Classifications

• • 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
  • 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
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/32—Alkali metal silicates
  • C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
• • 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
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • 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
  • 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
  • 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
• • 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
  • C09D7/66—Additives characterised by particle size
  • C09D7/67—Particle size smaller than 100 nm
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/02—Polysilicates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

• the present invention relates to a composition, a film, a laminate, and an optical member.
• Porous silicon oxide films have characteristics such as low refractive index, transparency, and electrical insulation, and are widely used in industry.
• application fields that utilize low refractive index include electronic device displays, automobile panels, lighting fixtures, solar utilization devices, camera lenses, face shields, anti-reflection coatings for eyeglasses, optical waveguides, and optical fiber cladding layers. is being considered.
• Patent Document 1 discloses a method for producing a binder liquid for forming a silicon oxide thin film that has excellent adhesion to a substrate and is suitable for forming a porous silicon oxide thin film. Furthermore, a method for producing a coating liquid for forming a silicon oxide thin film has been proposed, which involves mixing a binder liquid for forming a silicon oxide thin film, which is made of a reaction product of a hydrolysis and condensation reaction of a hydrolyzable silane compound, with silica fine particles. There is. Further, Patent Document 2 proposes a porous silicon oxide film with excellent antifogging properties.
• porous silicon oxide films described in Patent Documents 1 and 2 have a risk of cracking or peeling when the porous silicon oxide film is laminated with a substrate and subjected to dicing processing.
• the present invention has been made in view of the above problems, and provides a composition, a film obtained thereby, and a laminate that can obtain a film that is highly flexible and suppresses cracking and peeling during dicing processing. and an optical member.
• the present inventors found that the flexibility of the film of a composition containing chain silica fine particles, an alkoxysilane hydrolysis condensate, and a hydrophilic resin is high;
• the present invention was completed by discovering that cracking and peeling during dicing can be suppressed.
• the gist of the present invention is as follows.
• a composition containing chain silica fine particles, an alkoxysilane hydrolyzed condensate, and a hydrophilic resin [2] The composition according to [1] above, wherein the hydrophilic resin has a hydroxyl group. [3] The composition according to [1] or [2] above, wherein the content of hydroxyl groups directly bonded to the main chain of the hydrophilic resin is 35 mol% or less. [4] Any of [1] to [3] above, wherein the content of the hydrophilic resin exceeds 1 part by mass based on a total of 100 parts by mass of the chain silica fine particles and the alkoxysilane hydrolysis condensate.
• the content of the alkoxysilane hydrolyzed condensate is 5 to 30% by mass based on the total of 100% by mass of the chain silica fine particles, the alkoxysilane hydrolyzed condensate, and the hydrophilic resin.
• the content of the chain silica fine particles is 60 to 90% by mass with respect to a total of 100 mass% of the chain silica fine particles, the alkoxysilane hydrolysis condensate, and the hydrophilic resin. 1] to [5].
• the linear silica fine particles have an average primary particle diameter of 5 to 100 nm.
• the hydrophilic resin has an average degree of polymerization of 200 to 2,000.
• a film comprising the composition according to any one of [1] to [9] above.
• composition of the present invention as described above, a structure containing chain silica fine particles, an alkoxysilane hydrolysis condensate, and a hydrophilic resin is adopted. This makes it possible to provide a film or a laminate that has high flexibility and can suppress cracking or peeling during dicing.
• compositions, films, and laminate according to the present invention will be described in detail by citing their embodiments, but the present invention is not limited by the following explanation, and the present invention is not limited to the following explanations, and the compositions, films, and laminates according to the present invention are not limited to the following examples. However, it is also possible to modify and implement the invention as appropriate without departing from the spirit of the invention.
• ⁇ is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
• composition contains chain silica fine particles, an alkoxysilane hydrolysis condensate, and a hydrophilic resin.
• a film that is a molded object can be produced. Furthermore, a laminate can be obtained by laminating the film on a substrate. For example, this improves the flexibility of the film and prevents cracking or peeling when dicing the laminate to the product size, thereby improving adhesion and flexibility with the base material. A material having an excellent refractive index and an excellent refractive index for optical applications can be obtained.
• composition of the present invention there is no particular limitation on the form of the composition of the present invention, and it may be liquid or solid, but the following two are typical examples.
• Coating liquid containing chain silica fine particles, hydrophilic resin, alkoxysilane hydrolyzed condensate, and solvent (II) Film containing chain silica fine particles, hydrophilic resin, and alkoxysilane hydrolyzed condensate
• Linear silica particles are particles in which a plurality of primary particles are directly bonded through chemical bonds such as siloxane bonds without intervening joints made of other materials, resulting in continuous chain-like particles. It may be a linearly extending shape or a two-dimensionally or three-dimensionally curved shape. Further, it is preferable that the linear silica fine particles are continuous particles having an average primary particle diameter of about 5 to 30 nm, for example, and an average length of about 30 to 200 nm.
• the shape of the chain silica fine particles can be observed using an electron microscope (SEM etc.).
• the average length can be measured by dynamic light scattering.
• chain silica fine particles have large interparticle voids in the deposited state, the refractive index of the film can be lowered.
• silica particles other than chain silica fine particles for example, spherical silica particles
• the content ratio of matrix structures other than spherical silica particles becomes small, the haze increases and the appearance deteriorates significantly.
• chain silica fine particles it is possible to achieve both a low refractive index and an excellent appearance.
• the average primary particle diameter of the chain silica fine particles is preferably 6 nm or more, more preferably 7 nm or more. By setting the average primary particle diameter of the chain silica fine particles to 6 nm or more, the refractive index of the film can be reduced. On the other hand, the average primary particle diameter of the chain silica fine particles is preferably 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less. By setting the average primary particle diameter of the chain silica fine particles to 100 nm or less, a film with a desired thickness can be easily formed, and the roughness of the film surface, light scattering, and haze can be reduced. I can do it.
• chain silica fine particles include “Snowtex (registered trademark)-OUP” (average length: 40 to 100 nm) and “Snowtex (registered trademark)-UP” (average length: 40 to 100 nm) manufactured by Nissan Chemical Industries, Ltd.
• colloidal silica such as "Fine Cataloid F-120”. If necessary, it may be preferable to use a solvent substituted.
• Commercially available dispersion media include methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate, but these dispersion media can be used by changing to other components as appropriate depending on the application. can do.
• the content of the chain silica fine particles is the ratio of the chain silica fine particles, the alkoxysilane hydrolyzed condensate, and the hydrophilic resin to 100% by mass ("mass of the chain silica fine particles"/"mass of the chain silica fine particles +
• the mass of the alkoxysilane hydrolyzed condensate + the mass of the hydrophilic resin is preferably 60 to 90% by mass.
• the content of chain silica fine particles is 60% by mass or more, the porosity within the film increases, so that the refractive index can be lowered. It is more preferably 65% by mass or more, particularly preferably 70% by mass or more.
• the content is 90% by mass or less, the adhesion to the base material and the mechanical strength of the film are further improved. It is more preferably 85% by mass or less, particularly preferably 80% by mass or less.
• the alkoxysilane hydrolyzed condensate contained in the composition of the present invention is a compound having a siloxane bond, and is a hydrolyzed condensed compound of alkoxysilane.
• the method for producing the alkoxysilane hydrolysis condensate is not particularly limited, but it consists of a hydrolyzable silane compound and a multimer of the hydrolyzable silane compound, and is usually produced using water and an organic solvent.
• a composition produced from this hydrolyzable silane compound or a polymer of the hydrolyzable silane compound, water, and an organic solvent is called a silicate oligomer.
• the alkoxysilane hydrolysis condensate of the present invention preferably has a weight average molecular weight of 1,000 to 5,000. If the weight average molecular weight of the alkoxy hydrolyzed condensate is 1,000 or more, the silicate oligomer containing the alkoxy hydrolyzed condensate will be difficult to gel, resulting in good storage stability. More preferably 1,500 or more, particularly preferably 2,000 or more. Moreover, if it is 5,000 or less, the adhesion with the substrate will be better, and cracking and peeling during dicing will be suppressed. It is more preferably 4,000 or less, particularly preferably 3,000 or less. Such a weight average molecular weight corresponds to a polymer having an average degree of polymerization n of 2 to 100.
• the above weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Solvent Tetrahydrofuran Equipment name: TOSOH HLC-8220GPC
• the concentration of the alkoxy hydrolysis condensate in the silicate oligomer is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 8% by mass or less.
• the concentration of the alkoxy hydrolysis condensate in the silicate oligomer is preferably 0.1% by mass or more, more preferably 0.2% by mass or more.
• Such silicate oligomers are transparent and have a turbidity of usually 10 or less when measured using a kaolin turbidity meter.
• the organic solvent contained in the silicate oligomer is preferably a hydrophilic solvent.
• Hydrophilic solvents are not particularly limited, but generally include alcohols such as methanol, ethanol, propanol, and butanol, cellosolves such as ethyl cellosolve, butyl cellosolve, and propyl cellosolve, ethylene glycol, propylene glycol, and hexylene glycol. Glycols such as are used. These solvents may be used alone or in combination of two or more.
• the content of organic solvent in the silicate oligomer is not particularly limited, but is usually 40% by mass to 99% by mass.
• the hydrolyzable silane compound is a silane compound having a hydrolyzable group such as an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, an amide group, a ketoxime group, an isocyanate group, or a halogen atom.
• a hydrolyzable group such as an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, an amide group, a ketoxime group, an isocyanate group, or a halogen atom.
• hydrolyzable silane compounds mono- to tetrafunctional ones are known, depending on the number of hydrolyzable groups.
• an alkoxysilane compound is preferably used as the hydrolyzable silane compound.
• the alkyl group of the alkoxy group (-OR) include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
• alkoxysilane compounds include dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), tetramethoxysilane (TMOS), dimethyldiethoxysilane (DMDES), methyltriethoxysilane (MTES), and tetraethoxysilane. (TEOS), etc.
• DDMS dimethyldimethoxysilane
• MTMS methyltrimethoxysilane
• TMOS tetramethoxysilane
• DMDES dimethyldiethoxysilane
• MTES methyltriethoxysilane
• TEOS tetraethoxysilane.
• DDMS dimethyldimethoxysilane
• MTMS methyltrimethoxysilane
• TMOS tetramethoxysilane
• DMDES dimethyldiethoxysilane
• MTES methyltriethoxysilane
• TEOS te
• the polymer of the hydrolyzable silane compound is obtained by polymerizing (oligomerizing) the above-mentioned monomers by condensation.
• a silanol group (-Si-OH) is formed by hydrolysis of an alkoxy group.
• alcohol R-OH
• a siloxane bond (-Si-O-Si-O-) is formed by (dehydration) condensation of the silanol groups, and this condensation is repeated to form a siloxane oligomer.
• the multimer of the alkoxysilane compound a multimer of tetramethoxysilane in which R is a methyl group or a multimer of tetraethoxysilane in which R is an ethyl group is preferable from the viewpoint of hydrolyzability and condensability of the alkoxy group. .
• Multimer structures include linear, branched, cyclic, and network structures, but if a tetraalkoxysilane multimer is shown as having a linear structure, it has the following general formula (I). expressed. RO(Si(OR) 2O ) nR ...(I)
• R is an alkyl group
• n represents the degree of multimerization of the multimer.
• Commonly available multimers are compositions of multimers with different n and therefore have a molecular weight distribution. Note that the degree of abundance is expressed by the average n.
• the degree of polymerization of a tetrafunctional hydrolyzable silane compound such as tetraalkoxysilane or its polymer is sometimes expressed as "silica content.”
• Silicacontent is the mass proportion of silica (SiO 2 ) produced from the compound, and is obtained by stably hydrolyzing the compound and measuring the amount of silica produced by firing.
• sica content also indicates the ratio of silica produced per molecule of the compound, and is a value calculated using the following general formula (II).
• Silica content (parts by mass) Polymerization degree x Molecular weight of SiO 2 / Molecular weight of the compound... (II)
• a multimer having a multimerization degree n of usually 2 to 100, preferably 2 to 70, more preferably 2 to 50 is used. It is convenient to use commercially available products for such multimers. As the polymerization degree n increases, the molecular weight of the alkoxysilane hydrolysis condensate produced increases, the molecular weight distribution becomes broader, and the viscosity becomes higher.
• hydrolyzable silane compounds include MKC Silicate MS51, MKC Silicate MS56, MKC Silicate MS57, and MKC Silicate MS56S (all tetramethoxysilane polymers) manufactured by Mitsubishi Chemical Corporation, and Methyl manufactured by Colcoat.
• examples include silicate 51 (a multimer of tetramethoxysilane), methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, and ethyl silicate 40 and silicate 45 (both are multimers of tetraethoxysilane) manufactured by Tama Chemical Industries.
• the alkoxysilane hydrolysis condensate of the present invention contains a bifunctional hydrolyzable silane compound and a polymer of the hydrolyzable silane compound, and the content of the polymer of the hydrolyzable silane compound is 50% by mass or more.
• the hydrolyzable silane composition is manufactured using a hydrolyzable silane composition.
• the proportion of the polymer in this hydrolyzable silane composition is preferably 70% by mass or more. If the proportion of the polymer in the hydrolyzable silane composition is 70% by mass or more, a branched, cyclic, or network structure is appropriately formed in the reaction composition, and the adhesion between the film and the substrate is further improved. do. More preferably, it is 75% by mass or more.
• the proportion of the polymer in the hydrolyzable silane composition is preferably 90% by mass or less. If the proportion of the polymer in the hydrolyzable silane composition is 90% by mass or less, it will be less likely to gel and will have higher storage stability. Further, the proportion of the bifunctional hydrolyzable silane compound as a monomer in the hydrolyzable silane composition is preferably 10% by mass or more and 30% by mass or less. If the proportion of the bifunctional hydrolyzable silane compound is 10% by mass or more, the resulting silicate oligomer containing the alkoxysilane hydrolyzed condensate will be less likely to gel, resulting in better storage stability. On the other hand, if it is 30% by mass or less, the coating properties during film formation are better. This proportion is more preferably 25% by mass or less.
• JP-A-2021-182134 the conditions described in JP-A-2021-182134 are preferred. This reaction is carried out by continuously dropping an aqueous acid catalyst solution into a hydrophilic solvent solution in which the above hydrolyzable silane composition is dissolved under stirring conditions.
• the content of the alkoxysilane hydrolyzed condensate is determined by the ratio ("mass of the alkoxysilane hydrolyzed condensate")/"mass of the chain silica fine particle" to the total of the chain silica fine particles, the alkoxysilane hydrolyzed condensate, and the hydrophilic resin. +mass of alkoxysilane hydrolysis condensate+mass of hydrophilic resin" is preferably 5 to 30% by mass.
• the content of the alkoxysilane hydrolysis condensate is more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass.
• the composition of the present invention contains a hydrophilic resin.
• the hydrophilic resin preferably used in the present invention is one having a solubility in water, methanol, and ethanol of 5% by mass or more. When the solubility is 5% by mass or more, the affinity with chain silica fine particles and alkoxysilane hydrolysis condensate becomes better, the haze of the film becomes low, and the appearance becomes better.
• the solubility is preferably 8% by mass or more, more preferably 10% by mass or more.
• Examples of hydrophilic resins include natural polymers, water-soluble resins, and resin emulsions. Specific hydrophilic resins used in the composition of the present invention include casein, soybean protein, starch, and gelatin as examples of natural polymers.
• water-soluble resins examples include polyvinyl alcohol resins (PVA), cellulose resins (methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose ( CMC), chitins, and starches.
• PVA polyvinyl alcohol resins
• cellulose resins methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose ( CMC), chitins, and starches.
• examples of the resin having an ether bond include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), and polyvinyl ether (PVE).
• PAAM polyacrylamide
• PVP polyvinylpyrrolidone
• resin emulsions include styrene-butadiene copolymer, conjugated diene polymer emulsion such as methyl methacrylate-butadiene copolymer, acrylic polymer emulsion, and vinyl polymer emulsion such as ethylene-vinyl acetate copolymer. , ester polymer emulsion, urethane polymer emulsion, olefin polymer emulsion, epoxy polymer emulsion, vinylidene chloride polymer emulsion, and the like.
• the hydrophilic resin of the present invention preferably has a hydroxyl group.
• affinity with chain silica fine particles and alkoxysilane hydrolyzed condensate becomes better, and the haze of the film is lowered, resulting in a better appearance.
• hydrophilic resins include polyvinyl alcohol resins, cellulose resins (methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, and starches. can give.
• the content of hydroxyl groups directly bonded to the main chain of the hydrophilic resin is 35 mol% or less.
• the content of the aforementioned hydroxyl groups is more preferably 32 mol% or less, more preferably 30.8 mol% or less, even more preferably 30 mol% or less. on the other hand.
• the content of hydroxyl groups is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 11.6 mol% or more, even more preferably 15 mol% or more, and 17.8 mol%. % is particularly preferred. When the content of hydroxyl groups is 5 mol % or more, the haze of the film is low and the appearance is more excellent.
• the content of hydroxyl groups can be measured, for example, by 1 H-NMR.
• the hydrophilic resin is a vinyl alcohol resin
• the content of vinyl alcohol structural units (hereinafter, equivalent to formula (1)) is calculated from the degree of saponification, and calculated as the ratio of hydroxyl groups to the vinyl alcohol structural units. You can also.
• the content of hydrophilic resin is 1 mass as a ratio to the total of silica particles and alkoxysilane hydrolyzed condensate ("mass of hydrophilic resin” / "mass of silica particles + mass of alkoxysilane hydrolyzed condensate") It is preferable that the amount exceeds 100%.
• the content of the hydrophilic resin is more preferably 1.5 parts by mass or more, further preferably 2.0 parts by mass or more, and particularly preferably 2.5 parts by mass or more.
• the upper limit thereof is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less. When the content of the hydrophilic resin is 30 parts by mass or less, the haze of the film is low and the appearance is more excellent.
• the content of the hydrophilic resin is the ratio ("mass of hydrophilic resin” / "mass of chain silica particles + alkoxysilane
• the mass of the hydrolyzed condensate + the mass of the hydrophilic resin is preferably 5 to 30% by mass.
• the content of the hydrophilic resin is 5% by mass or more, the flexibility and dicing properties of the film will be good. It is more preferably 8% by mass or more, and particularly preferably 10% by mass or more.
• the content is 30% by mass or less, the haze of the film will be low and the appearance will be better.
• the content is more preferably 25% by mass or less, particularly preferably 20% by mass or less.
• polyvinyl alcohol resin in the composition of the present invention, polyvinyl alcohol resin can be suitably used as the hydrophilic resin.
• the polyvinyl alcohol-based resin contained in the composition of the present invention is not particularly limited in its specific structure as long as it has a vinyl alcohol structural unit represented by the following formula (1), and is typically acetic acid. It can be obtained by saponifying a polycarboxylic acid vinyl ester obtained by polymerizing a carboxylic acid vinyl ester monomer such as vinyl, but is not limited thereto.
• polyvinyl alcohol resin examples include unmodified polyvinyl alcohol and modified polyvinyl alcohol resin.
• the modified polyvinyl alcohol resin may be a copolymerized modified polyvinyl alcohol resin synthesized by copolymerizing a monomer other than the vinyl ester monomer that provides the polyvinyl alcohol structural unit, or a copolymerized modified polyvinyl alcohol resin synthesized by copolymerizing a monomer other than the vinyl ester monomer that provides the polyvinyl alcohol structural unit, or It may also be a modified polyvinyl alcohol resin in which the main chain or side chain is modified with an appropriate compound after synthesis.
• copolymerizable monomers that can be used in the copolymerized modified polyvinyl alcohol resin
• examples of copolymerizable monomers (unsaturated monomers) that can be used in the copolymerized modified polyvinyl alcohol resin include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene, and ⁇ -octadecene; - Derivatives such as hydroxyl group-containing ⁇ -olefins such as buten-1-ol, 4-penten-1-ol, and 5-hexen-1-ol and their acylated products; acrylic acid, methacrylic acid, crotonic acid, maleic acid, Unsaturated acids or their salts such as maleic anhydride, itaconic acid, undecylenic acid; monoesters or dialkyl esters; amides such as diacetone acrylamide, acrylamide, methacrylamide;
• examples of the copolymerized modified polyvinyl alcohol resin include polyvinyl alcohol resins having a primary hydroxyl group in the side chain.
• Such polyvinyl alcohol-based resins include, for example, side-chain 1,2-diol-modified PVA-based resins obtained by copolymerizing 3,4-diacetoxy-1-butene, vinyl ethylene carbonate, glycerin monoallyl ether, etc.; - Hydroxymethylvinylidene diacetate such as diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane; etc. are copolymerized and saponified. Examples include polyvinyl alcohol resins having hydroxymethyl groups in their side chains.
• Post-modification methods for post-modified polyvinyl alcohol resin include acetoacetate esterification, acetalization, urethanization, etherification, grafting, phosphoric acid esterification, and oxyalkylene conversion of unmodified polyvinyl alcohol or the above-mentioned modified polyvinyl alcohol resin. Examples include methods of oxidation, transesterification, and the like. From the viewpoint of membrane flexibility, polyvinyl alcohol resin modified with caprolactone by transesterification is more preferable.
• the content of vinyl alcohol structural units contained in the polyvinyl alcohol resin is preferably 30 to 90 mol%.
• the content of the vinyl alcohol structural unit is 30 mol % or more, the flexibility and flexibility of the film are improved, and cracking and peeling during dicing are suppressed. It is more preferably 32 mol% or more, even more preferably 35 mol% or more, and particularly preferably more than 46 mol%.
• the content of vinyl alcohol structural units is 90 mol % or less, the dispersibility in organic solvents is good, thickening of the liquid is suppressed, and the appearance of the obtained film is better. It is more preferably 85 mol% or less, particularly preferably 80 mol% or less.
• the functional group contained in the polyvinyl alcohol resin is preferably an oxyalkylene group, an acetoacetyl group, a carboxyl group, or a sulfoxyl group, and it is more preferable to contain an oxyalkylene group from the viewpoint of flexibility of the membrane.
• the average degree of polymerization of the polyvinyl alcohol resin is not particularly limited, but is preferably 200 to 2,000. When the average degree of polymerization is 200 or more, the flexibility and flexibility of the membrane are further improved. On the other hand, when it is 2000 or less, the dispersibility in organic solvents is further improved.
• the content of the polyvinyl alcohol resin is preferably more than 1 part by mass based on a total of 100 parts by mass of the chain silica fine particles and the alkoxysilane hydrolysis condensate.
• the content of the polyvinyl alcohol resin is more preferably 1.5 parts by mass or more, further preferably 2.0 parts by mass or more, and particularly preferably 2.5 parts by mass or more.
• the upper limit thereof is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less.
• the content of the hydrophilic resin is 30 parts by mass or less, the haze of the film is low and the appearance is more excellent.
• the content of the polyvinyl alcohol resin is more preferably 5 parts by mass or more, further preferably 6 parts by mass or more, and particularly preferably 8 parts by mass or more.
• the content is large, the dispersibility in organic solvents is good, thickening of the liquid is suppressed, and the appearance of the obtained film is good.
• the first film of the present invention can be a film obtained using the composition of the present invention.
• the film obtained by coating the composition of the present invention is generally used as a film formed on a transparent substrate, especially when used for optical purposes.
• This membrane is a porous membrane with many pores.
• the surface of the film is preferably smooth, and the unevenness level difference is preferably 5 nm or less, more preferably 3 nm or less, and particularly preferably 2 nm or less.
• the second membrane of the present invention can be a membrane containing a hydrophilic resin and having a porosity of 10 to 80%.
• the second film has excellent dicing properties, low haze, and low refractive index, so it has high industrial utility value.
• the second membrane of the present invention can utilize the membranes related to the first membrane of the present invention, and the parts common to these will be described together as the membrane of the present invention.
• the refractive index of the film of the present invention is usually 1.15 or more and 1.40 or less, and is appropriately selected and used depending on the purpose.
• the refractive index is preferably 1.20 or more and 1.35 or less.
• the minimum reflectance can be made as close to 0% as possible by selecting the refractive index of the film depending on the refractive index of the substrate.
• the refractive index is preferably 1.25 or less, more preferably 1.20 or less, and particularly preferably 1.18 or less.
• a lower refractive index is preferable because it increases the proportion of light that is totally reflected at the interface between the transparent substrate and the film, but on the other hand, it increases the porosity of the film, which may reduce the mechanical strength of the film. be.
• the structure of the membrane of the present invention is not particularly limited, and the pores are usually tunnel-shaped or connected pores in which independent pores are connected, but there are no particular limitations on the detailed structure of the pores.
• the pore size and porosity can be adjusted, and by adjusting these, it can be applied to a variety of applications in addition to optical applications. I can do it.
• the pore size and porosity can be adjusted by the composition and coating method of the film-forming coating liquid, which will be described later.
• the pore size of the membrane of the present invention is not particularly limited, but the pore size is usually preferably 0.1 to 50 nm, more preferably 1 to 20 nm, and particularly preferably 2 to 10 nm. If the pore size is too large, it is not suitable for anti-reflection films formed with a thin film of about 100 nm, for example, and defects will occur on the surface of the formed film, and the surface will become uneven, causing problems such as light scattering, etc. haze may increase. There is also the problem that the mechanical strength of the film is low due to the large number of defects.
• the porosity of the membrane of the present invention is preferably 10 to 80%, more preferably 10 to 78%, more preferably 20 to 78%, even more preferably 30 to 78%, particularly preferably 30 to 70%.
• the porosity is 10% or more, flexibility and optical properties are better, while when it is 80% or less, mechanical strength, haze, and surface smoothness are better.
• the pore size of the membrane of the present invention is measured by analyzing images observed using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Further, the porosity of the film can be determined by a relational expression between the porosity and the refractive index based on the Lorentz-Lorentz equation.
• TEM transmission electron microscope
• SEM scanning electron microscope
• the thickness of the film of the present invention is preferably 50 to 20,000 nm.
• the thickness is more preferably 1,000 nm or more, even more preferably 2,000 nm or more, and particularly preferably 3,000 nm or more.
• the thickness is 50 nm or more, optical effects are exhibited and mechanical strength is also improved.
• the thickness is 20,000 nm or less, the structure of the film tends to be uniform. It is more preferably 19,000 nm or less, particularly preferably 17,000 nm or less.
• the thickness can be measured by the method described in Examples below.
• the haze of the film of the present invention is preferably 0 to 3.0%.
• the haze is more preferably 2.5% or less, further preferably 2.0% or less, even more preferably 1.8% or less, and particularly preferably 1.0% or less. If the haze is 3.0% or less, the optical properties will be better. Most preferably, the lower limit is 0%. Haze can be measured by the method described in Examples below.
• a coating liquid for forming a film (corresponding to the composition of the present invention, hereinafter also referred to as "coating liquid for film formation") on a substrate,
• the obtained wet film is heated and dried to harden it.
• the film-forming coating liquid is produced, for example, by adding chain silica fine particles and a hydrophilic resin to a silicate oligomer containing an alkoxysilane hydrolyzed condensate. Further, it may contain a solvent as appropriate.
• the film-forming coating liquid is produced by mixing a silicate oligomer containing an alkoxysilane hydrolyzed condensate, chain silica fine particles, and a hydrophilic resin.
• the film-forming coating liquid is adjusted to an appropriate concentration in consideration of the coating properties when applied to the substrate, the thickness and smoothness of the coating film, and the like.
• the concentration adjustment is carried out by adding the above-mentioned hydrophilic solvent, but this concentration adjustment can be carried out before or after mixing the chain silica fine particles.
• the concentration of chain silica fine particles in the film-forming coating liquid is preferably 30% by mass or less, more preferably 25% by mass or less, particularly preferably 20% by mass or less, and most preferably 17% by mass or less.
• the concentration of chain silica fine particles in the coating liquid for film formation is preferably 1% by mass or more, more preferably 5% by mass or more.
• the mixing ratio of the silicate oligomer containing the alkoxysilane hydrolyzed condensate and the chain silica fine particles is particularly limited as long as it does not block the pores of the film when forming a film using the resulting film-forming coating liquid. Not limited. If the proportion of the silicate oligomer is too high, it becomes difficult to form pores during film formation, making it difficult to form a porous film with excellent optical performance, which is the original objective. On the other hand, if there is too little silicate oligomer, the bond between chain silica fine particles will be weak, resulting in insufficient mechanical strength and poor adhesion to the substrate, which may cause damage or peeling depending on the post-process or usage environment. There is a fear.
• the mixing ratio of the chain silica fine particle and the alkoxysilane hydrolyzed condensate is: chain silica fine particle: alkoxysilane.
• the ratio of the hydrolyzed condensate is preferably 1:0.01 to 2 (mass ratio), particularly preferably 1:0.05 to 1 (mass ratio).
• the content of the hydrophilic resin in the film-forming coating liquid is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. When the content is 0.05% by mass or more, the flexibility and flexibility of the film are further improved. On the other hand, it is preferably 10% by mass or less, more preferably 5% by mass or less. When the content is 10% by mass or less, thickening of the liquid is suppressed, and the appearance of the obtained film becomes better.
• the solvent contained in the coating liquid for film formation is water and/or an organic solvent.
• the solvent preferably contains a hydrophilic solvent, and examples of the hydrophilic solvent include, but are not particularly limited to, alcohols such as methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, propyl cellosolve, and the like. Glycols such as cellosolves, ethylene glycol, propylene glycol, and hexylene glycol are used. These solvents may be used alone or in combination of two or more. These solvents may be derived from the dispersion liquid of each raw material, or may be mixed when preparing the film-forming coating liquid.
• a film made of the composition of the present invention can be laminated on a substrate to form a laminate.
• a transparent substrate such as glass or plastic is used as the substrate to be laminated with the film.
• the transparent substrate has high light transmittance at a certain specific wavelength, and is appropriately selected depending on the application using ultraviolet light, visible light, or infrared light.
• the specific wavelength is not limited to the visible light range, but in applications for lenses, displays, optical devices such as solar cells, solar power generation, building materials, and anti-reflection coatings for the interior and exterior of automobiles, light with wavelengths in the visible light range is used. It is preferable to have high permeability to. Usually, those having a total light transmittance of 60% or more are used.
• the thickness and shape of the substrate are not particularly limited, and as long as they do not affect the performance of the film, they may have scattering or haze, or may have fine irregularities on the surface of the substrate.
• plastics constituting the substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), polymethyl methacrylate (PMMA), and cycloolefin polymer (COP).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PC polycarbonate
• PI polyimide
• PMMA polymethyl methacrylate
• COP cycloolefin polymer
• the surface of the base material can be applied to either surface-modified or untreated surfaces.
• the preferred method for laminating the film on the substrate is a coating method, including dip coating, spin coating, die coating, spray coating, gravure coating, roll coating, curtain coating, screen printing, and inkjet coating. Coating methods such as printing methods can be mentioned.
• the wet film formed by applying the film-forming coating solution to the substrate is dried to remove the solvent, and the drying temperature is usually 50 to 80°C, and a hot air dryer is preferably used. . Drying time is usually 1 to 10 minutes, preferably 1 to 5 minutes.
• UV rays include near UV (wavelength 200 to 380 nm), far UV (wavelength 10 to 200 nm), and extreme UV (wavelength 1 to 10 nm), but far UV is usually effective. It is.
• the ultraviolet radiation source include a low-pressure mercury lamp, a high-pressure mercury lamp, an excimer ultraviolet (excimer UV) lamp, a halide lamp, and a laser.
• the irradiation time of ultraviolet rays is usually 1 second to 3 minutes.
• the curing treatment is performed at a temperature of 80° C. to 150° C., and a hot air dryer or the like is suitably used.
• the curing time is usually 1 minute to 60 minutes, preferably 1 minute to 30 minutes.
• the optical member of the present invention may include the laminate of the present invention.
• the laminate itself may be used as an optical member, or the laminate may be used as part of an optical member.
• Examples of the optical member of the present invention include a diffractive optical element (DOE), a cladding material such as an optical fiber, an optical waveguide, an optical display, an AR glass, a camera lens, a medical lens, a microlens, and LiDAR.
• DOE diffractive optical element
• cladding material such as an optical fiber, an optical waveguide, an optical display, an AR glass, a camera lens, a medical lens, a microlens, and LiDAR.
• the film of the present invention can be suitably used as an antireflection film and the like.
• the film of the present invention can be suitably used for displays, automobile panels, lighting fixtures, sunlight utilization devices, camera lenses, face shields, eyeglasses, optical waveguides, and the like.
• it can be suitably used for diffractive optical elements (DOE), cladding materials such as optical fibers, optical waveguides, optical displays, AR glasses, camera lenses, medical lenses, microlenses, LiDAR, etc.
• DOE diffractive optical elements
• cladding materials such as optical fibers, optical waveguides, optical displays, AR glasses, camera lenses, medical lenses, microlenses, LiDAR, etc.
• it can be suitably used as a member for improving the color tone and brightness of displays.
• Average primary particle diameter of silica particles The average primary particle diameter of the silica fine particles was calculated by the BET method.
• the refractive index and film thickness of the porous silicon oxide film laminate (1) were calculated from the reflectance spectrum obtained by "Interferometric film thickness measuring device F20" manufactured by Filmetrics.
• Film formability during thin film production was evaluated based on the following criteria. ⁇ : A uniform film with a thickness of 2.0 ⁇ m or more can be produced without any problem. ⁇ : A film with a thickness of 2.0 ⁇ m or more cannot be produced.
• the porous silicon oxide film laminate (2) was cut from the glass side at room temperature using a cutting machine equipped with a diamond cutting wheel ("Qcut150A" manufactured by QATM).
• the cut cross section was observed with FE-SEM (JSM-7900F, manufactured by JEOL Ltd.), and the surface of the cut film was observed with a laser microscope (VK-9700, manufactured by Keyence Corporation), and evaluated according to the following criteria.
• (Crack) No film cracking observed in cross section.
• ⁇ Film cracking was observed in cross-sectional observation.
• (Peeling evaluation method 1) ⁇ : No film peeling observed on surface observation.
• ⁇ Film peeling was observed in surface observation.
• the porous silicon oxide film laminate (3) was wound around a cylindrical metal rod with a diameter of 1 mm at room temperature with the coating surface facing up, and the condition of the test piece was observed and evaluated according to the following criteria. ⁇ : There are no cracks or peeling in the film. ⁇ : The film is cracked and the wrapped portion is peeled off.
• the ratio of the polymer of the hydrolyzable silane compound in the total of the bifunctional hydrolyzable silane compound and the polymer of the hydrolyzable silane compound is 80% by mass.
• Example 1 Oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100” manufactured by Mitsubishi Chemical Corporation, concentration 40% by mass, degree of saponification 39 to 46 mol%, By adding 3.75 parts by mass of polymerization degree 200 and stirring for 30 minutes, 103.75 parts by mass of the coating liquid (D) for forming a porous silicon oxide film of the present invention was produced and evaluated. The results are shown in Table 1.
• Example 2 Except that the amount of oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100" manufactured by Mitsubishi Chemical Corporation, concentration 40% by mass, degree of saponification 39 to 46 mol%, degree of polymerization 200) was 7.50 parts by mass. In the same manner as in Example 1, 107.50 parts by mass of a coating liquid (D) for forming a porous silicon oxide film was produced and evaluated. The results are shown in Table 1.
• Example 3 Instead of oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100” manufactured by Mitsubishi Chemical Company, concentration 40% by mass, degree of saponification 39-46 mol%, degree of polymerization 200), CL-modified PVOH (product manufactured by Mitsubishi Chemical Company "" Except for using 7.50 parts by mass of Gohsenol NM-11Q, saponification degree 99.1 mol%, polymerization degree 1200, 52 mol% modified with caprolactone in the presence of Lewis acid, diluted to 10 wt% with ethanol). In the same manner as in Example 1, 107.50 parts by mass of the coating liquid (D) for forming a porous silicon oxide film was produced and evaluated. The results are shown in Table 1.
• Example 4 Instead of oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100" manufactured by Mitsubishi Chemical Company, concentration 40% by mass, degree of saponification 39-46 mol%, degree of polymerization 200), CL-modified PVOH (product manufactured by Mitsubishi Chemical Company "" Gohsenol NM-11Q” (saponification degree 99.1 mol%, polymerization degree 1200) in the presence of Lewis acid, 52 mol% modified with caprolactone and diluted to 10 wt% with ethanol) was used. In the same manner as in Example 1, 115.00 parts by mass of a coating liquid (D) for forming a porous silicon oxide film was produced and evaluated. The results are shown in Table 1.
• Example 5 Instead of oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100" manufactured by Mitsubishi Chemical Co., Ltd., concentration 40% by mass, degree of saponification 46-53 mol%, degree of polymerization 200), A porous material was prepared in the same manner as in Example 1, except that 3.75 parts by mass of Gosenex LW-200 (concentration 40% by mass, degree of saponification 39-46mol%, degree of polymerization 200) manufactured by 103.75 parts by mass of a silicon oxide film-forming coating liquid (D) was produced and evaluated. The results are shown in Table 1.
• Example 6 Instead of oxyalkylene group-modified polyvinyl alcohol (product "Gosenex LW-100” manufactured by Mitsubishi Chemical Company, concentration 40% by mass, degree of saponification 46-53 mol%, degree of polymerization 200), use polyvinyl alcohol (product manufactured by Mitsubishi Chemical Company). A porous silicon oxide film was formed in the same manner as in Example 1, except that 4.50 parts by mass of "GOHSENOL NK-05R” (concentration 10% by mass, degree of saponification 71-75mol%, degree of polymerization 500) was used. 104.50 parts by mass of a coating liquid (D) was produced and evaluated. The results are shown in Table 1.
• Example 7 Same as Example 5 except that 7.50 parts by mass of polyvinyl alcohol (product "Gohsenol NK-05R” manufactured by Mitsubishi Chemical Corporation, concentration 10% by mass, degree of saponification 71 to 75 mol%, degree of polymerization 500) was used. 107.50 parts by mass of a coating liquid (D) for forming a porous silicon oxide film was produced by the method and evaluated. The results are shown in Table 1.
• Example 8 The same procedure as in Example 5 was used, except that 15.00 parts by mass of polyvinyl alcohol (product "Gohsenol NK-05R” manufactured by Mitsubishi Chemical Corporation, concentration 10% by mass, degree of saponification 71 to 75 mol%, degree of polymerization 500) was used. 115.00 parts by mass of a coating liquid (D) for forming a porous silicon oxide film was produced by the method and evaluated. The results are shown in Table 1.
• Example 1 the coating liquid for forming a porous silicon oxide film was prepared in the same manner as in Example 1, except that oxyalkylene group-modified polyvinyl alcohol was not added to the coating liquid for forming a porous silicon oxide film (C). was manufactured and evaluated. The results are shown in Table 1.
• Example 2 A coating solution for forming a porous silicon oxide film was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1. Note that Comparative Example 2 has problems with film formability and the like, and the values of refractive index and porosity could not be clearly specified, so it is not measured in Table 1.
• a coating liquid (E) for forming a porous silicon oxide film was produced in the same manner as in Example 3.
• a porous oxide film was prepared in the same manner as in Example 6, except that the obtained coating liquid for forming a porous silicon oxide film (E) was used instead of the coating liquid for forming a porous silicon oxide film (C).
• a coating solution for forming a silicon film was manufactured and evaluated. The results are shown in Table 1.
• porous silicon oxide film laminate (1) (for evaluation of refractive index and porosity)
• a 6-inch Si wafer (manufactured by Advance Materials Technology) was cut into 2 cm pieces, the coating solution for forming a porous silicon oxide film obtained above was dropped onto it, and a spin coater ("MS-A150" manufactured by Mikasa) was coated. ) at 3500 rpm for 30 seconds to prepare a thin film.
• the porous silicon oxide film with a thickness of 3.5 ⁇ m and the Si wafer were bonded by placing it in a low-temperature constant temperature blower (manufactured by Yamato Scientific Co., Ltd.) and drying it at 120°C for 10 minutes.
• a laminate (1) was obtained. Using the obtained porous silicon oxide laminate (1), the refractive index and porosity were measured. The obtained evaluation results are shown in Table 1.
• the porous silicon oxide film with a thickness of 4.5 ⁇ m and the acrylic sheet were bonded by placing it in a low-temperature constant temperature blower (manufactured by Yamato Scientific Co., Ltd.) and drying it at 70°C for 10 minutes.
• a laminate (3) was obtained.
• the flexibility was evaluated using the obtained porous silicon oxide laminate (3).
• the obtained evaluation results are shown in Table 1.
• the results of this example show that the films and laminates made of the compositions of the present invention described in Examples 1 to 8 have excellent flexibility and can suppress film cracking and peeling during dicing. Furthermore, the film had a low refractive index and haze, and had excellent optical properties.
• the film of Comparative Example 1 had insufficient flexibility because the composition did not contain a hydrophilic resin, and cracked and peeled during dicing.
• the film of Comparative Example 2 uses spherical silica particles instead of chain silica particles, does not contain a hydrophilic resin, and is inferior in film formability, flexibility, and dicing properties. Furthermore, the film had high haze and poor optical properties.
• Comparative Example 3 uses spherical silica particles instead of chain silica particles, and is inferior in film formability, flexibility, and dicing properties. Furthermore, the film had high haze and poor optical properties. Furthermore, the haze and refractive index of the film are high, and the optical properties are also poor. Furthermore, the porosity was low.
• Porous silicon oxide films and laminates made of the composition of the present invention have high flexibility and can suppress cracking and peeling during dicing. It can be suitably used for optical members such as optical waveguides, optical films, AR glasses, camera lenses, medical lenses, microlenses, and LiDAR. In particular, it can be effectively applied to applications that require miniaturization of parts and followability.

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