WO2016117592A1 - Composition liquide pour formation de film à faible indice de réfraction - Google Patents

Composition liquide pour formation de film à faible indice de réfraction Download PDF

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Publication number
WO2016117592A1
WO2016117592A1 PCT/JP2016/051548 JP2016051548W WO2016117592A1 WO 2016117592 A1 WO2016117592 A1 WO 2016117592A1 JP 2016051548 W JP2016051548 W JP 2016051548W WO 2016117592 A1 WO2016117592 A1 WO 2016117592A1
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Prior art keywords
film
refractive index
low refractive
liquid composition
ether
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PCT/JP2016/051548
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English (en)
Japanese (ja)
Inventor
怜子 日向野
山崎　和彦
岳洋 米澤
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三菱マテリアル株式会社
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Priority claimed from JP2015025889A external-priority patent/JP6451376B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to CN201680006229.3A priority Critical patent/CN107207907B/zh
Priority to KR1020177018932A priority patent/KR102237333B1/ko
Publication of WO2016117592A1 publication Critical patent/WO2016117592A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a liquid composition for forming a low refractive index film.
  • the present invention relates to a liquid composition for forming a low refractive index film used for display panels, solar cells, optical lenses, camera modules, sensor modules, mirrors, glasses and the like. More specifically, the present invention relates to a liquid composition for forming a low refractive index film which is less likely to aggregate the colloidal silica particles in the liquid composition, has a low refractive index, and is excellent in water wettability and antifogging property on the film surface. is there.
  • This application claims priority based on Japanese Patent Application No. 2015-008192 filed in Japan on January 20, 2015, and Japanese Patent Application No. 2015-025889 filed in Japan on February 13, 2015. , The contents of which are incorporated herein.
  • a low refractive index film formed on the surface of a transparent substrate such as glass or plastic is a reflection of incident light on display panels such as cathode ray tubes, liquid crystals, organic EL, solar cells, optical lenses, glass for showcases, etc. It is used as an antireflection film for preventing the above.
  • display panels such as cathode ray tubes, liquid crystals, organic EL, solar cells, optical lenses, glass for showcases, etc. It is used as an antireflection film for preventing the above.
  • an antireflection film for improving visibility is provided on the display surface side of the display panel, and in the field of solar cells, the reflection of incident sunlight is prevented to increase the light absorption rate.
  • measures such as forming a low refractive index film as an antireflection film on the surface of a glass substrate are taken.
  • a single-layer film made of MgF 2 , cryolite or the like formed by a vapor phase method such as a vacuum evaporation method or a sputtering method has been put into practical use.
  • a multilayer film formed by alternately laminating a low refractive index film such as SiO 2 and a high refractive index film such as TiO 2 or ZrO 2 on a base material has a high antireflection effect. It has been known.
  • gas phase methods such as vacuum deposition and sputtering have problems in terms of manufacturing cost because the equipment is expensive.
  • the method of forming a multilayer film by alternately laminating a low refractive index film and a high refractive index film is not practical because the manufacturing process is complicated and takes time and labor.
  • a coating method such as a sol-gel method has attracted attention from the viewpoint of manufacturing cost.
  • a sol-gel method generally, a sol-gel solution is prepared, applied to a transparent substrate such as glass, and then dried or fired to form a film.
  • the film formed by the sol-gel method cannot obtain a desired low refractive index as compared with a film formed by a vapor phase method such as a vacuum vapor deposition method, and various problems such as poor adhesion to the substrate and occurrence of cracks. Challenges remained.
  • a silica sol (a) in which silica particles having a predetermined average particle diameter are dispersed, an alkoxysilane hydrolyzate, a metal alkoxide hydrolyzate, and a metal salt are included.
  • a coating liquid containing at least one component (b) selected from the group and obtained by mixing silica sol (a) and component (b) with an organic solvent in a desired ratio to a substrate A cured low refractive index antireflection film is disclosed (for example, see Patent Document 1).
  • an organic solvent-based silica sol obtained by substituting water in the aqueous silica sol with an organic solvent by a distillation method or the like is shown.
  • the organic solvent used in the organic solvent-based silica sol is preferably an alcohol such as methanol (flash point 12 ° C.), ethanol (flash point 13 ° C.), isopropanol (flash point 15 ° C.), butanol (flash point 37 ° C.), or ethyl cellosolve.
  • Flash point 43 ° C. Flash point 43 ° C.
  • butyl cellosolve flash point 64 ° C.
  • ethyl carbitol flash point 94 ° C.
  • butyl carbitol flash point 113 ° C.
  • diethyl cellosolve flash point 35 ° C.
  • diethyl carbitol flash point
  • a hydrophilic solvent of glycol ethers such as 82 ° C. is used.
  • Patent Document 1 by using the silica particles in a specific ratio, the film obtained using the coating liquid of Patent Document 1 has minute irregularities formed on the surface of the film, which decreases the refractive index. Describes that a good antireflection effect can be obtained.
  • the coating liquid (low refractive index film forming liquid composition) for forming the low refractive index antireflection film disclosed in Patent Document 1 alcohols and glycol ethers used in the solvent and the organic solvent-based silica sol are used. All the hydrophilic solvents have a low flash point of less than 140 ° C. Therefore, when the coating solution is used for a long-time continuous coating process in the air and the coating solution is left in the air, the solvent and the organic solvent are likely to volatilize from the coating solution, and the dispersion of silica particles in the coating solution is difficult. Become stable.
  • the silica particles When the silica particles are aggregated, the aggregates adhere like projections on a uniform thin film and do not form a uniform film, which may not function as an optical film. Further, the low refractive index film formed on this type of transparent substrate is required to have antifogging properties so as to maintain transparency in any environment. The anti-fogging property was insufficient with the low refractive index film obtained in (1).
  • An object of the present invention is to solve the above-mentioned problems, and to provide a low refractive index film that is less likely to aggregate the colloidal silica particles in the liquid composition, has a low refractive index, and is excellent in water wettability and antifogging property on the film surface. It is in providing the liquid composition for forming.
  • the present inventors include a certain proportion of a high boiling point solvent, that is, a solvent having a flash point of 140 to 160 ° C., the low refractive index film-forming liquid composition as a whole.
  • a high boiling point solvent that is, a solvent having a flash point of 140 to 160 ° C.
  • the present inventors have found that the composition of the entire liquid composition is stable and that aggregation is suppressed, and have reached the present invention.
  • a hydrolyzate of silicon alkoxide produced by adding a mixture of water and nitric acid to a tetramethoxysilane or tetraethoxysilane alcohol solution as a silicon alkoxide and stirring the mixture.
  • Low refractive index which is prepared by mixing silica sol in which colloidal silica particles are dispersed in a liquid medium and further mixing with an organic solvent of glycol ether, wherein the glycol ether has a flash point of 140 ° C. or higher and 160 ° C. or lower. It is a liquid composition for rate film formation.
  • a second aspect of the present invention is the invention based on the first aspect, wherein the glycol ether, which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower, is polyethylene glycol monomethyl ether, triethylene glycol monobutyl ether, Tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether or diethylene glycol monobenzyl ether.
  • the glycol ether which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower, is polyethylene glycol monomethyl ether, triethylene glycol monobutyl ether, Tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether or diethylene glycol monobenzyl ether.
  • a third aspect of the present invention is a method of forming a low refractive index film using the liquid composition for forming a low refractive index film according to the first or second aspect.
  • a fourth aspect of the present invention is a low refractive index film formed by the method of the third aspect.
  • a fifth aspect of the present invention is a composite film including the low refractive index film and the infrared shielding film according to the fourth aspect.
  • the liquid component of the liquid composition is It becomes difficult to volatilize, the dispersion of the colloidal silica particles is stabilized, and the colloidal silica particles are less likely to aggregate.
  • glycol ethers having a flash point of 140 ° C. or higher and 160 ° C. or lower have a high viscosity of 3 to 30 cP, and colloidal silica particles do not collide with each other in the liquid composition.
  • the film obtained from the liquid composition has a fine concavo-convex structure formed on the surface, and is excellent in water wettability and antifogging property on the film surface.
  • glycol ether which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower is polyethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol Since it is dimethyl ether or diethylene glycol monobenzyl ether, if such glycol ether is used as the solvent of the liquid composition, the colloidal silica in the liquid composition is less likely to aggregate, more reliably with a low refractive index, and water wettability on the film surface. And a low refractive index film excellent in antifogging property.
  • the low refractive index film-forming liquid composition according to the first or second aspect is used, and the low refractive index is excellent in water wettability and antifogging property on the film surface.
  • a refractive index film can be formed.
  • the fourth low refractive index film of the present invention has a low refractive index and is excellent in water wettability and antifogging property on the film surface.
  • the composite film according to the fifth aspect of the present invention includes the low refractive index film and the infrared shielding film according to the fourth aspect, the composite film has an effect of shielding infrared rays and has a low refractive index and a composite. Excellent wettability and anti-fogging property on the film surface.
  • the liquid composition for forming a low refractive index film of the present embodiment (hereinafter sometimes abbreviated as “liquid composition”) is obtained by adding water, nitric acid, and glycol ether to an alcohol solution of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide. It is prepared by mixing a hydrolyzate of silicon alkoxide produced by adding a mixture with an organic solvent and stirring, and a silica sol in which beaded colloidal silica particles are dispersed in a liquid medium.
  • the glycol ether is a liquid composition for forming a low refractive index film, which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower.
  • the amount is 0.5 to 8.0 parts by mass with respect to 1 part by mass of tetramethoxysilane or tetraethoxysilane as silicon alkoxide. It is preferred to add an amount of alcohol solution.
  • an organic solvent such as ethanol, isopropanol (IPA), propylene glycol monomethyl ether (PGME) can be used.
  • the first liquid is prepared by stirring a mixed solution of the silicon alkoxide and the alcohol solution, preferably at a temperature of 30 to 40 ° C. for 5 to 20 minutes.
  • the silicon alkoxide tetraethoxysilane is preferred from the viewpoint of versatility and safety of raw materials.
  • the second liquid is prepared by stirring for 5 to 20 minutes at a temperature of ⁇ 40 ° C.
  • the prepared first liquid is preferably maintained at a temperature of 30 to 80 ° C. using a water bath or the like, and then the second liquid is added to the first liquid and the temperature is preferably maintained. Stir for 30-180 minutes. Thereby, the hydrolyzate of the silicon alkoxide is generated.
  • a liquid composition for forming a low refractive index film according to this embodiment is prepared by adding and mixing a glycol ether, which is a hydrophilic solvent, at a flash point of 140 ° C. or higher to a mixed solution of a hydrolyzate of silicon alkoxide and silica sol. A thing is obtained. At this time, it is preferable to add 5 to 50 parts by mass of glycol ether with respect to 1 part by mass of SiO 2 in the hydrolyzate of silicon alkoxide.
  • glycol ethers having a flash point of 140 ° C. or higher and 160 ° C. or lower include polyethylene glycol monomethyl ether (flash point 145 ° C.), triethylene glycol monobutyl ether (flash point 156 ° C.), tetraethylene glycol.
  • examples include hydrophilic solvents such as dimethyl ether (flash point 141 ° C.), polyethylene glycol dimethyl ether (flash point 147 ° C.) or diethylene glycol monobenzyl ether (flash point 158 ° C.).
  • glycol ether having a flash point of less than 140 ° C. when the liquid composition is left in the atmosphere, the organic solvent is likely to volatilize from the liquid composition, and the dispersion of the beaded colloidal silica particles becomes unstable. Further, in the case of glycol ether exceeding 160 ° C., when forming a low refractive index film using this glycol ether, it is necessary to set the temperature for volatilizing this glycol ether to a high temperature exceeding 250 ° C.
  • the base material of the film is limited to those having heat resistance.
  • Glycol ether which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower, is a hydrophilic solvent, and therefore has excellent compatibility with water in the liquid composition.
  • glycol ether which is a solvent having a flash point of 140 ° C. or higher and 160 ° C. or lower, has a high viscosity of 3 to 30 cP, and colloidal silica particles hardly collide with each other in the liquid composition.
  • the silica sol contained in the liquid composition for forming a low refractive index film of the present embodiment is a sol in which beaded colloidal silica particles are dispersed in a liquid medium.
  • the silica particles contained in the silica sol in addition to the bead shape, spherical, needle-like or plate-like ones are widely known, but in this embodiment, the silica sol in which the bead-like colloidal silica particles are dispersed is used. Use.
  • the reason why the bead-like colloidal silica particles are dispersed is that the presence of the bead-like colloidal silica particles makes it easy to form pores in the formed film, and a film having a very low refractive index can be formed. Because. Further, the bead-like colloidal silica particles have a small particle size and can reduce the haze of the film.
  • the beaded colloidal silica particles are obtained by joining a plurality of spherical colloidal silica particles having an average particle diameter of 5 to 50 nm with metal oxide-containing silica.
  • the average particle diameter of the plurality of spherical colloidal silica particles constituting the beaded colloidal silica particles is limited to the above range because the refractive index of the formed film is sufficiently lowered when the average particle diameter is less than the lower limit.
  • the upper limit is exceeded, the haze of the film increases due to the unevenness of the film surface.
  • the average particle diameter of the plurality of spherical colloidal silica particles constituting the beaded colloidal silica particles is preferably in the range of 5 to 30 nm.
  • the average particle diameter of the spherical colloidal silica particles used was an average value obtained by measuring 200 particle shapes obtained by TEM observation.
  • examples of the metal oxide-containing silica that joins the spherical colloidal silica particles include amorphous silica, amorphous alumina, and the like.
  • the silica sol used preferably has a SiO 2 concentration of 5 to 40% by mass. If the SiO 2 concentration of the silica sol to be used is too low, the refractive index of the film after formation may not be sufficiently lowered. On the other hand, if it is too high, the SiO 2 in the silica sol tends to aggregate and the liquid may become unstable. .
  • a silica sol in which such beaded colloidal silica particles are dispersed for example, a silica sol described in Japanese Patent No. 4328935 can be used.
  • the hydrolyzate and the silica sol have a SiO 2 content of 3 to 3 parts by weight when the SiO 2 content in the hydrolyzate is 1 part by mass. It is prepared by mixing so as to be 45 parts by mass. If the ratio of silica sol is less than the lower limit, the refractive index of the film after formation does not sufficiently decrease, whereas if the upper limit is exceeded, the film thickness becomes uneven, resulting in increased film surface irregularities and increased haze. It is. Of these, the proportion of the silica sol, SiO 2 minutes of silica sol for SiO 2 minutes 1 part by weight of the hydrolyzate is preferably in the ratio of 10 to 30 parts by weight.
  • a method for forming the low refractive index film of this embodiment will be described.
  • a substrate such as glass or plastic is prepared, and the liquid composition for forming a low refractive index film of the present embodiment described above is prepared on the surface of the substrate. Apply by spin coating, die coating or spraying. After coating, it is preferably dried at a temperature of 50 to 100 ° C. for 5 to 60 minutes using a hot plate or an atmosphere firing furnace, and then preferably 100 to 300 ° C. using a hot plate or an atmosphere firing furnace. Bake at a temperature of 5 to 120 minutes to cure.
  • the film thus formed exhibits a very low refractive index of about 1.15 to 1.4 due to the generation of appropriate pores inside the film.
  • the film surface is excellent in wettability and exhibits high water repellency, it is easy to form another film on the formed film surface, so that it is excellent in versatility. Therefore, for example, an antireflection film used for preventing reflection of incident light in a display panel such as a cathode ray tube, a liquid crystal, an organic EL, a solar cell, a glass for a showcase, or a refractive index difference used for a sensor, a camera module, or the like.
  • the surface has a fine concavo-convex structure and is excellent in antifogging properties, it can be suitably used as a film for coating on the surface of mirrors, glasses, infrared shielding films and the like.
  • the liquid composition of this embodiment can also be applied (coated) to the surface of the infrared shielding film.
  • the composite film provided with the low refractive index film of this embodiment on the surface of the infrared shielding film will be described in detail.
  • the infrared shielding film is prepared by mixing a surface-modified ITO powder (indium tin oxide powder) and a dispersion medium to prepare a dispersion, and mixing the dispersion with an organic solvent to form an infrared shielding film-forming paint. Then, it is applied to the surface of a transparent substrate such as a glass substrate or a plastic film and dried to form.
  • the composite film is produced by forming the low refractive index film of this embodiment on the surface of the infrared shielding film by the method described above.
  • the base material to which the liquid composition for forming a low refractive index film of the present embodiment is applied is an infrared shielding film.
  • the surface-modified ITO powder is manufactured by the following method. First, a mixed aqueous solution in which an indium chloride (InCl 3 ) aqueous solution and tin dichloride (SnCl 2 .2H 2 O) are mixed is prepared. Next, the mixed aqueous solution and the aqueous ammonia (NH 3 ) solution are simultaneously dropped into water, adjusted to a predetermined pH, and then reacted at a predetermined liquid temperature for a predetermined time. Next, the precipitate formed by this reaction is repeatedly washed with ion-exchanged water.
  • InCl 3 indium chloride
  • SnCl 2 .2H 2 O tin dichloride
  • the precipitate (In / Sn coprecipitated hydroxide) is separated by filtration to obtain coprecipitated indium tin hydroxide.
  • the solid-liquid separated indium tin hydroxide is dried at a predetermined temperature for a predetermined time, and then baked in the air at a predetermined temperature for a predetermined time.
  • the aggregate formed by this firing is pulverized and loosened to obtain an ITO powder before surface modification.
  • the ITO powder is impregnated in a surface treatment solution in which distilled water is slightly mixed with absolute ethanol.
  • the ITO powder impregnated with the surface treatment liquid is heated at a predetermined temperature for a predetermined time in an inert gas atmosphere to obtain a surface-modified ITO powder.
  • TEOS tetraexylsilane
  • ion exchange water in an amount of 0.8 parts by mass and nitric acid in an amount of 0.01 parts by mass with respect to 1 part by mass of silicon alkoxide are charged into a beaker and mixed.
  • the second liquid was prepared by stirring at a temperature of 30 ° C. for 15 minutes.
  • the second liquid was added to the first liquid and stirred for 60 minutes while maintaining the temperature. Thereby, the hydrolyzate of the silicon alkoxide was obtained.
  • the obtained hydrolyzate and the silica sol in which the beaded colloidal silica particles are dispersed are stirred at a ratio that the SiO 2 content in the silica sol becomes 20 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate. And mixed. Furthermore, polyethylene glycol monomethyl ether (flash point 145 ° C.) as a glycol ether solvent having a flash point of 140 ° C. or higher is added to the mixed solution of the hydrolyzate and silica sol with respect to 1 part by mass of SiO 2 in the hydrolyzate. The mixture was stirred and mixed at a ratio of 22 parts by mass of polyethylene glycol monomethyl ether to obtain a liquid composition.
  • Example 2 A liquid composition was prepared in the same manner as in Example 1 except that the glycol ether solvent having a flash point of 140 ° C. or higher was changed to triethylene glycol monobutyl ether (flash point 156 ° C.).
  • Example 3 A liquid composition was prepared in the same manner as in Example 1 except that tetraethylene glycol dimethyl ether (flash point 141 ° C.) was used as a glycol ether solvent having a flash point of 140 ° C. or higher.
  • Example 4 A liquid composition was prepared in the same manner as in Example 1 except that polyethylene glycol dimethyl ether (flash point 147 ° C.) was used as a glycol ether solvent having a flash point of 140 ° C. or higher.
  • Example 5 A liquid composition was prepared in the same manner as in Example 1 except that diethylene glycol monobenzyl ether (flash point 158 ° C.) was used as a glycol ether solvent having a flash point of 140 ° C. or higher.
  • the prepared liquid composition was applied to the surface of a glass substrate by a spin coating method to form a coating film.
  • the glass substrate on which this coating film was formed was dried at a temperature of 50 ° C. for 10 minutes using an atmosphere firing furnace, and then baked and cured at a temperature of 250 ° C. using an atmosphere firing furnace to obtain a thickness.
  • a film of about 80 nm was formed on the surface of the glass substrate.
  • the refractive index of this film was measured using a spectroscopic ellipsometry apparatus (manufactured by JAWoollam Japan, model number: M-2000). The value of 633 nm in the analyzed optical constant was taken as the refractive index.
  • the antifogging property of the film surface was evaluated with respect to the film
  • the mass reduction rate in Comparative Example 1 was as high as 11.5%.
  • the mass reduction rate was extremely small at 2.7 to 4.2%, and it was found that the liquid compositions of Examples 1 to 5 had less cohesiveness of colloidal silica particles.
  • the visual observation of the liquid composition in Comparative Example 1, a white floating substance was confirmed, which was defective.
  • no suspended matter was observed, which was good.
  • the refractive index of the film is 1.28 in Comparative Example 1 and 1.22 to 1.27 in Examples 1 to 5, which is slightly lower than that of Comparative Example 1, and both films are Good at low refractive index. It is considered that the refractive index of the film depends on the solid matter of the liquid composition.
  • the water wettability (contact angle) of the film was as high as 7.1 degrees in Comparative Example 1.
  • the antifogging property of the film in Comparative Example 1, fogging occurred on the film surface on the glass substrate, and the antifogging effect was poor.
  • the film surface on the glass substrate did not generate any fogging and was clear and good.
  • Example 6 An ITO dispersion liquid (1.0 g) in which the surface-modified ITO powder was dispersed and 3.0 g of ethanol were mixed to prepare a coating material for forming an infrared shielding film.
  • This paint was spin-coated on a glass substrate at a rotation speed of 1000 rpm. After spin coating, the film was dried in an atmosphere firing furnace at a temperature of 50 ° C. for 10 minutes to form an infrared shielding film on the glass substrate.
  • the low refractive index film-forming liquid composition obtained in Example 2 was applied in the same manner as in Example 2 to form a low refractive index film. As a result, a composite film having a low refractive index film on the surface of the infrared shielding film was obtained.
  • the surface-modified ITO powder used in Example 6 was produced by the following method. 50 mL of an indium chloride (InCl 3 ) aqueous solution (containing 18 g of In metal) and 3.6 g of tin dichloride (SnCl 2 .2H 2 O) are mixed, and this mixed aqueous solution and an aqueous ammonia (NH 3 ) solution are added to 500 ml of water. The solution was added dropwise at the same time, adjusted to pH 7, and reacted at a liquid temperature of 30 ° C. for 30 minutes. The generated precipitate was repeatedly washed with ion-exchange water.
  • InCl 3 indium chloride
  • SnCl 2 .2H 2 O tin dichloride
  • NH 3 aqueous ammonia
  • the precipitate (In / Sn coprecipitated hydroxide) was separated by filtration to obtain coprecipitated indium tin hydroxide.
  • the solid-liquid separated indium tin hydroxide was dried at 110 ° C. overnight and then calcined at 550 ° C. for 3 hours in the atmosphere.
  • the aggregate formed by this firing was pulverized and loosened to obtain about 25 g of ITO powder before surface modification.
  • the ITO dispersion liquid in which the ITO powder subjected to the surface modification treatment used in Example 6 was dispersed was prepared by the following method. 20 g of the ITO powder subjected to the surface modification treatment and 29.42 g of the dispersion medium are placed in a Laboran standard bottle No. 10 together with 100 g of 0.5 mm ⁇ ZrO 2 beads, and dispersed with a paint shaker for 10 hours to obtain the ITO dispersion liquid. Obtained. ZrO 2 beads were used to uniformly disperse ITO powder in a dispersion medium.
  • This dispersion medium comprises 0.020 g of distilled water, 23.8 g of triethylene glycol-di-2-ethylhexanoate, 2.1 g of absolute ethanol, 1.0 g of phosphoric acid polyester, 2.0 g of 2-ethylhexanoic acid, and It is a mixed solution of 0.5 g of 2,4-pentanedione.
  • Example 7 The same solution as in Example 6 was prepared by mixing and dissolving 15 g of absolute ethanol, 0.99 g of epoxy acrylate resin beam set 577 (Arakawa Chemical) and 0.01 g of photopolymerization initiator Irgacure 907 (BASF). 4.0 g of the ITO dispersion prepared by the method was added to prepare an infrared shielding film-forming coating material. This paint was spin-coated on a glass substrate at a rotation speed of 1000 rpm. After spin coating, the film was dried in an atmosphere firing furnace at a temperature of 50 ° C. for 10 minutes.
  • the resin was cured by using a UV irradiation device (manufactured by USHIO) and irradiated with 3-pass ultraviolet rays at a metal halide lamp output of 80 W and a feed rate of 5.0 m / s to form an infrared shielding film.
  • a UV irradiation device manufactured by USHIO
  • 3-pass ultraviolet rays at a metal halide lamp output of 80 W and a feed rate of 5.0 m / s
  • the low refractive index film-forming liquid composition obtained in Example 2 was applied in the same manner as in Example 2 to form a low refractive index film.
  • a composite film having a low refractive index film on the surface of the infrared shielding film was obtained.
  • Example 8> 1.63 g of a mixed solution was prepared by mixing 0.33 g of the ITO dispersion prepared by the same method as in Example 6 and 1.30 g of absolute ethanol. The mixture was mixed with 1.00 g of the hydrolyzate of silicate alkoxide prepared in Example 1 to prepare an infrared shielding film-forming coating material. This paint was spin-coated on a glass substrate at a rotation speed of 1000 rpm. After spin coating, the film was dried at a temperature of 50 ° C. for 10 minutes in an atmosphere firing furnace to form an infrared shielding film.
  • Example 2 On the surface of this infrared shielding film, the low refractive index film-forming liquid composition obtained in Example 2 was applied in the same manner as in Example 2 to form a low refractive index film. As a result, a composite film having a low refractive index film on the surface of the infrared shielding film was obtained.
  • Infrared shielding properties were measured by irradiating the composite film with infrared rays having a wavelength of 1500 nm using an ultraviolet-visible spectrophotometer (Hitachi High Technologies: U-4100).
  • the composite films obtained in Examples 6 to 8 have a low refractive index of 1.22 to 1.24 and a water wettability (contact angle) of the film of 3.2 to It was found to be as low as 3.4 degrees and the water wettability of the film was high.
  • the composite films obtained in Examples 6 to 8 were clear and free from fogging on the film surface on the glass substrate. Further, when the composite film obtained in Examples 6 to 8 was irradiated with infrared rays having a wavelength of 1500 nm, the transmittance was 12 to 35%, indicating that the infrared rays were sufficiently shielded.
  • the liquid composition of the present invention is used to form a low refractive index film used for coating the surface of display panels, solar cells, optical lenses, camera modules, sensor modules, mirrors, glasses, infrared shielding films, and the like. it can.

Abstract

　Cette composition liquide pour formation de film à faible indice de réfraction est préparée par mélange d'un hydrolysat d'alcoxyde de silicium produit par ajout d'un mélange d'eau et d'acide nitrique à une solution alcoolique de tétraméthoxysilane ou de tétraéthoxysilane en tant qu'alcoxyde de silicium, puis agitation du mélange susmentionné, et d'un sol de silice dans lequel des particules de silice colloïdale sous forme de billes sont dispersées dans un milieu liquide, un solvant organique d'éther glycolique étant ensuite amalgamé. Cet éther glycolique est un solvant présentant un point éclair supérieur ou égal à 140℃ et inférieur ou égal à 160℃.
PCT/JP2016/051548 2015-01-20 2016-01-20 Composition liquide pour formation de film à faible indice de réfraction WO2016117592A1 (fr)

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