JP4953426B2 - Method for producing silica airgel membrane - Google Patents

Description

  The present invention relates to a method for producing a silica airgel film having nano-sized micropores, and more particularly to a method for producing a silica airgel film having a low refractive index and excellent toughness and water repellency and suitable for an antireflection film. .

Conventionally, the antireflection film has been formed by a physical vapor deposition method such as vacuum vapor deposition, sputtering, or ion plating. Since the single-layer antireflection film is designed to have a refractive index smaller than that of the substrate, a film forming material having a small refractive index is required for the antireflection film formed on the substrate having a small refractive index. Of those that can be formed by physical vapor deposition, the smallest refractive index is MgF ₂ having a refractive index of 1.38. It is said that an antireflection film for a lens made of glass having a refractive index of about 1.5 is ideally set to have a refractive index of 1.2 to 1.25. When the refractive index is in this range, the reflectance can be less than 1% in the visible light region, that is, in the wavelength range of 400 to 700 nm. On the other hand, the reflectance of the antireflection film made of MgF ₂ having a refractive index of 1.38 is less than 2%, but is not an ideal value.

  In recent years, liquid phase methods such as a sol-gel method and an SOG method have also been used for forming an antireflection film. The liquid phase method has an advantage that an antireflection film can be formed without requiring a large-scale apparatus such as a physical vapor deposition method and without exposing the substrate to a high temperature. However, the minimum refractive index of the antireflection film obtained by the liquid phase method is about 1.37, which is similar to that of the physical vapor deposition method, and the antireflection characteristics are not much different. Therefore, in any of the methods, in order to suppress the reflectance in the wavelength region of visible light to less than 1%, it is necessary to form a multilayer film by laminating a low refractive index material and a high refractive index material.

  Silica airgel is known as a material having a refractive index smaller than that of magnesium fluoride. When silica wet gel is prepared by hydrolysis reaction of alkoxysilane and dried with supercritical fluid such as carbon dioxide, water, organic solvent, etc., it has a density of 0.01 g / cc or less and has a refractive index of less than 1.1. Airgel can be produced. However, this production method has a problem that it requires a supercritical drying apparatus and is troublesome and expensive. Moreover, since the toughness of the obtained silica airgel is very small and brittle, there is a problem that it cannot be used.

US Pat. No. 5,948,482 (Patent Document 1) prepared (a) a sol containing SiO ₂ , (b) aged and gelled, (c) modified the surface with an organic group, (d) A method for producing a silica airgel film that forms a thin film by ultrasonic treatment is described. According to this production method, a silica airgel film having a porosity of 99% or more and showing a low refractive index can be obtained. However, the silica airgel film obtained by this production method has a problem that the mechanical strength is small and the scratch resistance is poor.

US Patent 5,948,482

  Accordingly, an object of the present invention is to provide a method for producing a silica airgel film having a low refractive index and excellent toughness and water repellency and suitable for an antireflection film.

As a result of diligent research in view of the above object, the present inventors reacted the silica wet gel with an organic modifier and then produced an organically modified silica-containing sol by ultrasonic treatment , After coating a substrate with a coating liquid containing an ultraviolet curable resin and a photopolymerization initiator, the ultraviolet curable resin (or the unsaturated group of the ultraviolet curable resin and the organically modified silica) is irradiated by ultraviolet irradiation. The inventors have found that a silica airgel film having excellent toughness and water repellency and having a low refractive index can be obtained by polymerization, and the present invention has been conceived.

That is, the method for producing a silica airgel film of the present invention is a method for producing a silica airgel film, wherein a wet gel is generated by hydrolysis polymerization of alkoxysilane and / or silsesquioxane, and the wet gel is converted into an organic modifier. The organic modified wet gel is produced by reacting with the organic modified silica, and the organic modified wet gel is sonicated at a frequency of 10 to 30 kHz, an output of 300 to 900 W, and a treatment time of 5 to 120 minutes. A sol is formed, and the coating liquid is prepared by mixing the organic-modified silica-containing sol, an ultraviolet curable resin composed of a fluororesin having a refractive index after curing of 1.5 or less, and a photopolymerization initiator. Applying to form an organically modified silica-containing sol layer, drying the organically modified silica-containing sol layer, volatilizing the dispersion medium, and irradiating with ultraviolet rays, the ultraviolet curable resin, and ultraviolet rays It is characterized in that an unsaturated group of a linear curable resin and organically modified silica is polymerized, and thus the cured resin is coated on the surface and the inner wall of the void, followed by baking to produce a silica airgel film having a refractive index of 1.2 to 1.3 .

  As the ultraviolet curable resin, it is preferable to use a resin that becomes a cured resin having a refractive index of 1.33 to 1.5 by a polymerization reaction. In order to obtain a dispersion containing the organically modified silica, a wet gel is formed by hydrolysis polymerization of alkoxysilane and / or silsesquioxane, the wet gel is reacted with an organic modifier, and dispersed by sonication. It is preferable to do so. The dispersion medium is preferably at least one selected from the group consisting of carboxylic acid esters, ketones and alcohols. The solvent for the wet gel is preferably an alcohol having 1 to 3 carbon atoms.

  As the alkoxysilane, monosilane having an unsaturated group and an alkoxyl group is preferably used. It is preferable to use a silane coupling agent as the organic modifier, and it is more preferable to use a silane coupling agent having an ultraviolet polymerizable unsaturated group. A monosilane having an unsaturated group and an alkoxyl group is used as the alkoxysilane, an oligomer is produced by polymerizing the monosilane using an acid catalyst, and the oligomer is polymerized using a base catalyst, whereby the wet gel is obtained. It is preferable to obtain. The layer is preferably baked at 50 to 150 ° C. after being irradiated with ultraviolet rays.

In the method of the present invention, a silica wet gel is reacted with an organic modifier and then subjected to ultrasonic treatment, and a coating solution containing an organic modified silica-containing sol , an ultraviolet curable resin, and a photopolymerization initiator is used as a base material. There is an advantage that a silica airgel film containing organically modified silica and a cured resin can be obtained simply by coating and irradiating with ultraviolet rays. Further, since the silica airgel film can be formed by a wet method without the need for firing at a high temperature, the silica airgel film can also be provided on a non-heat resistant substrate.

  The obtained silica airgel film has excellent toughness and water repellency because the surface and inner walls of the voids are coated with a resin cured by ultraviolet irradiation, and the nanometer-sized voids are not completely filled. It has the advantage of being a refractive index. In particular, a silica airgel film containing a binder having a refractive index of 1.365 to 1.385 and having a porosity of 30 to 53% has a low refractive index of 1.2 to 1.3. Thus, the silica airgel film having both the low refractive index, which is the feature of silica airgel, and the excellent toughness and water repellency due to the binder, is suitable for the antireflection film.

[1] Preparation of organically modified silica dispersion
(1) Formation of wet gel A silica gel forming compound and a catalyst are dissolved in a solvent, subjected to a hydrolysis polymerization reaction, and then aged to form a wet gel.

(a) Silica skeleton-forming compound
(a-1) Saturated alkoxysilane and silsesquioxane Silica sol and silica gel are produced by hydrolysis polymerization of alkoxysilane and / or silsesquioxane. The saturated alkoxysilane may be a monomer or an oligomer. The saturated alkoxysilane monomer preferably has 3 or more alkoxyl groups. By using a saturated alkoxysilane having three or more alkoxyl groups as a silica skeleton-forming raw material, an antireflection film having excellent uniformity can be obtained. Specific examples of the saturated alkoxysilane monomer include methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane is mentioned. As the saturated alkoxysilane oligomer, a polycondensation product of the above-mentioned monomers is preferable. Saturated alkoxysilane oligomers are obtained by hydrolysis polymerization of monomers.

Even when a saturated silsesquioxane is used as a raw material for forming a silica skeleton, an antireflection film having excellent uniformity can be obtained. Saturated silsesquioxane is a generic term for network-like polysiloxanes having a structural unit represented by the general formula RSiO _1.5 (where R represents an organic functional group). Examples of R include an alkyl group (which may be a straight chain or branched chain and having 1 to 6 carbon atoms), a phenyl group, and an alkoxy group (for example, a methoxy group, an ethoxy group, etc.). Silsesquioxane is known to have various structures such as a ladder type and a saddle type. Moreover, it has excellent weather resistance, transparency and hardness, and is suitable as a silica skeleton-forming raw material for silica airgel.

(a-2) Unsaturated alkoxysilane and silsesquioxane A monomer or oligomer of unsaturated alkoxysilane or silsesquioxane having an ultraviolet-polymerizable unsaturated group may be used as a silica skeleton-forming raw material. By using a material having an unsaturated group as a raw material for forming the silica skeleton, a silica airgel film having excellent toughness can be obtained even when the blending amount of the binder is small. The unsaturated alkoxysilane monomer has an organic group having at least one double bond or triple bond (hereinafter referred to as “unsaturated group”) and an alkoxyl group. The unsaturated group has 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms.

A preferred unsaturated alkoxysilane monomer is represented by the following general formula (1):
R ^a Si (OR ^b ) ₃ ... (1)
(Wherein R ^a represents an organic group having 2 to 10 carbon atoms having an unsaturated bond, and R ^b O represents an alkoxyl group having 1 to 4 carbon atoms).

The unsaturated group ^Ra is an organic group having at least one UV-polymerizable unsaturated bond, and may have a substituent such as a methyl group or an ethyl group. Vinyl group Examples of the unsaturated group R ^a, an allyl group, a methacryloxy group, an aminopropyl group, a glycidoxy group, and an alkenyl group and propargyl group. R ^b may be the same organic group as R ^a or a different organic group. Examples of the alkoxyl group R ^b O include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, and an s-butoxy group.

  Specific examples of unsaturated alkoxysilane monomers include trimethoxyvinylsilane, triethoxyvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, tributoxyvinylsilane, tripropoxyvinylsilane, allyltributoxysilane, allyltripropoxysilane, dimethoxydivinylsilane, diallyl Dimethoxysilane, diethoxydivinylsilane, diallyldiethoxysilane, trimethoxy (3-butenyl) silane, triethoxy (3-butenyl) silane, di (3-butenyl) dimethoxysilane and di (3-butenyl) diethoxysilane .

An oligomer of unsaturated alkoxysilane may be used as a raw material for forming a silica skeleton. The unsaturated alkoxysilane oligomer also has at least one unsaturated group and an alkoxyl group. The unsaturated alkoxysilane oligomer is represented by the following general formula (2)
Si _m O _m-1 R ^a _{2m + 2-x} OR ^b _x (2)
(However, R ^a has an unsaturated bond and represents an organic group having 2 to 10 carbon atoms, R ^b O represents an alkoxyl group having 1 to 4 carbon atoms, m represents an integer of 2 to 5, x Represents an integer of 4 to 7.) is preferred. Preferred examples of the unsaturated group R ^a and the alkoxyl group R ^b O are the same as those of the above alkoxysilane monomer.

  The condensation number m is preferably 2 or 3. An oligomer having a condensation number m of 5 or less can be easily obtained by polymerization of a monomer using an acid catalyst, as will be described later. The number x of alkoxyl groups is preferably 3-5. If it is less than 3, hydrolytic polycondensation of alkoxysilane does not occur sufficiently, so that three-dimensional crosslinking is difficult and it is difficult to form a wet gel. When the number x of alkoxyl groups is more than 5, the ratio of unsaturated groups is too small, and the mechanical strength is not improved sufficiently by the polymerization reaction. Specific examples of the alkoxysilane oligomer having an unsaturated group include disilane, trisilane, and tetrasilane obtained by condensation of the above unsaturated group alkoxysilane monomer.

(b) Solvent The solvent is preferably composed of water and alcohol. As the alcohol, methanol, ethanol, n-propyl alcohol, and isopropyl alcohol are preferable, and methanol is particularly preferable. The degree of activity of the hydrolysis polycondensation reaction depends on the molar ratio of water to the alkoxysilane or silsesquioxane monomer and / or oligomer (silica skeleton-forming compound). Accordingly, the molar ratio of water / alcohol does not directly affect the progress of the hydrolysis polycondensation reaction, but is preferably substantially 0.1 to 2. If the water / alcohol molar ratio is more than 2, the hydrolysis reaction proceeds too quickly. When the water / alcohol molar ratio is less than 0.1, the silica skeleton-forming compound is hardly hydrolyzed.

(c) Catalyst A catalyst for hydrolysis reaction is added to an aqueous solution of the silica skeleton-forming compound. The catalyst may be acidic or basic. For example, when an oligomer is obtained by condensing a silica skeleton-forming compound monomer in an aqueous solution containing an acidic catalyst and polymerized in a solution containing a basic catalyst, the hydrolysis reaction can proceed efficiently. . Examples of acidic catalysts include hydrochloric acid, nitric acid and acetic acid. Examples of basic catalysts include ammonia, amines, NaOH and KOH. Examples of preferred amines include alcohol amines and alkyl amines (for example, methylamine, dimethylamine, trimethylamine, n-butylamine, n-propylamine).

(d) Compounding ratio It is preferable to dissolve the silica skeleton-forming compound in a solvent so that the solvent / alkoxysilane molar ratio is 3 to 100. When the molar ratio is less than 3, the degree of polymerization of the alkoxysilane becomes too high, and when the molar ratio exceeds 100, the degree of polymerization of the alkoxysilane becomes too low. The catalyst / alkoxysilane molar ratio is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ , more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ . If the molar ratio is less than 1 × 10 ⁻⁷ , the alkoxysilane hydrolysis reaction does not occur sufficiently. Even if the molar ratio exceeds 1 × 10 ⁻¹ , the catalytic effect does not increase. The molar ratio of water / alkoxysilane is preferably 0.5-20, and more preferably 5-10.

(e) Aging The solution containing the silica skeleton-forming compound condensed by hydrolysis is aged by standing at 25 to 90 ° C. or slowly stirring for about 20 to 60 hours. Gelation proceeds by aging, and a wet gel containing silicon oxide is generated. In the present specification, the “wet gel containing silicon oxide” means a gel in a wet state containing particles made of silicon oxide and a solvent.

(2) Displacement of the dispersion medium The dispersion medium of the wet gel influences the surface tension that promotes or delays aging and / or the contact angle between the solid phase and the liquid phase, and the surface modification range in the organic modification process. It is also related to the evaporation rate of the dispersion medium in the coating process described later. The dispersion medium incorporated in the gel can be replaced with another dispersion medium by repeating the operation of pouring another dispersion medium, shaking and then decanting. Although the dispersion medium may be replaced before or after the organic modification reaction, it is preferably performed before the organic modification reaction from the viewpoint of reducing the number of steps.

  Examples of the substituted dispersion medium include ethanol, methanol, propanol, butanol, hexane, heptane, pentane, cyclohexane, toluene, acetonitrile, acetone, dioxane, methyl isobutyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethyl acetate. These dispersion media may be used alone or in combination.

  A preferred substituted dispersion medium is a ketone solvent. If the solvent is replaced with a ketone solvent by the ultrasonic treatment step described later, a highly dispersible organic-modified silica-containing sol can be obtained. Since the ketone solvent has an excellent affinity for silica (silicon oxide) and organically modified silica, the organically modified silica is well dispersed in the ketone solvent. A preferred ketone solvent has a boiling point of 60 ° C. or higher. Ketones having a boiling point of less than 60 ° C. are too volatile in the ultrasonic irradiation process described below. For example, when acetone is used as a dispersion medium, a large amount of acetone is volatilized during ultrasonic irradiation, so that it is difficult to adjust the concentration of the dispersion. In addition, there is also a problem that sufficient film formation time cannot be obtained because the film is volatilized too quickly in the film formation process. Furthermore, acetone is known to be harmful to the human body and is not preferable from the viewpoint of worker health.

  Particularly preferred ketone solvents are asymmetric ketones having different substituents on both sides of the carbonyl group. Since the asymmetric ketone has a large polarity, it has a particularly excellent affinity for silica and organically modified silica. In the dispersion, the organically modified silica preferably has a particle size of 200 nm or less. When the particle diameter of the organically modified silica is larger than 200 nm, it is difficult to form a silica airgel film having a substantially smooth surface.

  The substituent that the ketone has may be an alkyl group or an aryl group. Preferred alkyl groups are those having about 1 to 5 carbon atoms. Specific examples of the ketone solvent include methyl isobutyl ketone, ethyl isobutyl ketone, and methyl ethyl ketone.

(3) Organic modification
(a) Organic modifier An organic modifier solution is added to the wet gel to replace a hydrophilic group such as a hydroxyl group at the terminal of silicon oxide constituting the wet gel with a hydrophobic organic group. In order to allow the reaction with the organic modifier to proceed efficiently, it is preferable to add the organic modifier solution to a wet gel cut to about 5 to 30 mm square to increase the surface area.

(a-1) Saturated organic modifier A preferred saturated organic modifier is represented by the following formulas (3) to (8):
R ^c _p SiCl _q・ ・ ・ (3)
R ^c ₃ SiNHSiR ^c ₃ ... (4)
R ^c _p Si (OH) _q・ ・ ・ (5)
R ^c ₃ SiOSiR ^c ₃ ... (6)
R ^c _p Si (OR ^b ) _q・ ・ ・ (7)
R ^c _p Si (OCOCH ₃ ) _q・ ・ ・ (8)
(Wherein p represents an integer of 1 to 3, q represents an integer of 1 to 3 satisfying the condition of q = 4-p, R ^b O represents an alkoxyl group having 1 to 4 carbon atoms, and R ^c represents hydrogen. A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 carbon atoms), or a mixture thereof.

  Specific examples of saturated organic modifiers include triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, acetoxytrimethylsilane, acetoxysilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, Trimethylethoxysilane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide, 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, nonamethyl Trisilazane, hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethyl Examples include silanol and diphenylsilanediol.

(a-2) Unsaturated organic modifier When an unsaturated organic modifier is used, a silica airgel film having excellent toughness can be obtained even when the amount of the binder is small. Preferred examples of the unsaturated organic modifier include the following formulas (9) to (14):
R ^d _p SiCl _q ... (9)
R ^d ₃ SiNHSiR ^d ₃ ... (10)
R ^d _p Si (OH) _q・ ・ ・ (11)
R ^d ₃ SiOSiR ^d ₃ ... (12)
R ^d _p Si (OR ^d ) _q・ ・ ・ (13)
R ^d _p Si (OCOCH ₃ ) _q・ ・ ・ (14)
(However, p is an integer of 1 to 3, q represents an integer of 1 to 3 that satisfies the condition of q = 4-p, R ^d has an ultraviolet-polymerizable unsaturated bond, and has 2 to 10 carbon atoms. Represents an organic group. The unsaturated group R ^d may have a substituent such as a methyl group or an ethyl group. Vinyl group Examples of the unsaturated group R ^d, allyl group, methacryloxy group, an aminopropyl group, a glycidoxy group, and an alkenyl group and propargyl group. The unsaturated organic modifier may be one type or two or more types. A saturated organic modifier may be used in combination with the unsaturated organic modifier.

  The unsaturated organic modifier is preferably an unsaturated chlorosilane, more preferably an unsaturated monochlorosilane having three unsaturated groups. Specific examples of unsaturated organic modifiers include triallylchlorosilane, diallyldichlorosilane, triacetoxyallylsilane, diacetoxydiallylsilane, trichlorovinylsilane, dichlorodivinylsilane, triacetoxyvinylsilane, diacetoxydiallylsilane, trimethoxy (3-butenyl) Examples include silane, triethoxy (3-butenyl) silane, di (3-butenyl) dimethoxysilane, and di (3-butenyl) diethoxysilane.

(b) Organic modification reaction The organic modifier is preferably dissolved in a solvent such as hydrocarbons such as hexane, cyclohexane, pentane and heptane, ketones such as acetone, and aromatic compounds such as benzene and toluene. Although depending on the type and concentration of the organic modifier, the organic modification reaction is preferably allowed to proceed at 10 to 40 ° C. When it is less than 10 ° C., the organic modifier does not easily react with silicon oxide. If it exceeds 40 ° C., the organic modifier reacts easily with substances other than silicon oxide. During the reaction, it is preferable to stir the solution so that there is no distribution in the temperature and concentration of the solution. For example, when the organic modifier solution is a hexane solution of triethylchlorosilane, the silanol group is sufficiently silylated when held at 10 to 40 ° C. for about 20 to 40 hours (for example, 30 hours).

(4) Ultrasonic treatment The ultrasonic treatment can bring the gel-like and / or sol-form organic modified silica into a state suitable for coating. In the case of gel-like organically modified silica, it is considered that the gel aggregated by electrical force or van der Waals force is dissociated by ultrasonic treatment or the covalent bond between silicon and oxygen is broken, resulting in a dispersed state. It is done. Even in the case of a sol, aggregation of colloidal particles can be reduced by ultrasonic treatment. For the ultrasonic treatment, a dispersion device using an ultrasonic transducer can be used. The frequency of the ultrasonic wave to be irradiated is preferably 10 to 30 kHz. The output is preferably 300 to 900 W.

  The ultrasonic treatment time is preferably 5 to 120 minutes. The longer the ultrasonic wave is irradiated, the finer the gel and / or sol clusters become, and the less aggregated the state becomes. For this reason, colloidal particles of organically modified silica are close to monodisperse in a silica-containing sol obtained by ultrasonic treatment. When it is less than 5 minutes, the colloidal particles are not sufficiently dissociated. Even when the sonication time is longer than 120 minutes, the dissociation state of the organically modified silica colloidal particles hardly changes.

  In order to form a silica airgel film with a porosity of 79-57% and a refractive index of 1.1-1.2, the ultrasonic frequency is 10-30 kHz, the output is 300-900 W, and ultrasonic treatment The time is preferably 5 to 120 minutes.

  A dispersion medium may be added so that the concentration and fluidity of the silica-containing sol are in an appropriate range. A dispersion medium may be added prior to ultrasonic treatment, or a dispersion medium may be added after ultrasonic treatment to some extent. The mass ratio of the organically modified silica to the dispersion medium is preferably 0.1 to 20%. If the mass ratio of the organically modified silica to the dispersion medium is not in the range of 0.1 to 20%, it is difficult to form a uniform thin layer, which is not preferable.

  When a sol containing silicon oxide colloidal particles in a state close to monodispersion is used, an organic modified silica airgel film having a small porosity can be formed. When a sol containing colloidal particles in a large aggregated state is used, a silica airgel film having a large porosity can be formed. Therefore, the ultrasonic treatment time affects the porosity of the silica airgel film. An organically modified silica airgel film having a porosity of 25 to 90% can be obtained by applying a sol that has been subjected to ultrasonic treatment for 5 to 120 minutes.

[2] Preparation of UV Curable Resin Solution The UV curable resin that acts as a binder for organically modified silica preferably has compatibility with the dispersion of organically modified silica. The solvent is not particularly limited as long as it can dissolve the ultraviolet curable resin and is compatible with the organic modified silica dispersion. Therefore, what is necessary is just to select suitably from what was described above as a substituted dispersion medium of an organic modification silica dispersion liquid.

  The ultraviolet curable resin preferably has a refractive index of 1.5 or less after curing, and more preferably has a refractive index of 1.3 to 1.4. When an ultraviolet curable resin having a refractive index of 1.5 or less after curing is used, the refractive index of the silica airgel film can be set to 1.2 to 1.3. Fluorine-based non-crystalline ultraviolet curable resin is preferable because it has a refractive index of 1.5 or less and excellent transparency. Specific examples of the non-crystalline ultraviolet curable fluorine resin include a fluoroolefin copolymer, a polymer having a fluorine-containing aliphatic ring structure, and a fluorinated acrylate copolymer.

  An example of a fluoroolefin copolymer is a copolymer of 37 to 48% by mass of tetrafluoroethylene, 15 to 35% by mass of vinylidene fluoride, and 26 to 44% by mass of hexafluoropropylene. .

  Examples of the polymer having a fluorinated alicyclic structure include those obtained by polymerizing a monomer having a fluorinated alicyclic structure, and those obtained by cyclopolymerizing a fluorinated monomer having at least two polymerizable double bonds. A polymer obtained by polymerization of a monomer having a fluorine-containing ring structure is described in JP-B-63-18964. This polymer can be obtained by homopolymerization of a monomer having a fluorine-containing ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole) or copolymerization with a radical polymerizable monomer such as tetrafluoroethylene.

  Polymers obtained by cyclopolymerization of fluorine-containing monomers having at least two polymerizable double bonds are described in JP-A Nos. 63-238111 and 63-238115. This polymer is obtained by cyclopolymerization of monomers such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether), or copolymerization with a radical polymerizable monomer such as tetrafluoroethylene. Examples of the copolymer include a monomer having a fluorine-containing ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole) and at least two such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether). Examples thereof include those obtained by copolymerizing fluorine-containing monomers having two polymerizable double bonds.

  The binder may be made of a resin other than a fluorine-based resin, or a fluorine-based resin and another resin. Examples of resins other than fluorine-based resins include acrylic resins, silicone resins, epoxy resins, and urethane resins.

[3] Preparation of Coating Liquid The coating liquid contains organically modified silica, one or more ultraviolet curable resins, and a photopolymerization initiator. The coating solution is either (a) a dispersion containing organically modified silica and a solution containing an ultraviolet curable resin and a polymerization initiator, or (b) a dispersion containing organically modified silica and a polymerization initiator. Liquid and a solution containing an ultraviolet curable resin, or (c) a dispersion containing organically modified silica and a photopolymerization initiator, and a solution containing an ultraviolet curable resin and a photopolymerization initiator. It can be prepared by mixing or (d) adding a photopolymerization initiator after mixing a dispersion containing organically modified silica and a solution containing an ultraviolet curable resin. As described above, the content of the organically modified silica in the dispersion before mixing is preferably 0.1 to 20% by mass with respect to the dispersion medium. When the fluoroolefin copolymer is used as a binder, the concentration of the copolymer is preferably 0.5 to 2.0% by mass.

  The organic modified silica-containing dispersion and the ultraviolet curable resin solution are preferably mixed so that the volume ratio of the organic modified silica to the ultraviolet curable resin in the coating solution is 9: 1 to 1: 9. If the volume ratio of the ultraviolet curable resin in the coating solution exceeds 90%, the silica airgel voids are filled with the resin and the refractive index of the silica airgel film becomes too high. When the volume ratio of the ultraviolet curable resin is less than 10%, the ratio of the binder is too small, and the toughness of the silica airgel film is too small.

  The photopolymerization initiator is added to such an extent that the ultraviolet curable resin, or the unsaturated group of the ultraviolet curable resin and the organically modified silica can be polymerized in the ultraviolet irradiation step described later. A photopolymerization initiator may be added in advance to the ultraviolet curable resin solution and / or the organic modified silica-containing dispersion, or may be added after mixing both. The photopolymerization initiator is preferably 1 to 15% by mass in terms of solid content in the coating solution.

  Specific examples of photopolymerization initiators include benzoin and derivatives thereof (benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.), benzyl derivatives (benzyl dimethyl ketal, etc.), alkylphenones (acetophenone, 2,2-dimethoxy-2) -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One), anthraquinone and its derivatives (2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, etc.), thioxanthone and its derivatives (2,4-dimethylthioxanthone, 2-chlorothioxanthone) Etc.), Benzophenone And derivatives thereof (N, N-dimethylaminobenzophenone and the like).

[4] Formation of silica airgel film
(1) Coating When the coating solution is applied to a substrate or the like, the dispersion medium is volatilized and a film made of organically modified silica, an ultraviolet curable resin, and a photopolymerization initiator is formed. Examples of coating methods include spray coating, spin coating, dip coating, flow coating, and bar coating. A preferred coating method is a spray coating method. According to the spray coating method, a layer made of organic-modified silica-containing sol can be formed with a uniform thickness on an uneven surface.

(2) Drying The solvent in the coating solution is volatile and may be naturally dried. However, drying at a temperature of 50 to 100 ° C. can promote drying. The porosity of the organically modified silica decreases due to gel shrinkage caused by capillary pressure while the dispersion medium is volatilized, but recovers by the springback phenomenon when volatilization is completed. For this reason, the porosity of the organic modified silica airgel film obtained by drying is almost the same as the original porosity of the gel network, and shows a large value. The shrinkage and springback phenomenon of the silica gel network is described in detail in US Pat. No. 5,948,482.

(3) Ultraviolet irradiation Irradiation of ultraviolet light onto a coating film containing organically modified silica, an ultraviolet curable resin, and a photopolymerization initiator, and the ultraviolet curable resin, or the unsaturated of the ultraviolet curable resin and the organically modified silica Polymerize the group. It is preferable to irradiate the coating film with ultraviolet rays of about 50 to 10,000 mJ / cm ² using an ultraviolet irradiation device. Although depending on the thickness of the coating film, in the case of about 10 to 2000 nm, the irradiation time is preferably about 1 to 30 seconds.

(4) Firing The coated film is preferably fired at 50 to 150 ° C. By baking, the solvent in the layer, the hydroxyl groups on the surface, and the like can be removed to increase the strength of the film. Also, if the firing temperature is about 50 to 150 ° C., decomposition hardly occurs, so the silica airgel film after firing is cured by polymerization of unsaturated groups of ultraviolet curable resin or ultraviolet curable resin and organically modified silica. Has resin.

[5] Structure and Properties of Silica Airgel Film FIG. 1 schematically shows a cross section of the silica airgel film of the present invention. The silica airgel film is a porous film composed of an organically modified silica airgel 1 having a Si—O—Si bond and a cured resin layer 2 obtained by ultraviolet polymerization. Since the silica airgel film can be formed without requiring heating at a high temperature, the base material 10 on which the silica airgel film is formed may be a non-heat resistant material such as polyolefin. The cured resin layer 2 formed by ultraviolet polymerization covers the surface of the organic modified silica airgel 1 and the inner wall of the void, but does not completely fill the void of the organic modified silica airgel 1, so the silica airgel film has a nanometer size void. Has 1a.

  The refractive index of the silica airgel film depends on the porosity. The higher the porosity, the lower the refractive index, and the lower the porosity, the higher the refractive index. The refractive index also depends on the volume ratio between the organic modified silica airgel 1 and the cured resin layer 2, and the higher the volume ratio of the organic modified silica airgel 1, the smaller the refractive index, and the larger the volume ratio of the cured resin layer 2, the more refracted. The rate is large. The refractive index of the silica airgel film can be adjusted in the range of 1.15 to 1.35. For example, when the volume ratio of the organic modified silica airgel 1 and the cured resin layer 2 is 2: 1 to 1: 2, the refractive index can be 1.2 to 1.35.

  The thickness of the silica airgel film may be in a range that does not hinder firing or ultraviolet irradiation. When used as an antireflection film, the thickness is about 50 to 150 nm. The thickness of the silica airgel film can be appropriately adjusted depending on the concentration of the organic-modified silica-containing sol, the number of spray coatings, and the like.

  The organically modified silica airgel membrane is hydrophobic and exhibits excellent durability. This is thought to be because the surface does not have many hydroxyl groups and water does not easily enter the micropores. Further, the silica airgel film containing the cured resin layer 2 exhibits excellent toughness and water repellency.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
[Saturated alkoxysilane (silica skeleton forming compound) + saturated chlorosilane (organic modifier) + UV curable resin]
(1-i) Preparation of silica wet gel After mixing 5.21 g of tetraethoxysilane and 4.38 g of ethanol, 0.4 g of hydrochloric acid (0.01 N) was added and stirred for 90 minutes, and then 44.3 g of ethanol and aqueous ammonia solution ( 0.02 N) 0.5 g was added and stirred for 46 hours. When the resulting mixture was heated to 60 ° C. and aged for 46 hours, a wet gel was formed.

(1-ii) Preparation of organically modified silica dispersion The ethanol was added to the silica wet gel, shaken for 10 hours, and then decanted to remove unreacted substances and the like, and the dispersion medium of the wet gel was replaced with ethanol. . Next, methyl isobutyl ketone (MIBK) was added to the ethanol-dispersed wet gel, shaken for 10 hours, and decanted to replace the ethanol dispersion medium with MIBK.

  A trimethylchlorosilane solution (concentration: 5% by volume) using MIBK as a solvent was added to a silica wet gel, and stirred for 30 hours to organically modify the silicon oxide terminal. MIBK was added to the obtained organic modified silica wet gel, and the mixture was shaken for 24 hours and washed by decantation.

  After MIBK was added to the organic modified silica wet gel to a concentration of 3% by mass, sol-form organic modified silica (organic modified silica dispersion) was produced by ultrasonic irradiation (20 kHz, 500 W). The ultrasonic irradiation time was 20 minutes.

(1-iii) Preparation of UV curable resin solution
2-Propen-1-ol and perfluoro-3,6-dioxaoctane-1,8-dioic acid were added in 0.5 mol portions to a diethyl ether / MIBK mixed solvent and subjected to a dehydration condensation reaction. The obtained ester compound was copolymerized with 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate. An ultraviolet curable resin solution was prepared by dissolving the obtained copolymer and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator in MIBK. did. The concentration of the copolymer in the ultraviolet curable resin solution was 10% by mass, and the concentration of the polymerization initiator was 0.5% by mass.

(1-iv) Preparation of coating solution The organically modified silica dispersion obtained in step (1-ii) and the ultraviolet curable resin solution obtained in step (1-iii) were mixed at a volume ratio of 9: 1. A coating solution was obtained.

(1-v) Dip coat The coating solution is dip coated on one side of the silicon substrate, dried at 40 ° C for 5 minutes, and then irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (Fusion Systems). Then, it baked at 150 degreeC for 1 hour, and formed the silica airgel film | membrane.

Example 2
[Saturated alkoxysilane (silica skeleton forming compound) + saturated chlorosilane (organic modifier) + UV curable resin]
(2-i) Preparation of Silica Wet Gel Methyl silicate (MS51, average structure is tetramethoxysilane trimer) 5.90 g and methanol 50.55 g were mixed, then ammonia water (0.05 N) 3.20 g was added to add 30 Stir for minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(2-ii) Preparation of organically modified silica dispersion Step 1 of Example 1 except that the dispersion medium of the wet gel obtained in step (2-i) was substituted in the order of ethanol and MIBK and then reacted with trimethylchlorosilane. In the same manner as in -ii), an organically modified silica wet gel was obtained. After MIBK is added to the organic modified silica wet gel to a concentration of 3% by mass, sol-like organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated.

(2-iii) Preparation of coating solution The organically modified silica dispersion obtained in step (2-ii) and the ultraviolet curable resin solution prepared in step (1-iii) of Example 1 It mixed by volume ratio and was set as the coating liquid.

(2-iv) Dip coat Dip coat the coating solution on one side of the silicon substrate, dry at 40 ° C for 5 minutes, and then irradiate with UV irradiation at 1500 mJ / cm ² using an UV irradiation device (Fusion Systems). Baked at 150 ° C. to form a silica airgel film.

Example 3
[Unsaturated alkoxysilane (silica skeleton-forming compound) + saturated chlorosilane (organic modifier) + UV curable resin]
(3-i) Preparation of silica wet gel with unsaturated bonds
After 6.21 g of 3-methacryloxypropyltrimethoxysilane and 3.04 g of methanol were mixed, 0.4 g of hydrochloric acid (0.01 N) was added and stirred at 60 ° C. for 3 hours. To this was added 30.8 g of methanol and 0.5 g of an aqueous ammonia solution (0.02 N), and the mixture was stirred for 48 hours, then heated to 60 ° C. and aged for 72 hours to form a wet gel.

(3-ii) Preparation of organically modified silica dispersion Step 1 of Example 1 except that the dispersion medium of the wet gel obtained in step (3-i) was substituted in the order of ethanol and MIBK and then reacted with trimethylchlorosilane. In the same manner as in -ii), an organically modified silica wet gel was obtained. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-like organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. 3-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added to the organically modified silica dispersion at 3% by mass based on the solid content concentration of silica.

(3-iii) Preparation of coating solution 9 of the organically modified silica dispersion obtained in step (3-ii) and the ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(3-iv) Dip coat The coating solution is dip coated on a glass substrate, dried at 40 ° C. for 5 minutes, and irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 4
[Saturated alkoxysilane (silica skeleton forming compound) + unsaturated chlorosilane (organic modifier) + UV curable resin]
(4-i) Preparation of Silica Wet Gel Methyl silicate (MS51, average structure is tetramethoxysilane trimer) 5.90 g and methanol 50.55 g were mixed, then ammonia water (0.05 N) 3.20 g was added to add 30 Stir for minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(4-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of the wet gel obtained in step (4-i) in the order of ethanol and MIBK, allyldimethylchlorosilane solution (concentration of 5% by volume) using MIBK as a solvent. ) Was added and reacted in the same manner as in Step (1-ii) of Example 1 to obtain an organically modified silica wet gel. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-like organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(4-iii) Preparation of coating solution The organically modified silica dispersion obtained in step (4-ii) and an ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(4-iv) Dip coat Dip coat the coating solution on a glass substrate, dry at 40 ° C for 5 minutes, and then irradiate with UV irradiation at 1500 mJ / cm ² using an UV irradiation device (Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 5
[Unsaturated alkoxysilane (silica skeleton-forming compound) + unsaturated chlorosilane (organic modifier) + UV curable resin]
(5-i) Preparation of silica wet gel with unsaturated bonds
After 6.21 g of 3-methacryloxypropyltrimethoxysilane and 3.04 g of methanol were mixed, 0.4 g of hydrochloric acid (0.01 N) was added and stirred at 60 ° C. for 3 hours. After adding 30.8 g of methanol and 0.5 g of an aqueous ammonia solution (0.02 N) and stirring for 48 hours, the resulting mixture was heated to 60 ° C. and aged for 72 hours to form a wet gel.

(5-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of the wet gel obtained in step (5-i) in the order of ethanol and MIBK, an allyldimethylchlorosilane solution (concentration of 5% by volume) was added and reacted. An organically modified silica wet gel was obtained in the same manner as in step (1-ii) of Example 1 except for the above. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(5-iii) Preparation of coating solution The organically modified silica dispersion obtained in step (5-ii) and an ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(5-iv) Dip coating The coating solution is dip coated on a glass substrate, dried at 40 ° C. for 5 minutes, and irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 6
[Saturated alkoxysilane: unsaturated alkoxysilane (1: 2) (silica skeleton forming compound) + saturated chlorosilane (organic modifier) + UV curable resin]
(6-i) Preparation of Silica Wet Gel with Unsaturated Bond Methyl silicate (MS51, average structure is tetramethoxysilane trimer) 2.37 g, 3-methacryloxypropyltrimethoxysilane 3.22 g, methanol 40.44 g After mixing, 2.56 g of aqueous ammonia (0.05 N) was added and stirred for 30 minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(6-ii) Preparation of organically modified silica dispersion After replacing the wet gel dispersion medium obtained in step (6-i) with ethanol and MIBK in this order, a trimethylchlorosilane solution (concentration of 5% by volume) was added and reacted. Except that, an organically modified silica wet gel was obtained in the same manner as in Step (1-ii) of Example 1. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(6-iii) Preparation of coating solution 9 of the organically modified silica dispersion obtained in step (6-ii) and the ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(6-iv) Dip coating The coating solution is dip coated on a glass substrate, dried at 40 ° C. for 5 minutes, and irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 7
[Saturated alkoxysilane: unsaturated alkoxysilane (1: 2) (silica skeleton forming compound) + unsaturated chlorosilane (organic modifier) + UV curable resin]
(7-i) Preparation of silica wet gel with unsaturated bond 2.37 g of methyl silicate (MS51, average structure is tetramethoxysilane trimer), 3.22 g of 3-methacryloxypropyltrimethoxysilane, 40.44 g of methanol After mixing, 2.56 g of aqueous ammonia (0.05 N) was added and stirred for 30 minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(7-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of wet gel obtained in step (7-i) in the order of ethanol and MIBK, allyldimethylchlorosilane solution (concentration 5% by volume) was added. In the same manner as in Step (1-ii) of Example 1, an organically modified silica wet gel was obtained. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(7-iii) Preparation of coating solution 9 of the organically modified silica dispersion obtained in step (7-ii) and the ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(7-iv) Dip coat Dip coat the coating solution on a glass substrate, dry at 40 ° C for 5 minutes, and then irradiate with UV irradiation at 1500 mJ / cm ² using an UV irradiation device (Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 8
[Saturated alkoxysilane (silica skeleton forming compound) + saturated chlorosilane: unsaturated chlorosilane (1: 1) (organic modifier) + UV curable resin]
(8-i) Preparation of Silica Wet Gel Methyl silicate (MS51, average structure is tetramethoxysilane trimer) 5.90 g and methanol 50.55 g were mixed, then ammonia water (0.05 N) 3.20 g was added to add 30 Stir for minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(8-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of the wet gel obtained in step (8-i) in the order of ethanol and MIBK, a mixed solution of trimethylchlorosilane and allyldimethylchlorosilane using MIBK as a solvent An organic modified silica wet gel was obtained in the same manner as in Step (1-ii) of Example 1 except that (volume ratio; methyl isobutyl ketone: trimethylchlorosilane: allyldimethylchlorosilane = 90: 5: 5) was added. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(8-iii) Preparation of coating solution The organically modified silica dispersion obtained in step (8-ii) and the UV curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(8-iv) Dip coat Dip coat the coating solution on a glass substrate, dry at 40 ° C for 5 minutes, and then irradiate with ultraviolet light at 1500 mJ / cm ² using an ultraviolet irradiation device (Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 9
[Unsaturated alkoxysilane (silica skeleton-forming compound) + saturated chlorosilane: unsaturated chlorosilane (1: 1) (organic modifier) + UV curable resin]
(9-i) Preparation of silica wet gel with unsaturated bond
After 6.21 g of 3-methacryloxypropyltrimethoxysilane and 3.04 g of methanol were mixed, 0.4 g of hydrochloric acid (0.01 N) was added and stirred at 60 ° C. for 3 hours. After adding 30.8 g of methanol and 0.5 g of an aqueous ammonia solution (0.02 N) and stirring for 48 hours, the resulting mixture was heated to 60 ° C. and aged for 72 hours to form a wet gel.

(9-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of the wet gel obtained in step (9-i) in the order of ethanol and MIBK, a mixed solution of trimethylchlorosilane and allyldimethylchlorosilane using MIBK as a solvent An organic modified silica wet gel was obtained in the same manner as in Step (1-ii) of Example 1 except that (volume ratio; methyl isobutyl ketone: trimethylchlorosilane: allyldimethylchlorosilane = 90: 5: 5) was added. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(9-iii) Preparation of coating solution 9 of the organically modified silica dispersion obtained in step (9-ii) and the ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(9-iv) Dip coating The coating solution is dip coated on a glass substrate, dried at 40 ° C. for 5 minutes, and irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Example 10
[Saturated alkoxysilane: unsaturated alkoxysilane (1: 2) (silica skeleton forming compound) + saturated chlorosilane: unsaturated chlorosilane (1: 1) (organic modifier) + UV curable resin]
(10-i) Preparation of Silica Wet Gel with Unsaturated Bond Methyl silicate (MS51, average structure is tetramethoxysilane trimer) 2.37 g, 3-methacryloxypropyltrimethoxysilane 3.22 g, methanol 40.44 g After mixing, 2.56 g of aqueous ammonia (0.05 N) was added and stirred for 30 minutes. When the obtained mixed solution was aged at room temperature for 72 hours, a wet gel was formed.

(10-ii) Preparation of organically modified silica dispersion After replacing the dispersion medium of the wet gel obtained in step (10-i) in the order of ethanol and MIBK, a mixed solution of trimethylchlorosilane and allyldimethylchlorosilane using MIBK as a solvent An organic modified silica wet gel was obtained in the same manner as in Step (1-ii) of Example 1 except that (volume ratio; methyl isobutyl ketone: trimethylchlorosilane: allyldimethylchlorosilane = 90: 5: 5) was added. After MIBK is added to the organic modified silica wet gel to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) is obtained by irradiating with ultrasonic waves in the same manner as in step (1-ii) of Example 1. Generated. To this organic modified silica dispersion, 3% by mass of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator was added based on the solid content concentration of silica.

(10-iii) Preparation of coating solution 9 of the organically modified silica dispersion obtained in step (10-ii) and the ultraviolet curable resin solution prepared in the same manner as in step (1-iii) of Example 1 The mixture was mixed at a volume ratio of 1 to obtain a coating solution.

(10-iv) Dip coating The coating solution is dip coated on a glass substrate, dried at 40 ° C. for 5 minutes, and irradiated with ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion Systems). Firing at 150 ° C. formed a silica airgel film.

Comparative Example 1
(Ai) Preparation of organic-modified silica-containing sol After mixing 5.21 g of tetraethoxysilane and 4.38 g of ethanol, 0.4 g of hydrochloric acid (0.01 N) was added and stirred for 90 minutes. 44.3 g of ethanol and 0.5 g of an aqueous ammonia solution (0.02 N) were added and stirred for 46 hours, and then the resulting mixture was heated to 60 ° C. and aged for 46 hours to produce a wet gel.

  Ethanol was added to the silica wet gel and shaken for 10 hours, followed by decantation to remove unreacted materials and the like, and the dispersion medium of the wet gel was replaced with ethanol. Further, MIBK was added and shaken for 10 hours, followed by decantation to replace the ethanol dispersion medium with MIBK. A trimethylchlorosilane solution (concentration: 5% by volume) using MIBK as a solvent was added to a silica wet gel, and stirred for 30 hours to organically modify the silicon oxide terminal. The obtained organic modified silica wet gel was decanted by shaking with MIBK for 24 hours.

  After MIBK was added to the organic modified silica to a concentration of 1% by mass, sol-form organic modified silica (organic modified silica dispersion) was produced by ultrasonic irradiation (20 kHz, 500 W). The ultrasonic irradiation time was 20 minutes.

(A-ii) Dip coat
The organically modified silica dispersion obtained in (Ai) was dip coated on one surface of a silicon substrate, dried at 40 ° C. for 5 minutes, and then baked at 150 ° C. for 1 hour to form a silica airgel film.

注１：耐擦傷性
方法：不織布で任意にラビングして傷のつき具合を調べた。
評価；○ 傷無し
△ 傷が少し付く
× 傷が多く付く
注２：耐溶剤性
方法：不織布にエタノールを染み込ませてラビングして剥離の有無を調べた。
評価；○ 剥離無し
△ 一部剥離した
× 全面が剥離した (Performance evaluation)
The refractive index, scratch resistance and solvent resistance of the silica airgel films of each Example and Comparative Example were examined. The results are shown in Table 1.

Note 1: Scratch resistance Method: Rubbing was arbitrarily performed with a non-woven fabric, and the degree of scratching was examined.
Evaluation: ○ No scratch
△ Scratches a little
X Many scratches are attached. Note 2: Solvent resistance Method: Ethanol was impregnated into a non-woven fabric and rubbed to examine the presence or absence of peeling.
Evaluation: ○ No peeling
△ Partially peeled
× The entire surface peeled

It is sectional drawing which shows an example of the structure of the silica airgel film | membrane of this invention.

Explanation of symbols

1. Silica airgel
1a: void 2 ... binder
10 ... Base material

Claims (9)

A method for producing a silica airgel film,
A wet gel is produced by hydrolysis polymerization of alkoxysilane and / or silsesquioxane, and the wet gel is reacted with an organic modifier to produce an organic modified wet gel,
The organically modified wet gel is sonicated at a frequency of 10 to 30 kHz, an output of 300 to 900 W, and a treatment time of 5 to 120 minutes to produce an organically modified silica-containing sol,
The organic modified silica-containing sol, an ultraviolet curable resin composed of a fluororesin having a refractive index after curing of 1.5 or less, and a photopolymerization initiator are mixed to prepare a coating liquid,
Applying the coating liquid to form an organically modified silica-containing sol layer,
Drying the organically modified silica-containing sol layer, volatilizing the dispersion medium,
Irradiating ultraviolet rays to polymerize the ultraviolet curable resin, and the unsaturated groups of the ultraviolet curable resin and the organically modified silica, thereby covering the surface and the inner walls of the voids with the cured resin,
A method of firing to produce a silica airgel film having a refractive index of 1.2 to 1.3 . 2. The method for producing a silica airgel film according to claim 1 , wherein the ultraviolet curable resin is a resin that becomes a curable resin having a refractive index of 1.33 to 1.5 by a polymerization reaction. The method for producing a silica airgel film according to claim 1 or 2 , wherein a dispersion medium of the organically modified silica-containing sol is at least one selected from the group consisting of carboxylic acid ester, ketone and alcohol. . The method for producing a silica airgel film according to any one of claims 1 to 3 , wherein the solvent of the wet gel is an alcohol having 1 to 3 carbon atoms. The method for producing a silica airgel coating according to claim 1, wherein the use of monosilane having an unsaturated group and an alkoxyl group as the alkoxysilane. The method for producing a silica airgel film according to any one of claims 1 to 5 , wherein a silane coupling agent is used as the organic modifier. The method for producing a silica airgel film according to any one of claims 1 to 6 , wherein the organic modifier has an ultraviolet polymerizable unsaturated group. The method for producing a silica airgel film according to any one of claims 1 to 7 , wherein a monosilane having an unsaturated group and an alkoxyl group is used as the alkoxysilane, and an oligomer is produced by polymerizing the monosilane using an acid catalyst. The wet gel is obtained by polymerizing the oligomer using a base catalyst. The method for producing a silica airgel film according to any one of claims 1 to 8 , wherein firing is performed at 50 to 150 ° C.

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