.
- a silica sol having hollow silica fine particles prepared using water as a dispersion medium is solvent-substituted to obtain an organosol.
- an organosol having a silica solid content of 1 to 70% by weight is used by using an ultrafiltration membrane or a rotary evaporator.
- an organic solvent is used as a solvent when the solvent is replaced.
- the type of organic solvent is not particularly limited as long as it does not adversely affect the surface coating of the hollow silica fine particles with the silanic compound.
- solvents such as alcohols, glycols, esters, ketones, nitrogen compounds, aromatics and the like can be used. Usually, alcohols such as methanol and ethanol are selected.
- silica solid content depending on the type of solvent, 70% by weight or more is not practical if the content is less than 1% by weight, where the hollow silica fine particles are difficult to disperse in the solvent.
- an organosol having a silica concentration of 1 to 70% by weight is prepared, Silane compound and alkali catalyst are mixed in the range of 30 ° C to 300 ° C, and the amount of water is 0.1 to 50% by weight with respect to the amount of silica. It is characterized by reacting.
- the amount of the silanic compound added is usually 1 to 50 parts by weight per 100 parts by weight of the hollow silica fine particles. If it is less than 1 part by weight, the proportion of untreated hollow silica fine particles increases, which is not preferable. On the other hand, when it exceeds 50 parts by weight, the silane compound becomes excessive, which is not economical.
- the amount of Silane compound added is preferably 3 to 25 parts by weight.
- the silane compound applied to the production method of the present invention is R SIX (R is an organic group, X is water n (4-n)
- n is an integer of 0-3), specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyl Trimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyljetoxysilane, phenyltriethoxysilane, diphenylmethoxysilane, isobutyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, burturis (j8-methoxyethoxy) ) Silane, 3, 3, 3—Trifluoropropyltrimethyoxysilane, Methyl 3,3,3—Trifluoropropyldimethoxysilane, j8 (3,4 Tesylsilane, ⁇ -Glycidoxy
- silanes having an acrylic group silanes having a methacryl group, 3,3,3-trifluoropropyltrimethoxysilane and the like are particularly preferable.
- the amount of the alkali catalyst added is not particularly limited, but it depends on the type of the alkali catalyst.
- the alkali catalyst is preferably used for the organosol in which the hollow silica fine particles are dispersed. It is preferable to add in the range of ⁇ 2,000ppm! /. If it is less than 20 ppm, the reaction of the silane compound on the surface of the hollow silica fine particles may not sufficiently proceed. On the other hand, when added over 2,000 ppm, the dispersibility when hollow silica fine particles are dispersed in the binder may be reduced due to excess alkali, and the alkali catalyst is a composition for forming a transparent film. The effect of remaining in the object occurs.
- alkali catalyst is not particularly limited, but ammonia, alkali metal hydroxides, amine compounds and the like are preferably used. Alternatively, these alkalis may be added in the form of an aqueous solution.
- the water content in the reaction solution is preferably 0.1 to 50% by weight, more preferably 10% by weight or less, and further preferably 5% by weight or less based on the amount of silica.
- the surface treatment is effectively carried out by the reaction between the surface of the hollow silica fine particles and the silane compound.
- the amount is less than 1% by weight, the surface treatment efficiency is low and a stable surface treatment is not performed.
- the silane compounds tend to react with each other, and as a result, the surface treatment of the hollow silica fine particles is not performed. It will be enough.
- the reaction temperature when the silane compound is reacted with the hollow silica fine particles is less than 30 ° C, and the reaction rate is not practical.
- the boiling point of the solvent of the organosol usually, the evaporation of the solvent may cause an increase in the water content, etc., but this is not preferable.
- the reaction may be carried out at temperatures up to. A temperature range of 40 ° C to below the boiling point of the solvent is recommended for this reaction temperature.
- reaction time for reacting the hollow silica fine particles with the silane compound is less than 0.1 hour, the reaction may not sufficiently proceed, which is not practical. On the other hand, even if the reaction is continued for more than 100 hours, no improvement is seen in the yield, etc. There is no need to continue.
- the reaction time is preferably in the range of 3 to 30 hours.
- the order of adding the silanic compound and the alkali catalyst to the hollow silica fine particle-dispersed organosol is not particularly limited. 1) The alkali catalyst may be added first, and then the silane compound may be added. 2) Silane compound may be added first, followed by addition of alkali catalyst. 3) Silane compound and alkali catalyst may be added simultaneously, but 1) Or the order of addition in 2) is recommended.
- An organosol having a silica concentration of 1 to 70% by weight in which hollow silica fine particles of the present invention are dispersed is prepared, and a silane compound and an alkali catalyst are added to the organosol in a temperature range of 30 ° C. to 300 ° C.
- the silane compound and the hollow silica fine particles are reacted under the condition that the water content is 0.1 to 50% by weight with respect to the amount of the silane compound.
- Hollow silica in which the addition amount is in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the hollow silica fine particles, and the addition amount of the alkali catalyst is in the range of 20 to 2, OOOppm with respect to the organosol.
- a fine particle production method is recommended.
- the hollow silica fine particles obtained by this production method showed a weight loss of 1.0% by weight or more in the temperature range of 200 ° C to 500 ° C by thermogravimetry (TG).
- TG thermogravimetry
- DTA differential heat retention measurement
- a positive DTA peak is shown, and such a composition for forming a transparent film comprising hollow silica fine particles and a binder has good adhesion to the substrate, It is excellent in whitening prevention and scratch resistance.
- an organosol having a silica concentration of 1 to 70% by weight in which hollow silica fine particles are dispersed is prepared, and the organosol is added to the organosol in a temperature range of 30 ° C to 300 ° C.
- Silane compound, polyfunctional acrylate ester resin having Z or hydrophobic functional group, and alkali catalyst were added, and the water content was 0.1 to 50% by weight with respect to the amount of silica.
- An example is a method for producing hollow silica fine particles, which comprises reacting a silane compound with the hollow silica fine particles.
- Examples of the polyfunctional acrylate ester resin having a hydrophobic functional group that can be used here include pentaerythritol tritalylate, pentaerythritol tetratalylate, trimethylolpropane tri (meth) atarylate, pentaerythritol tetratalylate, Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexatalate, methylmethacrylate, ethylmethacrylate, butylmethacrylate, isobutylmethacrylate, 2-ethylhexylmethacrylate, iso Decylmethacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimetatalylate, perfluorooctyl methacrylate, trifluoroethyl methacrylate, ure
- the weight ratio to the hollow silica fine particles (solid content weight of the hydrophobic multifunctional acrylate ester resin Z weight of the hollow silica fine particles) Is not particularly limited, but is usually in the range of 0.001 to 2, or 0.0005 to 1.5.
- composition for forming a transparent film of the present invention comprises the hollow silica fine particles of the present invention and a binder.
- the noinder refers to a component that can form a film on the surface of a base material, and is selected from organic resins that meet conditions such as adhesion to the base material, hardness, and coatability.
- An organic resin, a hydrolyzable organosilicon compound or a partially hydrolyzed condensate thereof is used by being dispersed in a solvent as necessary.
- polyester resin acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicone resin, petital resin, phenol resin, Vinyl acetate resin, UV curable resin, electron beam cured resin, emulsion resin, water-soluble resin, hydrophilic resin, mixtures of these resins, copolymers of these resins
- resin for coatings such as modified products, hydrolyzable organosilicon compounds such as alkoxysilanes, and partial hydrolysis condensates thereof.
- a calo-water-decomposable organosilicon compound as a binder, for example, by adding water and a catalyst (acid or alkali) to a mixture of alkoxysilane and alcohol, partial hydrolysis of the alkoxysilane is performed.
- a catalyst acid or alkali
- a method can be used in which a decomposition condensate is prepared and used as a binder.
- the composition for forming a transparent film of the present invention contains 10 to parts by weight of the binder in terms of solid content with respect to 100 parts by weight (silica part) of the hollow silica fine particles.
- the amount of the Norder is less than 10 parts by weight, the hardness of the film may not be obtained, or the cured state may not be reached. If the amount exceeds 10,000 parts by weight, the low refractive index function cannot be achieved.
- a range of preferably 50 to L000 parts by weight is recommended.
- composition for forming a transparent film of the present invention may contain a photoinitiator, a curing catalyst, and the like depending on the method for curing the binder.
- photoinitiators and curing catalysts examples include radical initiators such as peroxides, azo compounds, titanium compounds, tin compounds, platinum catalysts, isocyanates, etc. It is not limited to these.
- the composition for forming a transparent film of the present invention is usually prepared by mixing an organosol in which the hollow silica fine particles of the present invention are dispersed and a binder.
- the binder may be dispersed in an organic solvent.
- the composition for forming a transparent film of the present invention can be usually obtained by sufficiently mixing and stirring the mixture in a weight ratio range using a mixer or the like.
- the composition for forming a transparent film of the present invention contains an organic solvent derived from an organosol or a binder, and is appropriately diluted with an organic solvent depending on the application.
- composition for forming a transparent film of the present invention is preferably diluted with 100 to 5000 parts by weight of an organic solvent with respect to 100 parts by weight of a solid content comprising the hollow silica fine particles of the present invention and a binder (solid content). Is used.
- the surface functional groups of the hollow silica fine particles coated on the surface of the substrate to be applied may be performed.
- solvents include
- Alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol;
- Ketones such as acetone, 2-butanone, ethylamyl ketone, diacetone alcohol, isophorone, cyclohexanone;
- Amides such as N, N dimethylformamide, N, N dimethylacetamide; jetyl ether, isopropyl ether, tetrahydrofuran, 1, 4 dioxane, 3,
- Ethers such as 4-dihydro 2H pyran
- Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether;
- Glyconoleate acetates such as 2-methoxyethinoreacetate, 2-ethoxychetinoreacetate, 2-butoxychetinoreaacetate;
- Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, and ethylene carbonate;
- Aromatic hydrocarbons such as benzene, toluene, xylene;
- Aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene;
- Sulfoxides such as dimethyl sulfoxide
- Examples thereof include pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl 2-pyrrolidone. These dispersion media may be used alone or in combination of two or more. Among these, a polar solvent can be particularly preferably used.
- composition for forming a transparent film of the present invention may contain a preservative, an antibacterial agent, an antifoaming agent, an ultraviolet deterioration preventing agent, a dye, a leveling agent and the like depending on the purpose and application.
- the surface charge amount (Q) As a preferred embodiment of the composition for forming a transparent film of the present invention, the surface charge amount (Q)
- the hollow silica fine particles having A in the range of 5 to 20 ⁇ eqZg, the binder and the polar solvent, and the concentration (C) of the hollow silica fine particles in the range of 0.1 to 20% by weight examples thereof include a composition for forming a transparent film, wherein the concentration (C) as a solid content is in the range of 1 to 50% by weight.
- the surface charge amount (Q) of the hollow silica fine particles is preferably in the range of 5 to 20 eqZg.
- the surface charge amount (Q) of the hollow silica fine particles is within the above range, such hollow silica fine particles are contained.
- the uneven distribution of the hollow silica fine particles is likely to occur, and the intermediate point in the thickness direction of the coating Hollow silica fine particles are unevenly distributed on the outer surface side and dispersed.
- a specific dispersion state of the hollow silica fine particles there are a single layer shape or a multilayer shape, and there are cases where they are scattered.
- the hollow silica fine particles When the surface charge amount (Q) of the hollow silica fine particles is less than 5 ⁇ eqZg, the hollow silica fine particles
- A exceeds 20 / z eqZg, the case where it is not a hollow silica fine particle is usually included.
- a film obtained by curing the composition for forming a transparent film containing the hollow silica fine particles is easily whitened, and the tendency of the hollow silica fine particles to be uniformly dispersed in the film is increased.
- the amount of the hollow silica fine particles in the transparent film-forming composition is such that the concentration (C) of the hollow silica fine particles is in the range of 0.1 to 20 wt%, and the solid content of the binder
- a transparent film-forming composition characterized in that the concentration (C) of is in the range of 1 to 50% by weight.
- the concentration (C) of the hollow silica fine particles is less than 0.1% by weight, the hollow silica fine particles are not contained.
- the hollow silica fine particles are unevenly distributed and optical characteristics and electrical characteristics due to dispersion are hardly exhibited.
- concentration of hollow silica fine particles (C) exceeds 20% by weight, a transparent silica particle containing hollow silica fine particles is contained.
- the tendency for the hollow silica fine particles to be monodispersed in the film formed by curing the composition for forming a bright film is increased.
- the concentration of hollow silica fine particles (C) is preferably 1 to 10% by weight.
- the hollow silica fine particles preferably have an average particle diameter in the range of 5 to 300 nm.
- a range of 10 to 200 nm is recommended, and a range of 10 to 100 nm is more preferable.
- the method for producing a composition for forming a transparent film is also applied to the method for producing a composition for forming a transparent film according to a preferred embodiment (1) of the composition for forming a transparent film.
- the composition for forming a transparent film has a surface strength (QA) of 5 to 20 / ⁇ . It includes metal oxide fine particles having a surface charge amount (QB) in the range of Sl lSO / z eqZg, a binder and a polar solvent.
- the surface charge amount (QB) of the metal oxide fine particles and the hollow silica fine particles The value of [(QB)-(QA)] is in the range of 20-100; z eqZg, and the concentration of hollow silica fine particles (C PA) is 0.1-20.
- the surface charge (QA) of the hollow silica fine particles is in the range of 5 to 20 eqZg
- the surface charge (Q ⁇ ) of the metal oxide fine particles is in the range of 51 to 150 / ⁇ ⁇
- the surface charge is (Q ⁇ ) and (
- QA) difference [(QB)-(QA;)] is in the range of 20 to: LOO / z eqZg, so that the transparent film-forming composition is cured to form a transparent film.
- the metal oxide fine particles are unevenly distributed and dispersed on the substrate side from the intermediate point in the thickness direction, and the hollow silica fine particles are present on the outer surface side from the intermediate point in the thickness direction. The uneven distribution and the tendency to disperse become stronger.
- the degree (C) is preferably in the range of 1 to LO weight%, respectively.
- the metal oxide fine particles when a transparent coating is used for the coating film, the metal oxide fine particles are ZrO, TiO, SbO, ZnO, AlO, SnO, or
- chain particles in which these particles are connected in a chain or silica-based fine particles having a refractive index of 1.45 or less are preferably used.
- fine particles having a refractive index of usually 1.60 or more, more preferably 1.80 or more are used as metal oxide fine particles.
- metal oxide fine particles usually 1.60 or more, more preferably 1.80 or more.
- Tin fluoride doped phosphorus (PTO) or the like is preferably used.
- the metal oxide fine particles are usually used as Sb.
- silica-based fine particles whose surfaces are coated with these conductive materials, or silica-based fine particles having cavities inside.
- metal oxide fine particles those treated with the silanic compound may be used if desired.
- hollow silica fine particles according to the fifth invention of the present invention may be used.
- metal oxide fine particles treated by applying metal oxide fine particles instead of hollow silica fine particles may be used.
- the substrate is coated with the substrate once and the substrate side from the intermediate point in the thickness direction in the transparent film.
- the metal oxide fine particles are unevenly distributed and dispersed, and the hollow silica fine particles are unevenly distributed and dispersed on the outer surface side from the intermediate point in the thickness direction.
- a substrate with a transparent coating can be obtained.
- metal oxide fine particles are further added in the method for producing the transparent film forming composition. Can be performed.
- the substrate with a transparent film of the present invention is obtained by curing the composition for forming a transparent film of the present invention on a substrate alone or via another film.
- the material of the base material is not particularly limited as long as it is a solid material capable of forming a film.
- glass polycarbonate, acrylic resin, PET, TAC (triacetyl cellulose), MS substrate (copolymer of methyl methacrylate and styrene, a polyolefin-based substrate, etc.
- MS substrate copolymer of methyl methacrylate and styrene, a polyolefin-based substrate, etc.
- examples include plastic sheets, plastic films, plastic lenses, plastic panels, cathode ray tubes, fluorescent display tubes, and liquid crystal display plates.
- Examples of the other coatings include a hard coat film, a planarizing film, a high refractive index film, an insulating film, a conductive resin film, a conductive metal fine particle film, a conductive metal oxide fine particle film, and a primer.
- the layer formed by can be mentioned.
- the transparent coated substrate of the present invention may be coated for another purpose.
- the transparent film-coated substrate of the present invention is obtained by applying the transparent film-forming composition to the substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, followed by drying. If necessary, it can be obtained by curing by heating or ultraviolet irradiation.
- the transparent film-forming composition of the present invention is applied to a substrate, preliminarily dried at 70 ° C. to 100 ° C., and then using a high pressure mercury lamp or a fusion lamp.
- the wavelength is cured by irradiating with ultraviolet rays in the range of 300 to 1, OOOOmi / Cm 2 according to the absorption wavelength of the initiator.
- the refractive index of the transparent film formed on the base material of the present invention varies depending on the mixing ratio of the hollow silica-based fine particles and the binder one component and the refractive index of the binder used, but it has a low refractive index of 1.15 to 1.42. It becomes.
- a transparent coating (film thickness ⁇ ! ⁇ )
- the hollow silica fine particles having an average particle diameter of 5 to 300 nm are dispersed in a noda on the substrate and the surface thereof. (10OOOOnm), wherein the hollow silica fine particles are unevenly distributed and dispersed on the outer surface side from the middle point in the thickness direction in the transparent film.
- a substrate with a transparent coating In which the hollow silica fine particles having an average particle diameter of 5 to 300 nm are dispersed in a noda on the substrate and the surface thereof. (10OOOOnm), wherein the hollow silica fine particles are unevenly distributed and dispersed on the outer surface side from the middle point in the thickness direction in the transparent film.
- hollow silica fine particles are unevenly distributed on the outer surface side from the intermediate point in the thickness direction of the coating, and the hollow silica fine particles are formed in a single layer shape. Or it exists in the form of multiple layers or dots.
- the transparent coating is caused by antireflection performance due to the low refractive index of the hollow silica fine particles or the conductivity of the hollow silica fine particles. Antistatic performance is strongly expressed.
- metal oxide fine particles having an average particle size of 1 to 50 nm and the hollow silica fine particles having an average particle size of 5 to 300 nm are dispersed in a binder on the substrate and the surface thereof.
- the hollow silica fine particles and the metal oxide fine particles each form a single layer or multiple layers, and therefore the properties resulting from the hollow silica fine particles (such as antireflection performance and antistatic performance). ) And properties (scratch properties, adhesion to a substrate, properties based on a high refractive index, conductivity, etc.) resulting from predetermined metal oxide fine particles.
- composition for forming a transparent film and the substrate with a transparent film containing the hollow silica fine particles of the present invention can be applied to various uses requiring low refractive index, scratch resistance, and adhesion, and the surface of the display It can be used for optical coatings such as coatings and lenses.
- reaction mother liquor was prepared and heated to 80 ° C.
- the pH of the reaction mother liquor 10. is 5, and 1.17 wt 0/0 of ⁇ aqueous sodium 9, OOOg as SiO in uterine fluid, 0.83 weight as Al O
- a fine particle dispersion was obtained. This was washed with an ultrafiltration membrane to obtain a composite oxide fine particle dispersion having a solid concentration of 13% by weight.
- E chill silicate SiO 28 weight 0/0
- the dispersion of the silica-based fine particles (2) was again hydrothermally treated at 200 ° C for 11 hours, and then washed with an ultrafiltration membrane while adding 5 L of pure water to adjust the solid content concentration to 20% by weight. did. Then, using an ultrafiltration membrane, the dispersion medium of this dispersion was replaced with ethanol, and the solid content concentration 2 A 0 wt% organosol was prepared.
- This organosol is an organosol in which hollow silica fine particles having an average particle diameter of 46 nm, a specific surface area of 123 m 2 Zg, and a pore volume of 0.4596 ml Zg are dispersed (hereinafter referred to as “hollow silica sol A”).
- An organosol consisting of a coated hollow fine particle was prepared.
- the average particle size was measured by dynamic light scattering method using laser light.
- the sample silica sol was diluted with 0.58% ammonia water to adjust the silica concentration to 1% by mass, and the average particle size was measured using the following particle size measuring apparatus.
- a sample obtained by drying 50 ml of sol at 110 ° C for 20 hours was measured by a nitrogen adsorption method (BET method) using a specific surface area measurement device (manufactured by UASA Iotas Co., Ltd., Multisoap 12). Set.
- HNO is added to 50 ml of silica sol to adjust the pH to 3.5, and 1-propano
- BET method nitrogen adsorption method
- 0.5 g of a sample is placed in a measurement cell, degassed for 20 minutes at 300 ° C in a mixed gas stream of nitrogen 30v% Z helium 70v%, and the sample is added to the above sample. Maintain the temperature of liquid nitrogen in a mixed gas stream and allow nitrogen to equilibrate to the sample. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time was detected, and the specific surface area of the silica sol was calculated using a calibration curve prepared in advance.
- thermothermal gravimetric simultaneous measurement was performed using a differential thermothermal gravimetric measuring device (Themoplus TG8110, manufactured by Rigaku Corporation).
- the measurement conditions are an air atmosphere, a temperature rising rate of 10 ° C Z min, and a temperature range of room temperature to 500 ° C.
- Example 1 For the sample for differential thermothermal gravimetric measurement (TGZDTA) measurement of hollow silica fine particles in Example 1 and all other examples and all comparative examples, after removing the organosol solvent prepared as described above, After thoroughly washing with hexane to remove hexane, it was dried with a vacuum drier and used as a powder sample (15 mg).
- the coated hollow silica fine particles used in Examples 1 to 10, Comparative Example 3, and Examples 13 to 16 are each kept at a differential heat in a temperature range of 200 ° C. to 500 ° C.
- DTA when the X axis was temperature and the Y axis was calorific value, each had a positive peak due to an exothermic reaction at the peak position (temperature) shown in Table 1.
- the surface charge of the hollow silica fine particles or metal oxide fine particles can be measured by using a surface potential titration device (Mutek Co., Ltd. pcd-03), and using a dispersion of hollow silica fine particles or metal oxide fine particles ( The surface charge per gram of the particle (; z eq / g) was determined by titrating with a 0.001N polysalt / diaryldimethylform . So The results are shown in Table 1.
- each measurement sample (lm ⁇ ) is collected in a syringe, and 0.01 g to 0.02 g is collected from a moisture meter (Karfe Fisher Co., Ltd., Karl Fischer moisture meter MKC). — Measured at 510).
- Karl Fischer moisture meter MKC Karl Fischer moisture meter MKC
- An organosol consisting of a coated hollow microparticle with a concentration of 2% by weight was prepared.
- Organosol consisting of coated hollow fine particles with a concentration of 20% by weight was prepared.
- An organosol consisting of 1% coated hollow fine particles was prepared.
- the amount is 200 ppm as ammonia and mixed well.
- 4 g of acrylic silane KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.
- An organosol consisting of 1% coated hollow fine particles was prepared.
- An organosol made of covered hollow fine particles was prepared.
- Example 7 200 g of the hollow silica sol A (silica solid content concentration 20% by weight) was prepared, and the solvent was replaced with methanol in an ultrafiltration membrane, and the organosol 100g (water) having a SiO content of 20% by weight.
- An organosol made of covered hollow fine particles was prepared.
- An organosol composed of coated hollow fine particles was prepared.
- KBM503) 4g (equivalent to 20 parts by weight with respect to 100 parts by weight of SiO) is added and filled.
- Heating was carried out at 50 ° C. for 15 hours while stirring at 1.0 wt% for 2 minutes. After the heating is completed, the reaction solution is cooled to room temperature, washed with an ultrafiltration membrane, and coated with a SiO concentration of 20% by weight. An organosol made of covered hollow fine particles was prepared.
- KBM503 4g (equivalent to 20 parts by weight per 100 parts by weight of SiO) and 28%
- the aqueous ammonia solution was adjusted to 400 ppm as ammonia with respect to 100 g of the organosol to prepare a reaction solution (water content was 1.0% by weight with respect to the SiO content). 50
- the mixture was heated to ° C and heated at 50 ° C with stirring for 15 hours. After heating, the reaction solution is cooled to normal temperature, washed with an ultrafiltration membrane, and coated from hollow fine particles with a SiO concentration of 20% by weight.
- An organosol was prepared.
- the amount was 0.5% by weight based on the SiO content.
- reaction solution water content was 0.5% by weight with respect to the SiO content
- the reaction solution was used. Warm this to 50 ° C and stir
- the mixture was heated at 50 ° C for 15 hours. After the heating is completed, the reaction solution is cooled to room temperature, washed with an ultrafiltration membrane, and an organosol made of coated hollow fine particles with a SiO concentration of 20% by weight is obtained.
- the amount was 0.5% by weight based on the SiO content).
- An organosol consisting of a coated hollow fine particle was prepared.
- Example 11 Each transparent film-forming composition obtained in Example 11 was applied to a PET film by a bar coater method and dried at 80 ° C. for 1 minute. I got the material.
- the coating performance of this substrate with a transparent coating includes whitening prevention, scratch resistance, adhesion, transparent coating refractive index, antiglare properties, pencil hardness, surface resistance, total light transmittance, haze, and wavelength of 550 nm.
- the light reflectance of was measured. The following measurements were similarly performed for Examples 13 to 16 and Comparative Example 4 shown below, and the results are shown in Table 1.
- the uncoated PET film had a total light transmittance of 90.7%, a haze of 2.0%, and a reflectance of light having a wavelength of 550 nm of 7.0%.
- the whitening prevention effect of the substrate with a transparent coating was measured, and the results are shown in Table 1.
- the whitening prevention effect was evaluated in the following three steps by placing the substrate with a transparent coating in a dryer at a temperature of 80 ° C for 30 minutes and visually observing the presence or absence of cracks or whitening of the coating.
- the substrate with the transparent coating was measured for scratch resistance, and the results are shown in Table 1.
- the scratch resistance was evaluated by the following four steps using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2 , visually observing the film surface.
- the refractive index of the transparent coating was measured with an ellipsometer (ULVAC, EMS-1).
- the back surface of the substrate with the transparent coating was evenly applied with black spray, 2 m away from the 30 W fluorescent lamp, and the reflection of the fluorescent lamp was visually confirmed to evaluate the antiglare property.
- the pencil hardness was measured with a pencil hardness tester according to JIS K 5400. That is, a pencil was set at an angle of 45 degrees with respect to the surface of the film, and a predetermined load was applied and the film was pulled at a constant speed to observe the presence or absence of scratches.
- the surface resistance was measured with a surface resistance meter (manufactured by Mitsubishi Yuka Co., Ltd .: LORESTA).
- the total light transmittance and haze were measured with a haze meter (Nippon Denshoku Co., Ltd., NDH2000).
- the reflectance of light with a wavelength of 550 nm was measured with a spectrophotometer (JASCO Corporation, Ubest-55).
- Silica-based hollow fine particle dispersion sol manufactured by Catalytic Chemical Industry Co., Ltd .: Through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1. 30 as low refractive index component The water content was 0.5% by weight based on the SiO content. To 100 g of this sol
- a silica-based hollow fine particle-dispersed sol that was surface-treated by stirring for a time was obtained (solid content 20.3%).
- the coating liquid for transparent film formation (A-1) was applied to a PET film (thickness 100 / ⁇ ⁇ , refractive index 1.65, substrate transmittance 88.0%, Hazel. 0%, reflectance 5.1%).
- - co - data in applying, after drying for 1 minute at 70 ° C, and a high-pressure mercury lamp (80W / C m) for 1 minute irradiating the cured substrate with a transparent film (1) preparation.
- the film thickness of the transparent coating at this time was 5 m.
- silica-based hollow fine particles formed a layer of lOOnm in the upper part, and the lower part was composed of only the matrix and the particles. The existence was not recognized.
- Silica-based hollow fine particle dispersion sol manufactured by Catalytic Chemical Industry Co., Ltd .: Through rear 1420, average particle size 60 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particles as low refractive index component A refractive index of 1.30 and a water content of 0.5% by weight with respect to the SiO content were used.
- Metaatari mouthoxypropyltrimethoxysilane 1.88 g (KBM-503 Si 0 component 81.2% manufactured by Shin-Etsu Silicon Co., Ltd.) was mixed, and 28% aqueous ammonia solution was added to 100 g of the organosol.
- silica-based hollow fine particle dispersion sol (Catalyst Kasei Kogyo Co., Ltd .: Through 1420-120, average particle size 120 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1.20 The water content was 0.5% by weight based on the SiO content. 100g of this sol
- Transparent film-forming paint (A-3) is applied to PET film (thickness 100 / ⁇ ⁇ , refractive index 1.65, substrate transmittance 88.0%, Hazel. 0%, reflectance 5.1%).
- - data in applying, after 1 minute drying at 70 ° C, and a high-pressure mercury lamp (80W / C m) of the cured by irradiation for 1 minute substrate with a transparent film (3) preparation. The film thickness at this time was 5 m. A part of the transparent coating was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow microparticles formed a layer with a thickness of 120 nm at the top, and the bottom was the presence of particles only with the matrix. Was not allowed o
- Silica-based hollow fine particle dispersion sol manufactured by Catalytic Chemical Industry Co., Ltd .: Through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1. 30 as low refractive index component The water content was 0.5% by weight based on the SiO content. To 100 g of this sol
- ATO fine particle dispersion sol as an antistatic high refractive index component (manufactured by Catalytic Chemical Industry Co., Ltd .: ELCO M V-3501, average particle diameter 8 nm, concentration 20.5 wt%, dispersion medium: ethanol, particle refractive index 1.75) was used. 100 g of this sol was mixed with 0.15 g of ⁇ -atarioxypropyltrimethoxysilane (KBM-5103 SiO component 81.2%, manufactured by Shin-Etsu Silicone Co., Ltd.), and ultrapure water 1 was added ( ⁇
- the surface-treated ATO fine particle dispersed sol was obtained by stirring for 5 hours (solid content: 20.0%).
- Paint for transparent coating (A-6) TAC film (thickness 80 / ⁇ ⁇ , refractive index 1.48, substrate transmittance 88.0% HazeO. 0%, reflectance 4.8%) coated with a bar coater and, after drying for 1 minute at 70 ° C, it was made regulating a high pressure mercury lamp (80W / C m) of the cured by irradiation for 1 minute substrate with a transparent film (4). The film thickness at this time was 5 m.
- Silica-based hollow fine particle dispersion sol manufactured by Catalytic Chemical Industry Co., Ltd .: Through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1. 30 as low refractive index component The water content was 0.5% by weight based on the SiO content.
- a silica-based hollow particle dispersed sol was obtained by mixing 1 fluorooctyltriethoxysilane l g (AY43-158E 100% manufactured by Toray Dow Co., Ltd.) and stirring the mixture for 5 hours at 40 ° C. (Solid content 20.3%).
- Paint transparent coating (R-1) on PET film (thickness 100 m, refractive index 1.65, substrate transmittance 88.0%, Hazel. 0%, reflectance 5.1%) data - in coating and dried for 1 minute at 70 ° C, high-pressure mercury lamp (80W / C m) for 1 minute irradiation with a transparent film substrate is cured by the (R -1) was prepared.
- the film thickness at this time was 5 m.
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Priority Applications (7)
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JP2007546417A JP5078620B2 (ja) | 2005-11-25 | 2006-11-17 | 中空シリカ微粒子、それを含む透明被膜形成用組成物、および透明被膜付基材 |
CN2006800439281A CN101312909B (zh) | 2005-11-25 | 2006-11-17 | 中空二氧化硅微粒、含有该微粒的透明涂膜形成用组合物、及覆有透明涂膜的基材 |
EP06832840.0A EP1972598B1 (en) | 2005-11-25 | 2006-11-17 | Hollow silica microparticle, composition for transparent coating formation containing the same, and substrate with transparent coating |
US12/085,367 US20090286070A1 (en) | 2005-11-25 | 2006-11-17 | Hollow Silica Microparticles, Compositions for Forming Transparent Coating Film Containing the Same, and Substrate Having Transparent Coating Film |
KR1020087015336A KR101365382B1 (ko) | 2005-11-25 | 2006-11-17 | 중공 실리카 미립자, 그것을 포함한 투명 피막 형성용조성물, 및 투명 피막 부착 기재 |
US13/352,870 US9441095B2 (en) | 2005-11-25 | 2012-01-18 | Method of producing hollow silica microparticles |
US14/698,579 US9834663B2 (en) | 2005-11-25 | 2015-04-28 | Composition for forming a transparent coating film including hollow silica particles |
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US12/085,367 A-371-Of-International US20090286070A1 (en) | 2005-11-25 | 2006-11-17 | Hollow Silica Microparticles, Compositions for Forming Transparent Coating Film Containing the Same, and Substrate Having Transparent Coating Film |
US13/352,870 Division US9441095B2 (en) | 2005-11-25 | 2012-01-18 | Method of producing hollow silica microparticles |
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JP (2) | JP5078620B2 (ja) |
KR (1) | KR101365382B1 (ja) |
CN (1) | CN101312909B (ja) |
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WO (1) | WO2007060884A1 (ja) |
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Also Published As
Publication number | Publication date |
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TWI488813B (zh) | 2015-06-21 |
TW200726717A (en) | 2007-07-16 |
JP5078620B2 (ja) | 2012-11-21 |
US9441095B2 (en) | 2016-09-13 |
EP1972598A4 (en) | 2011-11-02 |
US20120111231A1 (en) | 2012-05-10 |
US20150259512A1 (en) | 2015-09-17 |
KR101365382B1 (ko) | 2014-02-19 |
TW201431785A (zh) | 2014-08-16 |
JPWO2007060884A1 (ja) | 2009-05-07 |
TWI482738B (zh) | 2015-05-01 |
US9834663B2 (en) | 2017-12-05 |
CN101312909B (zh) | 2011-11-16 |
KR20080071608A (ko) | 2008-08-04 |
EP1972598A1 (en) | 2008-09-24 |
EP1972598B1 (en) | 2016-06-15 |
JP2013014506A (ja) | 2013-01-24 |
US20090286070A1 (en) | 2009-11-19 |
CN101312909A (zh) | 2008-11-26 |
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