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WO2013115367A1 - Composition filmogène présentant un indice de réfraction faible - Google Patents

Composition filmogène présentant un indice de réfraction faible Download PDF

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Publication number
WO2013115367A1
WO2013115367A1 PCT/JP2013/052359 JP2013052359W WO2013115367A1 WO 2013115367 A1 WO2013115367 A1 WO 2013115367A1 JP 2013052359 W JP2013052359 W JP 2013052359W WO 2013115367 A1 WO2013115367 A1 WO 2013115367A1
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Prior art keywords
film
forming composition
solvent
refractive index
inorganic particles
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Ceased
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PCT/JP2013/052359
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English (en)
Japanese (ja)
Inventor
加藤　拓
恵 嶋田
中島　誠
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2013556516A priority Critical patent/JP6044792B2/ja
Priority to KR1020147022727A priority patent/KR102244973B1/ko
Priority to KR1020207012923A priority patent/KR102285627B1/ko
Priority to CN201380007423.XA priority patent/CN104080869B/zh
Publication of WO2013115367A1 publication Critical patent/WO2013115367A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C09D183/02—Polysilicates
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • 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
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/107—Porous materials, e.g. for reducing the refractive index

Definitions

  • the present invention relates to a film-forming composition, and more particularly to a film-forming composition containing polysiloxane and inorganic fine particles.
  • An antireflection function is obtained by controlling the optical refractive index. This can be achieved by selecting a member having a low refractive index as a member constituting the device.
  • Patent Document 1 a fluorinated alkylsilane is applied to the surface of a substrate (Patent Document 1), and a polymer containing fluorine (Patent Document 2) is proposed. . These have achieved low refractive index by introducing fluorine, but it is difficult to make the refractive index 1.30 or less at a wavelength of 633 nm.
  • Patent Document 3 a method for reducing the refractive index by putting air having a refractive index of 1.0 into the film (Patent Document 3) and a method for decreasing the refractive index by making the center of the inorganic particles hollow (Patent Document 4) are proposed.
  • Patent Document 3 a method for reducing the refractive index by putting air having a refractive index of 1.0 into the film
  • Patent Document 4 a method for decreasing the refractive index by making the center of the inorganic particles hollow
  • the target low refractive index material is required to have high transparency, high heat resistance, high light resistance and high hardness, and it is very difficult to satisfy these required characteristics at once.
  • polysiloxane When inorganic particles are added, the film hardness may decrease. Polysiloxane has a high film hardness but does not exhibit a low refractive index. From these backgrounds, a method of combining inorganic particles and polysiloxane to obtain a low refractive index material is known as a known technique.
  • the polymer structure of polysiloxane varies depending on the method of synthesis, but polysiloxane is known which has been completely hydrolyzed by changing the hydrolysis solvent to a specific solvent (Patent Document 5). There has been no study of using a combination of inorganic particles and fully hydrolyzed polysiloxane as a low refractive index material.
  • Patent Documents 6 to 8 As a method for producing inorganic particles used for the low refractive index material, a method using hydrolysis of alkoxide is known (Patent Documents 6 to 8). And the method by ion exchange of water glass is known (patent documents 9 thru / or 10). A technique for controlling the particle shape by such a method is disclosed.
  • the present invention has been made in view of such circumstances, and has a low refractive index and is suitable for production of a film for a display device that can achieve high transparency, high heat resistance, high light resistance, and high hardness. It aims at providing the composition for film formation.
  • the present invention provides, as a first aspect, a silicon compound (A) having a weight average molecular weight of 1000 to 20000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent, and an inorganic material having an average particle diameter of 1 to 100 nm.
  • a film-forming composition comprising particles (B) and a solvent (C);
  • the silicon compound (A) is represented by the following formula (1): (Wherein R 1 represents an alkoxy group, an acyloxy group, or a halogen group)
  • the film-forming composition according to the first aspect which is a hydrolysis condensate of a hydrolyzable silane represented by:
  • the film-forming composition according to the second aspect wherein the hydrolyzable silane represented by the formula (1) is tetraethoxysilane or tetramethoxysilane
  • the non-alcohol solvent is a ketone or an ether
  • the film-forming composition according to any one of the first to third aspects wherein the non-alcohol solvent is acetone or tetrahydrofuran
  • the solvent (C) is a non-
  • a film-forming composition according to any one of the first to fifth aspects As a seventh aspect, the film forming composition according to any one of the first aspect to the sixth aspect, wherein the inorganic particles (B) are particles having a refractive index of 1.15 to 1.50, As an eighth aspect, the inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, and a dispersed particle size (particle size B) by the dynamic light scattering method.
  • the inorganic particles (B) are inorganic particles (B-2) having an outer shell and an inside, the inside being porous or hollow, and an average particle diameter of 15 to 100 nm.
  • the film forming composition according to any one of the first aspect to the seventh aspect As a tenth aspect, a silicon compound (A) in which a silicon compound (A) having a weight average molecular weight of 1,000 to 20,000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent is dissolved in the solvent (C).
  • a first aspect including a step of obtaining a varnish of the above and a step of mixing a sol of a dispersion medium (C ′) containing inorganic particles (B) having an average particle diameter of 1 to 100 nm and a varnish of the silicon compound (A).
  • the inorganic particles (B) are inorganic particles having an average particle diameter of 1 to 100 nm and a refractive index of 1.15 to 1.50 calculated from the specific surface area by the BET method.
  • a film forming composition according to any one of the first to ninth aspects is coated on a substrate and fired, and a refractive index of 1.15 to 1.30 at a wavelength of 633 nm.
  • a film having a pencil hardness of H to 9H defined by JIS standard K5600 As a thirteenth aspect, the method for forming a film according to the twelfth aspect, including a step of coating and baking the film forming composition according to any one of the first aspect to the ninth aspect on a substrate, As a fourteenth aspect, an antireflection film obtained from the film forming composition according to any one of the first aspect to the ninth aspect,
  • an apparatus having an electronic device obtained by using the film forming composition according to any one of the first to ninth aspects, and as a sixteenth aspect, an electronic device is a liquid crystal display, plasma The device according to the fifteenth aspect, which is a display, a cathode ray tube, an organic light emitting display,
  • the composition comprising the fully hydrolyzed polysiloxane of the present invention and silica fine particles having a dispersed particle size of 100 nm or less is a completely hydrolyzed polysiloxane having a high silanol reaction point of silanol on the surface of the silica fine particles having a low film hardness. Since it is thermally cured with siloxane, a film having a low refractive index and a high film hardness can be obtained. That is, the present invention provides a film-forming composition suitable for producing a film for a display device that has a low refractive index and can achieve high transparency, high heat resistance, high light resistance, and high hardness.
  • the film obtained by the present invention can satisfy low refractive index, high transparency, high heat resistance, high light resistance, and high hardness at one time, and can be used for liquid crystal display, plasma display, cathode ray tube, organic light emission. It can be suitably used as an electronic device such as a display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, and an organic thin film transistor.
  • an electronic device such as a display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, and an organic thin film transistor.
  • FIG. 1 H-NMR spectrum of P1 Diagram showing 1 H-NMR spectrum of P2
  • the figure which shows the light transmittance after the 200 degreeC heat resistant test of V1 for 5 minutes The figure which shows the light transmittance after the heat resistance test of 250 degreeC for 5 minutes of V1
  • the figure which shows the light transmittance after 300 degreeC 5 minute heat resistance test of V1 The figure which shows the light transmittance after the 200 degreeC 5-minute heat resistance test of V2.
  • the figure which shows the light transmittance before the light resistance test of V1 The figure which shows the light transmittance after the light resistance test of V1
  • the figure which shows the light transmittance before the light resistance test of V2 The figure which shows the light transmittance after the light resistance test of V2
  • the figure which shows the light transmittance before the constant temperature and humidity test of V1 The figure which shows the light transmittance after the constant temperature and humidity test of V1
  • the figure which shows the light transmittance before the constant temperature and humidity test of V2. The figure which shows the light transmittance after the constant temperature and humidity test of V2.
  • the partially hydrolyzed polysiloxane refers to a polymer obtained by using an alcohol containing a functional group such as a hydroxyl group as a solvent during hydrolysis or polycondensation.
  • the partially hydrolyzed polysiloxane is hydrolyzed and in the polycondensation stage, the alcohol produced from the solvent alcohol or the monomer silane alkoxide reacts with the silanol group produced by the hydrolysis and remains in the form of silane alkoxide. .
  • polysiloxane having a large residual ratio of silane alkoxides is obtained when alcohol is selected as a solvent for hydrolysis and condensation.
  • the fully hydrolyzed polysiloxane refers to a polymer obtained by using a non-alcohol containing no hydroxyl group as a solvent for hydrolysis and condensation.
  • the non-alcohol solvent which is a solvent for hydrolysis and polycondensation, does not have a hydroxyl group that clogs the silanol of the polymer, so that the polymer obtained has a high residual ratio of silanol. It becomes siloxane.
  • the silane alkoxide contained in the partially hydrolyzed polysiloxane shows an organic group such as carbon and is a part that increases the refractive index.
  • a fully hydrolyzed polysiloxane since a fully hydrolyzed polysiloxane has a very low residual ratio of silane alkoxide, it has almost no portion that increases the refractive index such as carbon.
  • the fully hydrolyzed polysiloxane contains a large amount of silanol, polycondensation can be initiated when heat is applied as an external stimulus to silanol on the surface of the silica fine particles, and a strong and high hardness film can be formed.
  • the partially hydrolyzed polytheos a large amount of silane alkoxide remains, so when it reacts with silanol of silica fine particles, it must go through hydrolysis once, and it is necessary to add an additive or the like separately.
  • examples of the additive include a silanol production accelerator and a silane alkoxide decomposition accelerator, but these additives contain organic groups and metals to increase the refractive index and are not suitable for the composition of the present invention. is there.
  • the ratio of the average particle size (particle size A) calculated from the specific surface area by the BET method to the dispersed particle size (particle size B) by the dynamic light scattering method is determined by deforming the inorganic particles. It is considered to be one of the scales shown.
  • the ratio of the particle diameter A calculated as being spherical with the particle diameter B in the actual liquid the degree of irregularity of the inorganic particles is estimated. It is considered that as the ratio of (particle diameter B) / (particle diameter A) increases, the irregular shape of the inorganic particles proceeds and the voids in the resulting coating increase.
  • the inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, and a dispersed particle size (particle size B) by the dynamic light scattering method of 50 to 250 nm.
  • particle size A average particle size
  • particle size B dispersed particle size
  • the present invention is calculated from a silicon compound (A) having a weight average molecular weight of 1,000 to 20,000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent, and a specific surface area by the BET method.
  • a film-forming composition comprising inorganic particles (B) having an average particle diameter of 1 to 100 nm and a solvent (C).
  • the solid content concentration of the film-forming coating solution only needs to be adjusted so as to obtain the film thickness of the target film-forming film, and is 0.1 to 50% by mass, 1 to 30% by mass, or 5
  • the concentration range may be 20 to 20% by mass.
  • the solid content is the remaining ratio after the solvent is removed from the film-forming composition.
  • the silicon compound (A) can be added in the range of 0.1 to 50 parts by mass, preferably 0.1 to 30 parts by mass. In order to maintain the film quality and obtain a stable low refractive index, the amount is more preferably 1 to 20 parts by mass.
  • the silicon compound (A) used in the present invention is a hydrolysis condensate of a hydrolyzable silane represented by the formula (1).
  • This hydrolysis-condensation product may contain a hydrolysis product.
  • the hydrolyzate is a product in which the hydrolyzable group of the silane monomer is hydrolyzed to produce a silanol group.
  • the hydrolyzed condensate is a hydrolyzed condensate in which silanol groups in the hydrolyzed product undergo dehydration condensation and forms a polysiloxane, and the terminal of the condensate usually has a silanol group.
  • Most of the silicon compound (A) is a hydrolysis condensate (polysiloxane), but may have a hydrolyzate that is a precursor thereof.
  • R 1 in Formula (1) represents an alkoxy group, an acyloxy group, or a halogen group.
  • alkoxy group examples include an alkoxy group having 1 to 20 carbon atoms, and examples include an alkoxy group having a linear, branched, or cyclic alkyl moiety.
  • acyloxy group examples include an acyloxy group having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, and an isobutylcarbonyloxy group.
  • halogen group as the hydrolyzing group examples include fluorine, chlorine, bromine, iodine and the like.
  • hydrolyzable silane represented by the above formula (1) examples include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, tetrachlorosilane, and the like.
  • the present invention is not limited to these.
  • tetramethoxysilane and tetraethoxysilane can be preferably used.
  • a commercially available product can be used as the hydrolyzable silane.
  • the silicon compound (A) containing the hydrolysis condensate obtained by hydrolyzing and condensing the water-decomposable silane represented by the formula (1) can be a condensate having a weight average molecular weight of 1000 to 20000, or 1000 to 5000. . These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.
  • Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin Acid, gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthal
  • Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine. And zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene, and the like.
  • inorganic base examples include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
  • metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.
  • a volatile inorganic acid such as hydrochloric acid
  • hydrolysis of an alkoxysilyl group, an acyloxysilyl group, and a halogenated silyl group 0.1 to 100 mol, or 0.1 to 10 mol, or 1 to 5 mol, or 1 mol per mol of the hydrolyzable group, or 2 to 3.5 moles of water are used.
  • the reaction temperature for carrying out the hydrolysis and condensation is usually in the range of 20 ° C. (room temperature) to the reflux temperature under normal pressure of the solvent used for the hydrolysis. Moreover, it can carry out under pressure, for example, can heat up to about 200 degreeC of liquid temperature.
  • Examples of the method for obtaining the silicon compound (A) containing the hydrolysis condensate (polysiloxane) include a method of heating a mixture of hydrolyzable silane, non-alcohol solvent, pure water and acid catalyst. Specifically, the hydrolyzable silane is dissolved in acetone in advance, and hydrochloric acid and pure water are added to form an aqueous hydrochloric acid solution, which is then dropped into the hydrolyzable silane solution and heated.
  • the amount of hydrochloric acid is generally 0.0001 to 0.5 mol with respect to 1 mol of all hydrolyzable groups (total alkoxy groups) of the hydrolyzable silane.
  • the heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and is preferably performed, for example, for several tens of minutes to several tens of hours under reflux in a sealed container so that the liquid does not evaporate or volatilize. Is called.
  • Non-alcohol solvents used for hydrolysis and condensation include, for example, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methyl Aliphatic hydrocarbon solvents such as cyclohexane; aromatics such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, isopropyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene, di-isopropyl benzene, trimethyl benzene, etc.
  • Group hydrocarbon solvents acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pe Ketone solvents such as tilketone, ethyl-n-butylketone, methyl-n-hexylketone, di-isobutylketone, cyclohexanone, methylcyclohexanone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, And ether solvents such as tetrahydrofuran and 2-methyltetrahydrofuran. These solvents can be used alone or in combination of two or more. Of these, ketone solvents such as acetone and ether solvents such as tetrahydrofuran are preferable
  • Hydrolyzable silane is hydrolyzed in a non-alcohol solvent, and the hydrolyzate is subjected to a condensation reaction to obtain a hydrolyzed condensate (polysiloxane).
  • the condensate is dissolved in the hydrolyzed solvent. Obtained as a siloxane varnish.
  • the solvent of the silicon compound (A) containing the obtained hydrolysis condensate may be substituted.
  • acetone is selected as a solvent for hydrolysis and condensation (solvent for synthesis)
  • the same amount of substitution solvent as that for the synthesis is added.
  • the acetone may be distilled off azeotropically with an evaporator or the like.
  • reactants for example, methanol, ethanol
  • a volatile acid catalyst it can be removed at the same time.
  • This replacement solvent becomes a solvent component when the silicon compound (A) containing the hydrolysis condensate (polysiloxane) is used as a varnish.
  • the boiling point is preferably lower than that of the substitution solvent.
  • the solvent for hydrolysis and condensation includes acetone, tetrahydrofuran and the like, and the substitution solvent includes propylene glycol monomethyl ether acetate and the like.
  • the solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) may be the same as the non-alcohol solvent used for hydrolysis and condensation polymerization of the hydrolyzable silane. Good or another solvent may be used. And the solvent in the varnish of the silicon compound (A) containing a hydrolysis-condensation product (polysiloxane) can be said solvent (C).
  • the concentration of the silicon compound (A) in the varnish can be used in the range of 0.1 to 60% by mass.
  • solvent (C) examples include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl.
  • Ether ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether Ter, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol
  • the solvent which is the component (C) of the present invention is preferably a non-alcohol solvent similar to the solvent from which the component (A) was obtained, but is not particularly limited as long as the storage stability of the coating liquid for film formation of the present invention is not significantly impaired.
  • the general organic solvent mentioned above can be used.
  • the solvent (C) is more preferably butanol, di- Acetone alcohol, methyl ethyl ketone, methyl isobutyl ketone, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Examples include propylene glycol monobutyl ether, cyclohexanone, acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester.
  • the silicon compound (A) containing the hydrolysis-condensation product (polysiloxane) of the present invention is obtained by using a non-alcohol containing no hydroxyl group as a solvent for hydrolysis and polycondensation.
  • This polysiloxane is called polysiloxane and has a high hydrolysis rate.
  • a polymer obtained by using an alcohol containing a hydroxyl group as a solvent for hydrolysis or polycondensation is referred to as a partially hydrolyzed polysiloxane for distinction.
  • the major difference between the fully hydrolyzed type and the partially hydrolyzed type is that the abundance of silanol (Si—OH) at the end of the polymer is different.
  • the fully hydrolyzed polysiloxane has a partially hydrolyzed type of polysiloxane. There are more than polysiloxanes.
  • the abundance of Si—OH may be quantified by 1 H-NMR with the same solid content using a varnish substituted with a non-alcohol solvent. The quantification can be determined by comparing the number of protons obtained by integrating the Si-OH peak of polysiloxane and calculating the peak area with the number of protons obtained by integrating the peak of the internal standard or the solvent and calculating the peak area.
  • the calculated proton number of the fully hydrolyzed polysiloxane Si—OH is 0.1 or more, preferably 0.2 or more.
  • the partially hydrolyzed polysiloxane is defined as the number of protons calculated by the Si—OH of the polysiloxane being less than 0.1 when the number of protons calculated from the internal standard or the peak of the solvent is 1.00. .
  • the component (B) used in the present invention is inorganic particles (B) having an average particle diameter of 1 to 100 nm.
  • the refractive index of the inorganic particles (B) is selected from the range of 1.15 to 1.50, 1.20 to 1.50, 1.30 to 1.50, or 1.30 to 1.45. Can do.
  • the kind of inorganic particles constituting the composition of the present invention together with the above fully hydrolyzed polysiloxane is not particularly limited, but in the present invention, silicon oxide or a composite oxide containing silicon is particularly used. Is preferred.
  • the inorganic particles may be used alone or in combination of two or more.
  • the oxide constituting the inorganic particles include SiO 2 and composite oxides containing SiO 2 .
  • This composite oxide is a mixture of two or more inorganic oxides at the particle production stage.
  • these compounds can be used alone or in admixture of two or more, and may be used in admixture with other oxides.
  • inorganic particles (B-1) having an average particle diameter of 1 to 100 nm, 5 to 100 nm, or 5 to 60 nm calculated from the specific surface area by the BET method can be used.
  • the component (B) used in the present invention has an average particle diameter calculated from a specific surface area by the BET method of 1 to 100 nm, 5 to 100 nm, or 5 to 60 nm, and a refractive index of 1.15 to 1. .50 inorganic particles (B-1) can be used.
  • the inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, a dispersed particle size (particle size B) by the dynamic light scattering method of 50 to 250 nm, Examples thereof include inorganic particles (B-1) having a diameter B / particle diameter A of 1.1 or more.
  • the average particle size (particle size A) calculated from the specific surface area by the BET method is 5 to 60 nm, and the dispersed particle size (particle size B) by the dynamic light scattering method. Is preferably 50 to 250 nm.
  • the relationship between the particle diameter A and the particle diameter B is such that the particle diameter B / particle diameter A is 1.1 or more, for example 1.1 to 50.0, or 1.1 to 20.0, or 1.1 to 10.0. Or 1.1 to 5.0, or 1.4 to 20.0, or 1.4 to 10.0, or 1.4 to 5.0.
  • the particle diameter fine particles having different average particle diameters or dispersed particle diameters may be mixed and used.
  • the particles when using the inorganic particles, the particles may be used as they are, and those in a colloidal state in which the particles are previously dispersed in water or an organic solvent (in which colloidal particles are dispersed in a dispersion medium, ie, sol). It may be used.
  • concentration of the inorganic particles in the sol can be used in the range of 0.1 to 60% by mass.
  • An organic solvent sol in which a dispersion medium of a water sol in which inorganic particles are dispersed in an aqueous medium is replaced with an organic solvent from water can be used.
  • This dispersion medium (C ′) is combined with the solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) and used in the present invention. It can be.
  • the same dispersion medium (C ′) as the solvent (C) can be used.
  • particles obtained by surface treatment of inorganic particles with silicon oxide, organosilicon compounds, organometallic compounds, or the like may be used.
  • the treatment with silicon oxide is a method in which a silicon oxide substance is grown on a particle surface in a dispersion containing inorganic particles by a known method.
  • the treatment with an organosilicon compound or an organometallic compound means that these compounds are added to a dispersion containing inorganic particles, and these compounds or reaction products of these compounds are adsorbed or bonded to the surface of the inorganic particles.
  • the organosilicon compound include silane coupling agents and silanes.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl).
  • Ethyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (a Noethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminoprop
  • silane examples include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, dimethyldisilane.
  • Ethoxysilane phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, etc. It is done.
  • organometallic compound examples include titanate coupling agents and aluminum coupling agents
  • specific examples of titanate coupling agents include pre-act KR TTS, KR 46B, KR 38B, KR 138S, KR238S, 338X
  • Specific examples of KR 44, KR 9SA, KR ET5, KR ET (Ajinomoto Fine Techno Co., Ltd.) and aluminum coupling agents include Plenact AL-M (Ajinomoto Fine Techno Co., Ltd.) and the like.
  • organic silicon compounds and organometallic compounds are preferably used in an amount of 2 to 100 parts by mass with respect to 100 parts by mass of the inorganic particles.
  • the metal oxide colloidal particles used for the inorganic particles (B-1) can be produced by a known method such as an ion exchange method, a peptization method, a hydrolysis method, or a reaction method.
  • Examples of the ion exchange method include a method in which the metal salt is treated with an ion exchange resin to remove counter ions and generate particles.
  • Peptides include neutralization of the metal salt with an acid or base, hydrolysis of the metal alkoxide, or precipitation obtained by hydrolysis of the metal basic salt under heating, or Examples thereof include a method of removing unnecessary electrolyte from the gel or adding ions necessary for dispersion. Examples of the reaction method include a method of reacting the metal powder with an acid.
  • inorganic particles (B-2) having an outer shell and an interior, the interior being porous or hollow, and an average particle diameter of 15 to 100 nm can be used.
  • Silica particles can be used as the inorganic particles (B-2).
  • the production method thereof is, for example, an alkaline composite inorganic oxide or its After forming an aqueous solution of particles, elements other than silicon are removed to form cavities inside the particles, and then a silica coating layer is formed on the fine particles by adding a silicic acid solution.
  • the refractive index of the inorganic particles (B-2) can be in the range of 1.15 to 1.50.
  • the composite inorganic oxide has an (inorganic oxide other than silica) / (silica) molar ratio in the range of 0.2 to 1.2, or 0.3 to 1.0, and the electrolyte salt and silica are (electrolyte salt).
  • ) / (Silica) molar ratio can be adjusted to a range of 0.1 to 10 to form a solution of a composite inorganic oxide or particles thereof.
  • An alkaline solution having a pH of 10.0 or more can be used.
  • examples of inorganic oxides other than silica include aluminum oxide, titanium oxide, boron oxide, zirconium oxide, and antimony oxide.
  • the silica coating layer can also be formed by adding an alkaline aqueous solution and an acidic silicic acid solution obtained by dealkalizing an alkali metal silicate hydrolyzate or alkali metal silicate to the fine particle dispersion.
  • silica coating layer As a result of observation with an electron microscope, a film (outer shell) of about 6 to 10 nm is formed on this silica coating layer.
  • Silica particles having a hollow structure have an average particle diameter of 15 to 100 nm as observed with an electron microscope and a refractive index of 1.15 to 1.50.
  • This dispersion of hollow particles can be made into an organic solvent-dispersed sol by solvent substitution with the above-mentioned dispersion medium at a silica particle concentration of 0.1 to 60% by mass.
  • the method for preparing the film forming composition for a display device and the coating liquid for forming a film of the present invention is not particularly limited. It suffices if the (A) component, (B) component, and (C) component are uniformly mixed. The order of mixing components (A) to (C) is not particularly limited as long as a uniform varnish can be obtained.
  • the solid content of the film-forming composition contains the silicon compound (A) and inorganic particles (B), but may contain other components.
  • other components such as a leveling agent and a surfactant are included as long as the effects of the present invention are not impaired. May be.
  • surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene, and the like.
  • Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301 , EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, F-553, F-554, R-08, R-30, R-30-N (Dainippon In
  • surfactants may be used alone or in combination of two or more.
  • the ratio is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the silicon compound (A). Part by mass.
  • the method of mixing the other components, the solvent, the leveling agent or the surfactant described above may be performed simultaneously with the addition of the inorganic particles (B) and the solvent (C) to the silicon compound (A). ) It may be after mixing and is not particularly limited.
  • the film-forming composition of the present invention can be applied to a substrate and thermally cured to obtain a desired film.
  • a known or well-known method can be adopted as the coating method. For example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, blade coating method, air knife coating method Etc. can be adopted.
  • the base materials used in this case are silicon, indium tin oxide (ITO), indium zinc oxide (IZO), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene (PE), ionomer (IO), polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polycycloolefin (PCO), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), polypropylene (PP), polycarbonate (PC), polystyrene (PS) , Polyacrylonitrile (PAN), ethylene vinyl acetate copolymer (EVA), ethylene vinyl alcohol copolymer (EVOH), ethylene methacrylic acid copolymer (EMMA), polymethacrylic acid (PMMA), nylon, plastic, glass, stone Include a substrate made of ceramics or the like.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • PET polyethylene terephthalate
  • TAC tri
  • the baking equipment is not particularly limited, and may be fired in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like, using a hot plate, an oven, or a furnace, for example. Thereby, it is possible to obtain a film having a uniform film forming surface.
  • the firing temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 to 200 ° C., for example. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.
  • the firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions in which the physical properties of the polysiloxane film are adapted to the required characteristics of the electronic device can be selected.
  • the film-forming composition containing the silicon compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention, the inorganic particles (B) and the solvent (C) has a uniform varnish formed by hybridizing these components. A dispersion is preferred.
  • hybridization means mixing solutes having different properties and mixing them in a solution state. Even if different solutes have chemical or physical interaction, they are present. The dispersibility may be maintained as long as it is not necessary.
  • Hybridization is not particularly limited as long as the final varnish stability can be obtained.
  • a silicon compound (A) containing a hydrolysis condensate (polysiloxane) is mixed with a dispersion of silica particles (silica sol) in a solution state (varnish), and (2) a hydrolysis condensate (polysiloxane).
  • Various methods such as dispersion of silica fine particles in a solution (in varnish) of the silicon compound (A) containing a hydrolytic condensate (polysiloxane) from the viewpoint of handling properties are included.
  • a method in which A) is mixed with a dispersion of inorganic particles (silica sol) in a solution (varnish) state is preferable.
  • the stability of the final hybridized varnish is due to precipitation due to reduced dispersibility, drastic changes in primary particle size or secondary particle size, poor applicability, coloring (whitening, yellowing), and poor film quality. Don't cause it.
  • the content of the silica particles in the composition may be in a range that does not impair the dispersibility of the final varnish obtained, and is controlled according to the intended refractive index, transmittance, and heat resistance of the coating film to be produced. It is possible.
  • the storage conditions are not particularly limited as long as they do not cause precipitation, a significant change in the primary particle size or the secondary particle size, deterioration in applicability, coloring (whitening, yellowing), and film quality.
  • it may be stored at 23 ° C. (room temperature storage), 5 ° C. (refrigerated storage) and ⁇ 20 ° C. (frozen storage).
  • ⁇ 20 ° C. freezer storage
  • the film obtained from the film-forming composition (coating solution) of the present invention has a pencil hardness of H or higher as defined by JIS standard K 5600.
  • Pencil hardness is as high as 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, 6B or less. It is written.
  • Pencil hardness is one of the required performances required for a coating when a device is manufactured. If the device is easily scratched by external scratches, a device defect is generated. Therefore, a film hardness of H or higher is required. There are many cases.
  • the film-forming composition is coated on a substrate and baked.
  • the refractive index of 1.15 to 1.30, or 1.20 to 1.30 at a wavelength of 633 nm, and JIS standard K5600
  • the film has a pencil hardness of H to 9H, H to 5H, or H to 3H.
  • the film made of the composition of the present invention thus obtained can satisfy a low refractive index, high transparency, high heat resistance, high light resistance, and high hardness at the same time.
  • Cathode ray tubes organic light emitting displays, electronic paper, optical semiconductors (LEDs), solid-state imaging devices, solar cells, organic thin film transistors, and other electronic devices.
  • an antireflective substrate and antireflective film for televisions, digital signage, mobile phones, personal digital assistants, notebook computers and the like.
  • Average particle diameter (nm) 2720 / specific surface area (m 2 / g) [Refractive index of particles]
  • Apparatus Abago refractometer organic solvent manufactured by Atago Co., Ltd.
  • Organic solvent Solvent 1 (having a lower refractive index than particles), solvent 2 (having a higher refractive index than particles) Solvents 1 and 2 are selected so that they can be mixed with each other.
  • Measurement method After the inorganic particles were dried at 150 ° C., the powder pulverized in a mortar was immersed in the solvent 1, and then the solvent 2 was added little by little until the fine particles became almost transparent. The refractive index of this liquid was measured using an Abbe refractometer. The measurement was performed at 23 ° C.
  • the solvent 1 and the solvent 2 are solvents such as 1,1,1,3,3,3-hexafluoro-2-propanol, 2-propanol, chloroform, carbon tetrachloride, toluene, glycerin and the like. Can be mentioned.
  • reaction solution is cooled to room temperature, 70.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution, and ethanol, water, hydrochloric acid and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to hydrolyzed condensate.
  • PGMEA propylene glycol monomethyl ether acetate
  • the obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P1).
  • the weight average molecular weight of the obtained P1 by GPC was Mw2800 in terms of polystyrene.
  • PGMEA was added so that the PGMEA varnish of P1 was 6 mass percent in terms of solid residue at 140 ° C., and 1 H-NMR was measured. The result is shown in FIG.
  • the reaction solution is cooled to room temperature, 70.00 g of PGMEA is added to the reaction solution, ethanol as a solvent, ethanol, water and hydrochloric acid as reaction by-products are distilled off under reduced pressure, and concentrated to a hydrolysis-condensation product ( Polymer) PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC.
  • the obtained polymer is a varnish of a silicon compound (A) containing a hydrolysis condensate (polysiloxane) and a varnish of a partially hydrolyzed polysiloxane (abbreviated as P2).
  • the weight average molecular weight of the obtained P2 by GPC was Mw 4000 in terms of polystyrene.
  • the PGMEA varnish of P2 was added with PGMEA so that the solid residue at 140 ° C. was 6 mass percent, and 1 H-NMR was measured. The result is shown in FIG.
  • reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO 2 .Al 2 O 3 primary particle dispersion with a solid content concentration of 20% by mass.
  • the pH of this reaction solution was 12.9. 170 g of pure water was added to 50 g of this primary particle dispersion and heated to 98 ° C., and while maintaining this temperature, 5,040 g of sodium sulfate having a concentration of 0.5% by mass was added, and then the SiO 2 concentration was 1.
  • a dispersion of complex oxide fine particles was obtained by adding 300 g of a 17% by weight aqueous sodium silicate solution and 900 g of a 0.5% by weight aqueous sodium aluminate solution as Al 2 O 3 . Next, 311 g of pure water was added to 138 g of the dispersion of composite oxide fine particles that had been washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (concentration 35.5% by mass) was added dropwise to adjust the pH to 1. 0.0, and dealumination was performed.
  • the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 2.76 L of a hydrochloric acid aqueous solution of pH 3 and 1.38 L of pure water to obtain an aqueous dispersion of silica-based fine particles having a solid content concentration of 20% by mass.
  • a mixture of 45 g of this aqueous dispersion, 15 g of pure water, 52.5 g of ethanol, and 18.8 g of 28% aqueous ammonia was heated to 35 ° C., and then 3.1 g of ethyl silicate (SiO 2 concentration 28 mass%) was added. Addition to form a silica coating.
  • the dispersion medium is replaced with water using an ultrafiltration membrane, and the mixture is aged at 200 ° C.
  • silica sol (S4) had an average particle diameter of 46 nm and a refractive index of 1.28.
  • the obtained V1 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the film was measured for the refractive index of light having a wavelength of 633 nm using an ellipsometer, and the pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • Example 2 In a 20 mL eggplant-shaped flask, 14.0000 g of S1 obtained in Synthesis Example 3 was weighed, and then 3.91979 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added, and 0.7750 g of Synthesis Example 1 obtained.
  • P1 the solid content of polysiloxane is 5 parts by mass with respect to the solid content of S1
  • BYK-307 manufactured by BYK Japan Japan Co., Ltd. is diluted with PGMEA as a surfactant to 0.1% by mass.
  • 0.2170 g of the prepared solution was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V2) having a total solid content of 12.0% by mass.
  • the obtained V2 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • Example 1 A varnish (RV1) was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P2. RV1 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 2 A varnish (RV2) was obtained in the same manner as in Example 2 except that P1 in Example 2 was replaced with P2. RV2 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 3 A varnish (V3) was obtained in the same manner as in Example 1 except that S1 in Example 1 was replaced with S2 obtained in Synthesis Example 4. V3 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 4 A varnish (V4) was obtained in the same manner as in Example 2 except that S1 in Example 2 was replaced with S2 obtained in Synthesis Example 4. V4 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 5 A varnish (V5) was obtained in the same manner as in Example 1 except that S1 in Example 1 was replaced with S3 obtained in Synthesis Example 5. V5 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 6 A varnish (V6) was obtained in the same manner as in Example 2 except that S1 in Example 2 was replaced with S3 obtained in Synthesis Example 5. V6 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 7 In a 20 mL eggplant-shaped flask, 7.0000 g of S1 obtained in Synthesis Example 3 was weighed, 7.0000 g of S2 obtained in Synthesis Example 4 was added, and then 4.1256 g of propylene glycol monomethyl ether acetate (PGMEA and Abbreviation), and 1.5500 g of P1 obtained in Synthesis Example 1 (the solid content of polysiloxane is 10 parts by mass with respect to the total solid content of S1 and S2), and as a surfactant, Big Chemie Japan ( 0.2Kg of BYK-307 manufactured by Co., Ltd. diluted with PGMEA to 0.1 mass% was added, mixed at room temperature until completely uniform, and varnish with a total solid content of 12.0 mass% (Abbreviated as V7).
  • PGMEA and Abbreviation propylene glycol monomethyl ether acetate
  • the obtained V7 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • Example 8 A varnish (V8) was obtained in the same manner as in Example 7 except that S1 in Example 7 was replaced with S3 obtained in Synthesis Example 5. V8 was spin-coated and baked on a silicon substrate in the same manner as in Example 7, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • Example 9 A varnish (V9) was obtained in the same manner as in Example 7 except that S2 in Example 7 was replaced with S3 obtained in Synthesis Example 5. V9 was spin-coated and fired on a silicon substrate in the same manner as in Example 7, and the refractive index or pencil hardness was measured. The results are shown in Table 2.
  • the obtained RV3 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • the obtained RV6 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the obtained coating film had cracks, and a uniform film forming surface could not be obtained.
  • the film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • Example 10 In a 20 mL eggplant-shaped flask, weighed 5.4540 g of S-4 obtained in Synthesis Example 6, then added 3.6777 g of 2-propanol, and added 0.7791 g of P1 (S4 solids obtained in Synthesis Example 1). 10 parts by mass of the polysiloxane solid content) was added, and BYK-307 manufactured by Big Chemie Japan Co., Ltd. as a surfactant was diluted with PGMEA to obtain 0.1091 g of a solution of 0.1091 g. In addition, it was mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as V10) having a total solid content of 12.0% by mass.
  • V10 a varnish
  • the obtained V10 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film.
  • the film was measured for the refractive index of light having a wavelength of 633 nm using an ellipsometer, and the pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.
  • the film of V1 to V2, the film of V3 to V4, and the film of V5 to V6 are compared. Although each film had a different particle shape, there was no difference in film hardness in pencil hardness, and when polysiloxane was added at 5 phr, it was H when 10 phr was added. It was found that the difference in the shape of the inorganic particles contributes to the refractive index, and the refractive index decreases as the particle diameter B / particle diameter A becomes 1.1 or more and the shape of the silica particles becomes curved and deformed. As a result, it is considered that the ratio of the air layer having a refractive index of 1.0 is mixed into the film and the refractive index is lowered as the particle shape is curved and becomes irregular.
  • the films of V7, V8 to V9 are compared. These are examples of adjusting the composition using two types of silica particles. Even when two types of silica particles were used, a pencil hardness of H or higher was achieved by combining with completely hydrolyzed polysiloxane, and the refractive index at a wavelength of 633 nm was 1.3 or lower. It was found that the refractive index of the film in the case of using different types of silica particles tends to be driven by the refractive index of the silica particles exhibiting a lower refractive index. RV3, RV4 to RV5 are comparative examples in which the silica particles are formed alone.
  • RV6 to RV7 are comparative examples formed by polysiloxane alone. Although the polysiloxane single film exhibited a very high pencil hardness, the refractive index at a wavelength of 633 nm was 1.4 or more, and a refractive index of 1.3 or less at a target wavelength of 633 nm could not be achieved.
  • the refractive index at a wavelength of 633 nm is 1.30 or less, and the hardness by pencil hardness is H or more.
  • Example 11 V1 obtained in Example 1 was spin-coated on a silicon substrate and quartz using a spin coater so that the film thickness was 500 nm, and (A) temporarily dried at 100 ° C. for 1 minute using a hot plate. Next, firing at 200 ° C. for 5 minutes, (B) Temporary drying at 100 ° C. for 1 minute, then firing at 250 ° C. for 5 minutes, (C) Temporary drying at 100 ° C. for 1 minute, then 300 ° C. for 5 minutes Each was fired to obtain a coating.
  • the film was measured for film thickness and refractive index at a wavelength of 633 nm using an ellipsometer, pencil hardness was measured using an electric pencil scratch hardness tester, and transmittance was measured using an ultraviolet-visible spectrophotometer. The results are shown in Table 3 and FIGS. 3 to 5. .
  • the refractive index and pencil hardness were measured on a film on a silicon substrate, and the transmittance was measured on a quartz substrate.
  • the background at the time of measuring the transmittance was a quartz substrate not coated with a film.
  • the transmittance measurement wavelength was 200 to 800 nm.
  • Example 12 The refractive index, pencil hardness, and transmittance were measured in the same manner as in Example 11 except that V1 used in Example 11 was replaced with V2. The results are shown in Table 4 and FIGS. [Table 4] From the results shown in Tables 3 to 4 and FIGS. 3 to 8, it was found that each film was good without being affected by the baking temperature, with no change in film thickness, refractive index, pencil hardness, and transmittance until high temperature baking at 300 ° C. .
  • the low refractive index film has a very wide process margin because it is required that the physical property value does not change significantly depending on the baking process to be produced.
  • Solvent resistance is a characteristic that is required when a post-process for patterning is performed by recoating a resist or the like on the film. If there is no solvent resistance, the film dissolves in the resist solvent when recoating, and the film And the resist may be mixed and the original characteristics may not be exhibited.
  • Example 13 In Example 1, the solvent resistance test of the V1 film produced on the silicon substrate was performed. The film thickness after firing was 500.1 nm, which was taken as the initial film thickness. Each coating was completely immersed in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, acetone, and ethyl lactate and allowed to stand for 5 minutes. Next, after drying with air, baking was performed on a hot plate at 200 ° C. for 1 minute to completely evaporate the residual solvent, and then the film thickness was measured and compared with the initial film thickness.
  • Example 14 In Example 2, a solvent resistance test was conducted in the same manner as in Example 12 except that the V2 film produced on the silicon substrate was used. The film thickness after firing was 500.5 nm, which was taken as the initial film thickness. When the initial film thickness is 100%, propylene glycol monomethyl ether is 100.0%, propylene glycol monomethyl ether acetate is 100.0%, cyclohexanone is 100.0%, acetone is 100.0%, and ethyl lactate is 100.%. It was found that the solvent resistance was good against various organic solvents.
  • Example 13 From the results of Example 13 to Example 14, it was found that the fired film exhibited solvent resistance, and it was found that the film had sufficient recoating performance.
  • ⁇ Light resistance test> In the light resistance test, light irradiation was performed at the Japan Weathering Test Center, and a xenon arc lamp having an illuminance of 180 W / m 2 and an exposure wavelength of 275 nm or more was used as a light source. SX75-AP type manufactured by Suga Test Instruments Co., Ltd. was used as the test machine.
  • Example 15 The light resistance test of the V1 film produced in Example 1 was conducted. The light irradiation time was 500 hours, and the film thickness, refractive index, pencil hardness, and transmittance before and after the light irradiation were measured. The results are shown in Table 5 and FIGS. [Table 5]
  • Example 16 The light resistance test of the V2 film produced in Example 2 was conducted. The light irradiation time was 500 hours, and the film thickness, refractive index, pencil hardness, and transmittance before and after the light irradiation were measured. The results are shown in Table 6 and FIGS. [Table 6] From the results of Tables 5 to 6 and FIGS. 9 to 12, it was found that the coating of the present invention has a very strong light resistance.
  • This light irradiation condition is a light irradiation condition generally used for the light resistance test of LCD, but no change was observed in film thickness, refractive index, pencil hardness, and transmittance.
  • Example 17 The constant temperature and humidity test of the V1 film prepared in Example 1 was performed. The film after the test was baked at 200 ° C. for 1 minute using a hot plate. The film thickness, refractive index, pencil hardness, and transmittance before and after the test were measured. The results are shown in Table 7 and FIGS. [Table 7]
  • Example 18 The constant temperature and humidity test of the V2 film prepared in Example 2 was performed. The film after the test was baked at 200 ° C. for 1 minute using a hot plate. The film thickness, refractive index, pencil hardness, and transmittance before and after the test were measured. The results are shown in Table 8 and FIGS. [Table 8] From the results of Tables 7 to 8 and FIGS. 13 to 16, the coating of the present invention maintains good transmittance even after the constant temperature and humidity test, and the refractive index at a wavelength of 633 nm is good without any significant change. I understood.
  • the obtained film has a refractive index of 1.15 to 1.30 at a wavelength of 633 nm, a pencil hardness of H or higher (for example, H to 9H, H to 5H, or H to 3H), and is heat resistant.
  • a low refractive index film having light resistance and high reliability can be obtained.
  • the film of the present invention has solvent resistance, there is no mixing when a resist or the like is recoated, and it can be stably incorporated into a device manufacturing process.
  • the storage stability is good, it leads to stable manufacturing and stable supply when manufacturing the target display device, thereby reducing costs and improving device manufacturing throughput, resulting in improved yield.
  • it can be suitably used as an electronic device such as a liquid crystal display, a plasma display, a cathode ray tube, an organic light emitting display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, and an organic thin film transistor.
  • an antireflective substrate and antireflective film for televisions, digital signage, mobile phones, personal digital assistants, notebook computers and the like.

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JP2015220087A (ja) * 2014-05-16 2015-12-07 東洋インキＳｃホールディングス株式会社 光散乱層用樹脂組成物、光散乱層、および有機エレクトロルミネッセンス装置
JP2016089024A (ja) * 2014-11-04 2016-05-23 日本タングステン株式会社 コーティング膜、その製造方法およびコーティング膜形成方法
JP2017132926A (ja) * 2016-01-28 2017-08-03 三菱マテリアル株式会社 被膜形成用組成物及びその製造方法、並びに被膜
CN110719942A (zh) * 2017-06-07 2020-01-21 默克专利有限公司 感光性硅氧烷组合物以及使用其而形成的固化膜
JPWO2020203430A1 (fr) * 2019-03-29 2020-10-08
CN112573526A (zh) * 2019-09-30 2021-03-30 日挥触媒化成株式会社 在外壳内侧具有空洞的粒子及其制造方法、含其的涂布液、及带含其的透明被膜的基材

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US10676643B2 (en) * 2016-03-31 2020-06-09 Nissan Chemical Industries, Ltd. Coating film-forming composition and process for producing the same
EP3323864A1 (fr) * 2016-11-22 2018-05-23 BASF Coatings GmbH Revêtement optique à faible indice de réfraction
CN113183481B (zh) * 2020-01-10 2022-10-28 中国科学院化学研究所 一种可重复使用的类玻璃或类玻璃制品及其制备方法与回收再利用方法
CN112251137B (zh) * 2020-10-14 2022-05-10 中国工程物理研究院激光聚变研究中心 晶体涂膜元件及其制备方法、晶体膜系

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CN112573526A (zh) * 2019-09-30 2021-03-30 日挥触媒化成株式会社 在外壳内侧具有空洞的粒子及其制造方法、含其的涂布液、及带含其的透明被膜的基材
CN112573526B (zh) * 2019-09-30 2024-03-29 日挥触媒化成株式会社 在外壳内侧具有空洞的粒子及其制造方法、含其的涂布液、及带含其的透明被膜的基材

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