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WO2015166863A1 - Composition liquide, et composant en verre - Google Patents

Composition liquide, et composant en verre Download PDF

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Publication number
WO2015166863A1
WO2015166863A1 PCT/JP2015/062285 JP2015062285W WO2015166863A1 WO 2015166863 A1 WO2015166863 A1 WO 2015166863A1 JP 2015062285 W JP2015062285 W JP 2015062285W WO 2015166863 A1 WO2015166863 A1 WO 2015166863A1
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WO
WIPO (PCT)
Prior art keywords
group
liquid composition
compound
hydrolyzable
silane compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/062285
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English (en)
Japanese (ja)
Inventor
晋平 森田
広和 小平
米田　貴重
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2015166863A1 publication Critical patent/WO2015166863A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a liquid composition for forming an ultraviolet absorbing film on the surface of an article such as glass, and a glass article having an ultraviolet absorbing film formed using the liquid composition.
  • transparent substrates such as window glass for vehicles such as automobiles and window glass for building materials attached to buildings such as houses and buildings have the ability to absorb ultraviolet rays incident on the interior of cars and indoors through these, and are resistant. Attempts have been made to form a UV-absorbing film having mechanical durability such as wear.
  • a silica-based UV-absorbing film is conventionally formed on a substrate using a liquid composition in which an organic UV-absorbing agent is mixed with a silane compound. Attempts have been made.
  • Patent Document 1 discloses that a silica-based ultraviolet absorbing film is formed on a substrate using a coating liquid containing a hydrolyzable silane compound and a compound in which a hydrolyzable silyl group is introduced into an organic ultraviolet absorber. Attempts have been made.
  • the present invention has been made from the above viewpoint, and has a liquid composition capable of forming a UV-absorbing film having high UV-absorbing ability and antifouling property and having excellent abrasion resistance on the surface of an article such as glass, and It is an object of the present invention to provide a glass article having an ultraviolet absorbing film having a high ultraviolet absorbing ability and antifouling property formed using the liquid composition and having excellent wear resistance.
  • the present invention provides a liquid composition and a glass article having the following constitution.
  • An ultraviolet absorber (a) containing one or more selected from benzophenone compounds, triazine compounds, and benzotriazole compounds, a silicon compound (b) having a surface tension of 17.5 to 30 mN / m,
  • R H1 n1 SiX 1 4-n1 (In the formula (1), n1 is an integer of 0 to 3, R H1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms having no fluorine atom, and X 1 is hydrolyzable. When a plurality of R H1 and X 1 are present, these may be different or the same.) [2] The liquid composition according to [1], wherein the content of the silicon compound (b) with respect to the total solid content in the liquid composition is 0.01 to 10% by mass.
  • the silicon compound (b) includes a hydrolyzable silane compound (b1) represented by the following formula (b1), a hydrolyzable silane compound (b2) represented by the following formula (b2), and the following formula (b3).
  • R f is a divalent organic group having 1 to 20 carbon atoms which may have an etheric oxygen atom containing at least one fluoroalkylene group
  • A is a fluorine atom or —Si (R 2 ) b X 2 (3-b)
  • R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and does not have a fluorine atom
  • X 2 represents a hydrolyzable group.
  • a is 1 or 2
  • b is 0 or 1
  • a + b is 1 or 2.
  • R 3 (SiR 4 2 O) k —SiR 4 2 —Y 1 —Si (R 5 ) n2 (X 3 ) 3-n2 (b2)
  • R 3 represents an alkyl group having 1 to 10 carbon atoms or —Y 1 —Si (R 5 ) n2 (X 3 ) 3-n2 group
  • R 4 each independently represents the number of carbon atoms. 1 to 3 alkyl groups
  • Y 1 independently represents an alkylene group having 2 to 4 carbon atoms
  • R 5 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms having no fluorine atom.
  • X 3 represents a hydrolyzable group
  • k is an integer of 10 to 200
  • n2 is 0, 1 or 2.
  • R 6 3 Si—O— (SiR 7 2 O) m1 — (SiR 7 R 8 O) m2 —SiR 6 3 (b3)
  • R 6 is independently an alkyl group having 1 to 20 carbon atoms
  • R 7 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group
  • R 8 is A monovalent organic group having 1 to 20 carbon atoms and having a polyoxyalkylene group, an amide group or an ester group
  • m1 is an integer from 0 to 200
  • m2 is from 0 to 200
  • m1 + m2 is an integer from 10 to 200.
  • the ultraviolet absorber (a) comprises a benzophenone compound
  • the silicon compound (b) is obtained by using the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound (b2) as a partial hydrolysis cocondensate with the hydrolyzable silane compound (c).
  • the glass article according to [9] wherein a water contact angle on the surface of the coating is 70 degrees or more, and a haze in the glass article is 1% or less.
  • the liquid composition of the present invention it is possible to form a UV-absorbing film having both high UV-absorbing ability and antifouling property and excellent wear resistance on the surface of an article such as glass.
  • ADVANTAGE OF THE INVENTION According to this invention, the glass article which has the ultraviolet-ray absorption film which has high ultraviolet-absorption ability and antifouling property, and was excellent in abrasion resistance can be provided.
  • the liquid composition of the present invention comprises an ultraviolet absorber (a) containing one or more selected from benzophenone compounds, triazine compounds, and benzotriazole compounds, silicon having a surface tension of 17.5 to 30 mN / m. It contains a compound (b), a hydrolyzable silane compound (c) represented by the following formula (1) (excluding the silicon compound (b)), and a solvent (d).
  • a ultraviolet absorber
  • a containing one or more selected from benzophenone compounds, triazine compounds, and benzotriazole compounds, silicon having a surface tension of 17.5 to 30 mN / m. It contains a compound (b), a hydrolyzable silane compound (c) represented by the following formula (1) (excluding the silicon compound (b)), and a solvent (d).
  • R H1 n1 SiX 1 4-n1 (1) (In the formula (1), n1 is an integer of 0 to 3, R H1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms having no fluorine atom, and X 1 is hydrolyzable. When a plurality of R H1 and X 1 are present, these may be different or the same.)
  • the hydrolyzable silane compound (c) is mainly hydrolytically condensed to form a siloxane bond represented by —Si—O—Si—, which is linearly or three-dimensionally high. By increasing the molecular weight, it hardens to form a film.
  • the ultraviolet absorber (a) may be indicated as the component (a).
  • the “hydrolyzable silane compound” includes an unreacted hydrolyzable silane compound, one partial hydrolyzed condensate thereof, and two or more partially hydrolyzed cocondensates unless otherwise specified. Used as a term.
  • hydrolyzable silane compound when referring to a specific “hydrolyzable silane compound”, for example, when referring to a hydrolyzable silane compound (c), an unreacted hydrolyzable silane compound (c), a partial hydrolysis condensate thereof, and other hydrolysis It is used as a term including the unit of the hydrolyzable silane compound (c) in the partially hydrolyzed cocondensate with the functional silane compound.
  • the terms “(meth) acrylic” and “(meth) acrylo” such as (meth) acrylic acid ester and (meth) acryloxy group used in the present specification are “acrylic” and “methacrylic”. Both are terms that mean both “acrylo...” and “methacrylo...”.
  • the ultraviolet absorber (a) contained in the liquid composition of the present invention contains one or more selected from benzophenone compounds, triazine compounds, and benzotriazole compounds.
  • benzotriazole-based compound specifically, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (as a commercial product, TINUVIN 326 (Trade name, manufactured by Ciba Japan), etc.), octyl-3- [3-tert-4-hydroxy-5- [5-chloro-2H-benzotriazol-2-yl] propionate, 2- (2H-benzo Triazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6) -Tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-
  • triazine compound examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-bis-butoxyphenyl) -1,3,5-triazine, 2 -(2-Hydroxy-4- [1-octylcarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, TINUVIN477 (trade name, Ciba Japan Ltd.) Ltd.) and the like
  • benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2 ′, 3 (or any of 4, 5, 6) -trihydroxybenzophenone, 2,2 ′, 4,4′-.
  • examples thereof include tetrahydroxybenzophenone, 2,4-dihydroxy-2 ′, 4′-dimethoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone.
  • 2,2 ', 4,4'-tetrahydroxybenzophenone is preferably used.
  • the ultraviolet absorber (a) one of these compounds can be used alone, or two or more can be used in combination.
  • a hydroxyl group-containing benzophenone compound is preferably used among the compounds exemplified above because of its high solubility in a solvent and an absorption wavelength band in a desirable range.
  • ultraviolet absorbing materials other than these are combined with one or more selected from the above-mentioned benzophenone compounds, triazine compounds, and benzotriazole compounds. You may use as an agent (a).
  • the ultraviolet absorber (a) a compound that is soluble in an organic solvent described later that is usually contained in a liquid composition is preferable.
  • the ultraviolet absorber (a) is dispersed as fine particles in a dispersion medium to obtain a dispersion, and the dispersion Is preferably contained in the liquid composition.
  • the dispersion in which the fine particles of the ultraviolet absorbent (a) are dispersed is a dispersion obtained by dispersing using a dispersant. Preferably there is.
  • the dispersion medium in the dispersion liquid of the ultraviolet absorber (a) fine particles constitutes a part of the organic solvent contained in the composition in the resulting composition
  • a compound having compatibility with an organic solvent is preferably used as a dispersion medium.
  • the content of the ultraviolet absorber (a) in the liquid composition is such that the obtained coating film has sufficient ultraviolet absorbing ability and the mechanical strength in the coating film is ensured from the viewpoint of 100 of the hydrolyzable silane compound (c).
  • the amount is preferably 1 to 200 parts by mass, more preferably 5 to 180 parts by mass, and particularly preferably 15 to 150 parts by mass with respect to parts by mass.
  • a ultraviolet absorber (a) in order to prevent a ultraviolet absorber (a) from bleeding out from the coating film obtained, it is also possible to make a ultraviolet absorber (a) into the following structures as needed. That is, a functional group having reactivity with the reactive group of the hydrolyzable silane compound (c) may be introduced into the ultraviolet absorber (a).
  • the compound used for this introduction is regarded as a part of the hydrolyzable silane compound (c) when calculating the content of the ultraviolet absorber (a) in the liquid composition.
  • Examples of the functional group introduced into the ultraviolet absorber (a) include a functional group having reactivity with the hydrolyzable group of the hydrolyzable silane compound contained in the hydrolyzable silane compound (c), for example, hydrolysis.
  • a silyl group having a functional group is preferred. Specifically, it contains a silyl group having a hydrolyzable group obtained by introducing a silyl group having a hydrolyzable group into a benzophenone compound, a triazine compound, and a benzotriazole compound by an appropriate method. At least one selected from the above-mentioned respective compounds can be contained in the liquid composition as an ultraviolet absorber (a).
  • the ultraviolet absorber which consists of the said compound containing the silyl group which has a hydrolysable group is hereafter called silylated ultraviolet absorber.
  • a reaction product of a hydroxyl group-containing benzophenone compound preferably used in the present invention and a hydrolyzable silane compound having a reactivity with a hydroxyl group, for example, an epoxy group (hereinafter referred to as “silylated benzophenone compound”).
  • silylated benzophenone compound can also be used as the ultraviolet absorber (a).
  • the silylated benzophenone-based compound as the component (a) is contained in the liquid composition together with the hydrolyzable silane compound as the component (c), they are co-crosslinked by a hydrolysis reaction to form a silicon oxide matrix.
  • the hydroxyl group-containing benzophenone compound residue derived from the silylated benzophenone compound is fixed to the silicon oxide matrix, and bleeding out is prevented.
  • the obtained coating film can retain the ultraviolet absorbing ability over a long period of time.
  • silylated ultraviolet absorber will be described using a silylated benzophenone compound as an example.
  • a benzophenone compound having a hydroxyl group as a raw material of the silylated benzophenone compound an excellent ultraviolet absorption after the benzophenone compound having 2 to 4 hydroxyl groups represented by the following general formula (a1) is silylated It is preferably used because of its ability.
  • the hydroxyl group-containing benzophenone compound has more preferably 3 or 4 hydroxyl groups.
  • the compound represented by the formula (a1) may be referred to as the compound (a1). The same applies to compounds represented by other formulas.
  • Xs may be the same or different and each represents a hydrogen atom or a hydroxyl group, at least one of which is a hydroxyl group.
  • benzophenone compounds having a hydroxyl group represented by the general formula (a1) 2,4-dihydroxybenzophenone, 2,2 ′, 3 (or any of 4, 5, 6) -trihydroxybenzophenone 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like are more preferable, and 2,2 ′, 4,4′-tetrahydroxybenzophenone is particularly preferable.
  • the hydroxyl group-containing benzophenone compound can be used alone or as a mixture of two or more.
  • a hydrolyzable silane compound containing a group reactive with a hydroxyl group particularly a hydrolyzable silane compound containing an epoxy group, used in a reaction for silylated such a hydroxyl group-containing benzophenone compound,
  • examples thereof include trifunctional or bifunctional hydrolyzable silane compounds in which a non-hydrolyzable monovalent organic group is bonded to a silicon atom.
  • the epoxy group-containing hydrolyzable silane compound is particularly preferably 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane and the like are used.
  • the epoxy group-containing hydrolyzable silane compound can be used alone or as a mixture of two or more.
  • At least one hydroxyl group-containing benzophenone compound and at least one epoxy group-containing hydrolyzable silane compound are reacted in the presence of a catalyst as necessary.
  • the amount of the epoxy group-containing hydrolyzable silane compound used in the reaction is not particularly limited, but is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.3 mol per mol of the hydroxyl group-containing benzophenone compound. 0 mole.
  • the amount of the epoxy group-containing hydrolyzable silane compound relative to 1 mol of the hydroxyl group-containing benzophenone compound is less than 0.5 mol, when added to the liquid composition, there are many hydroxyl group-containing benzophenone compounds that are not silylated. May cause bleed-out.
  • quaternary ammonium salt as described in JP-A-58-10591 is preferable.
  • the quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and the like.
  • the amount of the catalyst to be added to the reaction system is not particularly limited, but the addition amount is 0.005 to 10 parts by mass with respect to 100 parts by mass in total of the hydroxyl group-containing benzophenone compound and the epoxy group-containing hydrolyzable silane compound.
  • the amount is preferably, and more preferably 0.01 to 5 parts by mass.
  • the addition amount of the catalyst is less than 0.005 parts by mass with respect to a total of 100 parts by mass of the hydroxyl group-containing benzophenone compound and the epoxy group-containing hydrolyzable silane compound, the reaction takes a long time, and when it exceeds 10 parts by mass, When this reaction product is added to the liquid composition, the catalyst may reduce the stability of the composition.
  • the silylation reaction is carried out by heating a mixture of a hydroxyl group-containing benzophenone compound and an epoxy group-containing hydrolyzable silane compound, preferably in the above ratio, in the temperature range of 50 to 150 ° C. for 4 to 20 hours in the presence of a catalyst. It can be carried out.
  • This reaction may be performed in the absence of a solvent or in a solvent that dissolves both the hydroxyl group-containing benzophenone compound and the epoxy group-containing hydrolyzable silane compound.
  • the reaction is easy to control and easy to handle.
  • a method using a solvent is preferred. Examples of such a solvent include toluene, xylene, ethyl acetate, butyl acetate and the like.
  • the amount of the solvent to be used is about 10 to 300 parts by mass with respect to 100 parts by mass in total of the hydroxyl group-containing benzophenone compound and the epoxy group-containing hydrolyzable silane compound.
  • the silylated benzophenone compound preferably used in the present invention is obtained by reacting 1 to 2 hydroxyl groups of a benzophenone compound containing 3 or more hydroxyl groups with an epoxy group of an epoxy group-containing hydrolyzable silane compound. More preferably, 4- (2-hydroxy-3- (3- (trimethoxysilyl) propoxy) propoxy) -2,2 ′, 4 ′ represented by the following formula (a2) is preferable. -Trihydroxybenzophenone and the like. In the following formula (a2), Me represents a methyl group.
  • the amount of the silylated benzophenone compound is calculated as follows. What is necessary is just to adjust so that it may become content of the ultraviolet absorber (a) in the liquid composition to show.
  • the silylated benzophenone-based compound in the silyl group having a hydrolyzable group, for example, in the compound (a2), the amount of —Si (OMe) 3 is converted to SiO 2 and the hydrolyzable silane compound ( It is included in the amount of c).
  • the part of the silylated benzophenone compound other than the silyl group having a hydrolyzable group that is, the amount of the hydroxyl group-containing benzophenone compound residue containing a linking group is defined as the content of the ultraviolet absorber (a).
  • the mass part of the ultraviolet absorber (a) with respect to 100 parts by mass of the hydrolyzable silane compound (c) thus obtained is calculated.
  • the silicon compound (b) contained in the liquid composition of the present invention is a compound having a surface tension of 17.5 to 30 mN / m, and imparts antifouling properties to the surface of a film obtained using the liquid composition. It has a function.
  • surface tension in the present specification refers to a value measured by a bubble pressure method (maximum bubble pressure method). Specifically, it is a value measured using a temperature of 22 ° C. and gaseous air. More specifically, the surface tension measured under the above conditions using a surface tension meter (manufactured by Eiko Seiki Co., Ltd .: Science line t60) is used as a reference in this specification.
  • the surface tension of the silicon compound (b) exceeds 30.0 mN / m, sufficient antifouling property cannot be imparted to the surface of the coating.
  • the surface tension of the silicon compound (b) is less than 17.5 mN / m, the compatibility with the other components in the composition, particularly the hydrolyzable silane compound (c) is not sufficient, and the coating can be uneven. The appearance is damaged. Specifically, the haze value is increased in the obtained film, and a uniform film thickness cannot be obtained as a whole on the surface on which the film is formed.
  • the surface tension of the silicon compound (b) is preferably 17.6 to 25.0 mN / m, and more preferably 17.7 to 20.0 mN / m.
  • the liquid composition of the present invention contains a silicon compound (b) having a surface tension in the above range
  • the liquid composition is applied onto a substrate such as glass, and the solvent is removed as necessary, followed by curing.
  • the silicon compound (b) moves to the upper surface of the film and can impart excellent antifouling properties to the upper surface of the finally obtained film, and the uniformity of the liquid composition is impaired. There is no.
  • the content of the silicon compound (b) in the liquid composition of the present invention is preferably 0.01 to 10% by mass with respect to the total solid content in the liquid composition, and the type of the silicon compound (b), for example, hydrolysis Depending on the functional silane compound (b1), hydrolyzable silane compound (b2), and diorganosilicone oil (b3), 0.1 to 3% by mass is more preferred.
  • solid content means a film formation component among the components which a liquid composition contains, and all components other than the volatile component which volatilizes by heating etc. in film formation processes, such as solvent (d). Indicates. When the content of the silicon compound (b) in the liquid composition is in the above range, sufficient antifouling property can be imparted to the upper surface of the obtained ultraviolet absorbing film, and the appearance of the film is not impaired.
  • a silicon compound (b) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • content of the silicon compound (b) in a liquid composition is adjusted suitably.
  • the silicon compound (b1) and / or the hydrolyzable silane compound (b2) is used as the silicon compound (b)
  • the silicon compound (b) is converted into a hydroxyl group (by a hydrolysis reaction together with the hydrolyzable silane compound (c)).
  • a compound having a (silanol group) is formed, and then a Si—O—Si bond is formed by a condensation reaction between molecules, whereby the silicon compound (b) is easily immobilized on the coating.
  • the hydrolyzable silane compound (b1) is a compound represented by the following general formula (b1), and is a silicon compound (b) having a surface tension of 17.5 to 30 mN / m.
  • R f is a divalent organic group having 1 to 20 carbon atoms which may have an etheric oxygen atom containing at least one fluoroalkylene group
  • A is a fluorine atom or —Si (R 2 ) b X 2 (3-b)
  • R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and does not have a fluorine atom
  • X 2 represents a hydrolyzable group.
  • a is 1 or 2
  • b is 0 or 1
  • a + b is 1 or 2.
  • Compound (b1) is a fluorine-containing hydrolyzable silane compound having one or two bifunctional or trifunctional hydrolyzable silyl groups.
  • R 2 is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a methyl group.
  • a is 1 and b is 0 or 1.
  • X 2 include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which at least one hydrogen of the amino group is substituted with an alkyl group.
  • a compound represented by the following formula (21) is particularly preferable.
  • TR f1 -Q 1 -SiX 21 3 (21) (In the formula (21), R f1 is a perfluoroalkylene group having 1 to 15 carbon atoms which may contain an etheric oxygen atom, T is a fluorine atom or —Q 2 —SiX 22 3 , and X 21 and X 22 is a hydrolyzable group, and three X 21 and X 22 may be the same or different from each other, and Q 1 and Q 2 do not contain a fluorine atom having 1 to 10 carbon atoms.
  • a divalent organic group, wherein the number of carbon atoms in TR f1 -Q 1- is 20 or less.
  • R f1 when T is a fluorine atom, R f1 is preferably a perfluoroalkylene group having 1 to 8 carbon atoms and a perfluoroalkylene group containing an etheric oxygen atom having 4 to 10 carbon atoms, A perfluoroalkylene group having 1 to 8 atoms is more preferred, and a perfluoroalkylene group having 6 carbon atoms is particularly preferred.
  • R f1 when T is —Q 2 —SiX 22 3 , R f1 includes a perfluoroalkylene group having 3 to 15 carbon atoms and an etheric oxygen atom having 3 to 15 carbon atoms. A perfluoroalkylene group is preferred, and a perfluoroalkylene group having 4 to 6 carbon atoms is particularly preferred.
  • R f1 examples include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable.
  • R f1 include the following groups. - (CF 2) -, - (CF 2) 2 -, - (CF 2) 3 -, - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -, -CF 2 CF 2 OCF 2 CF 2 OCF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 —.
  • Q 1 and Q 2 are represented by the fact that Si is bonded to the right bond and R f1 is bonded to the left bond, specifically, — (CH 2 ) i1 — (i1 is 1 to 5) Integer)), —CH 2 O (CH 2 ) i2 — (i2 is an integer of 1 to 4), —SO 2 NR 1 — (CH 2 ) i3 — (R 1 is a hydrogen atom, a methyl group, or an ethyl group) I3 is an integer of 1 to 4, and the total number of carbon atoms of R 1 and (CH 2 ) i3 is an integer of 4 or less.), — (C ⁇ O) —NR 1 — (CH 2 ) i4 — (R 1 is the same as above, i4 is an integer of 1 to 4, and the total number of carbon atoms of R 1 and (CH 2 ) i4 is an integer of 4 or less). Is preferred.
  • Q 1 and Q 2 —
  • Q 1 and Q 2 are preferably groups represented by — (CH 2 ) i1 —. i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.
  • Q 1 and Q 2 include — (CH 2 ) i1 —, —CH 2 O (CH 2 ) i2 —, —SO 2 NR 1 — ( Groups represented by CH 2 ) i3 — and — (C ⁇ O) —NR 1 — (CH 2 ) i4 — are preferred.
  • — (CH 2 ) i1 — is more preferable, i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.
  • T is a fluorine atom
  • specific examples of the compound (21) include the following compounds. F (CF 2 ) CH 2 CH 2 Si (OCH 3 ) 3 (surface tension; 23.4 mN / m), F (CF 2 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 3 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 (surface tension; 18.4 mN / m), F (CF 2 ) 6 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 (surface tension; 18.4 mN / m), F (CF 2 ) 6 CH 2 CH 2 CH 2 Si (OCH 3 ) 3
  • specific examples of the compound (21) include the following compounds. (CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 , (CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 , (CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 CH 2 Si (OCH 3 ) 3
  • F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 surface tension; 18.4 mN / m is particularly preferable.
  • the compound (b1) may be used alone or in combination of two or more.
  • Compound (b1) can be produced by a known method. Moreover, you may use a commercial item.
  • the content thereof is preferably 0.01 to 10% by mass with respect to the total solid content in the liquid composition, 0.1 to 3 The mass% is more preferable.
  • the content of the hydrolyzable silane compound (b1) in the liquid composition is in the above range, sufficient antifouling property can be imparted to the upper surface of the resulting UV-absorbing coating, and the transparency of the coating is reduced. And there is no risk of damaging the appearance due to uneven thickness.
  • the hydrolyzable silane compound (b2) is a compound represented by the following general formula (b2), and is a silicon compound (b) having a surface tension of 17.5 to 30 mN / m.
  • R 3 represents an alkyl group having 1 to 10 carbon atoms or —Y 1 —Si (R 5 ) n2 (X 3 ) 3-n2 group
  • R 4 each independently represents the number of carbon atoms.
  • Y 1 independently represents an alkylene group having 2 to 4 carbon atoms
  • R 5 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms having no fluorine atom
  • X 3 represents a hydrolyzable group
  • k is an integer of 10 to 200
  • n2 is 0, 1 or 2.
  • the compound (b2) is a linear polyorganosiloxane in which a hydrolyzable silyl group is bonded to one end or both ends via an alkylene group.
  • R 3 is an alkyl group having 1 to 10 carbon atoms
  • the compound (b2) is a linear polyorganosiloxane having a hydrolyzable silyl group at one end.
  • R 3 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms.
  • the repeating unit of SiR 4 2 O and R 4 in —SiR 4 2 — linked thereto are each independently an alkyl group having 1 to 3 carbon atoms, and having 1 to 3 carbon atoms A linear alkyl group is preferred, and a methyl group is more preferred.
  • R 4 may be different from each other, but is preferably the same.
  • K which is the number of repetitions of SiR 4 2 O is an integer of 10 to 200, preferably 10 to 150, more preferably 15 to 120. If the number of k is in the above range, sufficient antifouling property can be imparted to the surface of the resulting coating.
  • the compound (b2) is often used as a mixture in which the number of repeating units of SiR 4 2 O is different.
  • the number of each repeating unit is shown by an average value. In the case of an average value, the number of repeating units is not necessarily an integer, but a preferable range of numerical values is the same as described above.
  • X 3 in the hydrolyzable silyl group (—Si (R 5 ) n2 (X 3 ) 3-n2 ) possessed by the terminal of the compound (b2) represents a hydrolyzable group.
  • R 3 is a group represented by —Y 1 —Si (R 5 ) n2 (X 3 ) 3-n2
  • the compound (b2) is a linear polyorganosiloxane having hydrolyzable silyl groups at both ends. Therefore, it is preferable in that it has excellent moisture resistance and chemical resistance as compared with a compound having a hydrolyzable silyl group at one end.
  • the hydrolyzable silyl groups at both ends may be the same or different.
  • R 5 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and having no fluorine atom.
  • the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group.
  • R 5 is preferably a monovalent saturated hydrocarbon group.
  • the number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.
  • R 5 is preferably an alkyl group having 1 to 6 carbon atoms because synthesis is simple, and an alkyl group having 1 to 3 carbon atoms is more preferable from the viewpoint of easy acquisition and handling of raw materials.
  • R 5 in the hydrolyzable silyl group possessed by the compound (b2) is “n2”.
  • R 5 may be the same group or different groups, and the same group is preferable from the viewpoint of easy availability.
  • Y 1 which is a group linking — (SiR 4 2 O) k —SiR 4 2 — and a hydrolyzable silyl group independently represents an alkylene group having 2 to 4 carbon atoms. . Y 1 is preferably an alkylene group having 2 or 3 carbon atoms.
  • Y 1 is an alkylene group having 2 carbon atoms
  • Y 1 is represented as —C 2 H 4 — in the molecular formula of the formula (b2), and this is represented by —CH 2 CH 2 — and —CH (CH 3 ) —
  • a mixture such as These are mixtures that are difficult to separate in the production process, and even if used as a mixture, the effects of the present invention are not affected.
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene group having 3 carbon atoms
  • Y 1 is an alkylene
  • the compound (b2) include the following compounds.
  • k is an integer of 10 to 150.
  • the compound (b2) may be used alone or in combination of two or more.
  • Compound (b2) is a known method, for example, a silane in which a vinyl group-containing group and a hydrolyzable group are bonded to a silicon atom in the presence of a hydrosilylation catalyst in a linear polydiorganosiloxane having a hydrosilyl group at the terminal. Reacting a compound, or reacting a linear polydiorganosiloxane having a vinyl group-containing group at its end with a silane compound in which a hydrogen atom and a hydrolyzable group are bonded to a silicon atom in the presence of a hydrosilylation catalyst, etc. Can be manufactured.
  • the content thereof is preferably 0.01 to 10% by mass, preferably 0.1 to 3%, based on the total solid content in the liquid composition.
  • the mass% is more preferable.
  • diorganosilicone oil (b3) a silicon compound having a surface tension of 17.5 to 30 mN / m among silicon compounds generally classified as a diorganosilicone oil can be applied without particular limitation.
  • Specific examples of the diorganosilicone oil (b3) include a compound (b3) represented by the following formula (b3) (however, the surface tension is 17.5 to 30 mN / m).
  • R 6 3 Si—O— (SiR 7 2 O) m1 — (SiR 7 R 8 O) m2 —SiR 6 3 (b3)
  • R 6 is independently an alkyl group having 1 to 20 carbon atoms
  • R 7 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group
  • R 8 is A monovalent organic group having 1 to 20 carbon atoms and having a polyoxyalkylene group, an amide group or an ester group
  • m1 is an integer from 0 to 200
  • m2 is from 0 to 200
  • m1 + m2 is an integer from 10 to 200.
  • R 6 and R 7 in the formula (b3) are preferably a methyl group
  • R 8 is — (CH 2 ) m3 —O— (CH 2 —CH 2 —O—) m4 — (CH 2- CHCH 3 —O—) m5 —R 9
  • m3 is an integer from 2 to 10
  • m4 is from 0 to 200
  • m5 is from 0 to 200
  • m4 + m5 is an integer from 1 to 200).
  • diorganosilicone oil (b3) may be used alone or in combination of two or more.
  • the diorganosilicone oil (b3) can be produced by a known method.
  • commercially available products such as BYK-307 (trade name, manufactured by Big Chemie, polyether-modified polydimethylsiloxane, surface tension: 26.4 mN / m) may be used.
  • the content thereof is preferably 0.01 to 10% by mass, preferably 0.5 to 3% by mass with respect to the total solid content in the liquid composition. % Is more preferable.
  • the content of the diorganosilicone oil (b3) in the liquid composition is in the above range, sufficient antifouling property can be imparted to the upper surface of the obtained UV-absorbing film, and the transparency and thickness of the film There is no risk of damaging the appearance due to unevenness.
  • the film formed using the liquid composition of the present invention contains a cured product of a hydrolyzable silane compound mainly composed of the hydrolyzable silane compound (c) as a film forming component.
  • the content of the hydrolyzable silane compound (c) in the liquid composition is preferably 5 to 90% by mass and more preferably 10 to 50% by mass with respect to the total solid content in the liquid composition.
  • the content of the hydrolyzable silane compound (c) includes, for example, the amount of the hydrolyzable silyl group in the case where the ultraviolet absorber (a) has a hydrolyzable silyl group.
  • the hydrolyzable silane compound (c) is a compound (1) represented by the following formula (1), and is a compound excluding the hydrolyzable silane compound (b1) and the hydrolyzable silane compound (b2).
  • R H1 n1 SiX 1 4-n1 (1) In the formula (1), n1 is an integer of 0 to 3, R H1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms having no fluorine atom, and X 1 is hydrolyzable. When a plurality of R H1 and X 1 are present, these may be different or the same.
  • Compound (1) comprises a number of monofunctional ⁇ tetrafunctional hydrolyzable silane compound having 1 to 4 hydrolyzable groups represented by "4-n1" (X 1).
  • the compound (1) one type may be used alone, or two or more types may be used in combination.
  • a trifunctional or tetrafunctional hydrolyzable silane compound is usually used to form a three-dimensional siloxane bond.
  • a monofunctional hydrolyzable silane compound and a bifunctional hydrolyzable silane compound May be used.
  • the hydrolyzable group (X 1 ) of the compound (1) is preferably an organooxy group such as an alkoxy group, an alkenyloxy group, an acyloxy group, an iminoxy group, an aminoxy group, and particularly preferably an alkoxy group.
  • an alkoxy group having 1 to 4 carbon atoms and an alkoxy-substituted alkoxy group having 2 to 4 carbon atoms are preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • Tetrafunctional hydrolyzable silane compound is represented by SiX 1 4.
  • the hydrolyzable group (X 1 ) is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group and an ethoxy group.
  • SiX 1 4 specifically, tetramethoxysilane, tetraethoxysilane, tetra -n- propoxysilane, tetra -n- butoxysilane, tetra -sec- butoxysilane, tetra -tert- butoxysilane.
  • tetraethoxysilane, tetramethoxysilane or the like is preferably used. These may be used alone or in combination of two or more.
  • the trifunctional hydrolyzable silane compound is a compound in which three hydrolyzable groups and one R H1 are bonded to a silicon atom. Three of the hydrolyzable groups may be the same as or different from each other.
  • the hydrolyzable group is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group and an ethoxy group.
  • R H1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms and having no fluorine atom.
  • the unsubstituted hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or an aryl group, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
  • trifunctional hydrolyzable silane compounds in which R H1 is an unsubstituted hydrocarbon group include methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, methyltrimethoxysilane.
  • These may be used alone or in combination of two or more.
  • R H1 may have include an epoxy group, a (meth) acryloxy group, a primary or secondary amino group, an oxetanyl group, a vinyl group, a styryl group, a ureido group, a mercapto group, an isocyanate group, and a cyano group.
  • Group, halogen atom and the like An epoxy group, (meth) acryloxy group, primary or secondary amino group, oxetanyl group, vinyl group, ureido group, mercapto group and the like are preferable.
  • an epoxy group, a primary or secondary amino group, and a (meth) acryloxy group are preferable.
  • the group having an epoxy group is preferably a glycidoxy group or a 3,4-epoxycyclohexyl group, and the primary or secondary amino group is an amino group, a monoalkylamino group, a phenylamino group, or N- (aminoalkyl).
  • An amino group or the like is preferable.
  • trifunctional hydrolyzable silane compound in which R H1 is a substituted hydrocarbon group examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, di- (3-methacryloxy) propyltriethoxysilane, etc. .
  • 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane and the like are particularly preferred. These may be used alone or in combination of two or more.
  • the hydrolyzable silane compound (c) is preferably composed of (1) only a tetrafunctional hydrolyzable silane compound or (2) a tetrafunctional hydrolyzable silane compound and a trifunctional hydrolyzable silane compound. Consists of. In the present invention, (1) it is particularly preferable to be composed only of a tetrafunctional hydrolyzable silane compound. In the case of (1), in particular, the liquid composition further contains a flexible component (f) described later in order to obtain sufficient crack resistance while ensuring a certain thickness of the coating film obtained. It is preferable.
  • the content ratio of the tetrafunctional hydrolyzable silane compound to the trifunctional hydrolyzable silane compound is a mass ratio of tetrafunctional hydrolyzable silane compound / 3 trifunctional hydrolyzable silane compound. 30/70 to 95/5 is preferable, 40/60 to 90/10 is more preferable, and 50/50 to 85/15 is particularly preferable.
  • the bifunctional hydrolyzable silane compound is optionally used in (1) and (2) as necessary.
  • the content is preferably 30% by mass or less based on the total mass of the hydrolyzable silane compound.
  • the hydrolyzable silane compound is at least partially partially hydrolyzed (co) condensed rather than consisting of only the unreacted hydrolyzable silane compound, that is, the monomer of the hydrolyzable silane compound. It is preferable in terms of stability and uniform reactivity of the hydrolyzable silane compound in the liquid composition.
  • the hydrolyzable silane compound (c) is blended into the liquid composition as a partial hydrolysis condensate of the hydrolyzable silane compound (c) (monomer), or the hydrolyzable silane compound (c). It is preferable to mix the (monomer) with other components contained in the liquid composition and then partially hydrolyze and condense at least a part thereof to form a liquid composition.
  • the silicon compound (b) (monomer) is a partially hydrolyzed condensate. Or after mixing silicon compound (b) (monomer) with other components contained in the liquid composition, at least a portion thereof is partially hydrolyzed to form a liquid composition. It is preferable.
  • the hydrolyzable silane compound (c), the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound ( b2) may be blended as each of the partial hydrolysis condensates or as these partial hydrolysis cocondensates.
  • the hydrolyzable silane compound (c) and the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound (b2) as a partially hydrolyzed cocondensate Is preferred.
  • the partial hydrolysis cocondensation may be performed in advance or after being mixed with other components contained in the liquid composition.
  • the partially hydrolyzed (co) condensate is an oligomer (multimer) produced by hydrolysis and subsequent dehydration condensation of a hydrolyzable silane compound.
  • the partially hydrolyzed (co) condensate is a high molecular weight compound that is usually soluble in a solvent.
  • the partially hydrolyzed (co) condensate has a hydrolyzable group and a silanol group, and further has a property of being hydrolyzed (co) condensed to be a final cured product.
  • a partially hydrolyzed condensate can be obtained from only one kind of hydrolyzable silane compound, and a partially hydrolyzed condensate that is a cocondensate thereof can be obtained from two or more kinds of hydrolyzable silane compounds. it can.
  • the partial hydrolysis (co) condensation of the hydrolyzable silane compound is performed, for example, by using a reaction solution obtained by adding water to a lower alcohol solution of the hydrolyzable silane compound in the presence of an acid catalyst at 1 to 48 at 1 to 48 ° C. This can be done by stirring for a period of time.
  • the acid catalyst used in the reaction include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid, formic acid, acetic acid, propionic acid, glycolic acid, oxalic acid, malonic acid, succinic acid, maleic acid, and phthalic acid.
  • examples thereof include carboxylic acids such as acid, citric acid and malic acid, and sulfonic acids such as methanesulfonic acid.
  • the amount of acid to be added can be set without particular limitation as long as it can function as a catalyst. Specifically, the amount of acid added is 0.001 to 3.0 moles relative to the volume of the reaction solution containing the hydrolyzable silane compound. An amount of about / L can be mentioned.
  • the liquid composition contains water and an organic solvent for the hydrolysis as the solvent (d).
  • the organic solvent is compatible with water and dissolves components such as the ultraviolet absorber (a), silicon compound (b), hydrolyzable silane compound (c), and an infrared absorber (e) described later. It means a dispersion medium that disperses solid fine particles, and means an organic compound that is liquid at room temperature with a relatively low boiling point.
  • An organic solvent consists of organic compounds, such as alcohol, and 2 or more types of mixtures may be sufficient as it.
  • the dispersion medium and the solvent may be the same organic solvent or different organic solvents.
  • the organic solvent in the liquid composition is a mixture of the dispersion medium and the solvent.
  • the dispersion medium and the solvent are a combination having compatibility so that the mixture becomes a uniform mixture.
  • each compounding ingredient such as ultraviolet absorber (a), silicon compound (b), hydrolysable silane compound (c), and infrared absorber (e)
  • each compounding ingredient such as ultraviolet absorber (a), silicon compound (b), hydrolysable silane compound (c), and infrared absorber (e)
  • it may be used as a part of the organic solvent or water of the liquid composition.
  • the content of water in the liquid composition is calculated as an amount including water brought together with various components in addition to the amount added alone as water.
  • the amount of water contained in the liquid composition is not particularly limited as long as it is an amount sufficient to hydrolyze (co) condensate the hydrolyzable silicon compound contained.
  • the amount is preferably 1 to 20 equivalents, more preferably 4 to 18 equivalents, with respect to the SiO 2 equivalent of the hydrolyzable silicon compound contained.
  • the amount of water is less than 1 equivalent in the above molar ratio, hydrolysis does not easily proceed, and depending on the substrate, the liquid composition may be repelled or haze may increase during application. The speed may increase and long-term storage may not be sufficient.
  • organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetyl acetone; tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether Ethers such as diisopropyl ether; esters such as ethyl acetate, butyl acetate, isobutyl acetate, methoxyethyl acetate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1 -Propanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, 1-methoxy-2-propanol, 2-ethoxyethanol, diacetone alcohol Alcohols and the like; n-hexane,
  • the amount of the organic solvent to be used is appropriately adjusted depending on the types and blending ratios of the components (a) to (c) and (e).
  • the organic solvent contains at least 20% by mass of alcohol, preferably 50% by mass or more.
  • Alcohols used in such organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxy Ethanol, 4-methyl-2-pentanol, 2-butoxyethanol and the like are preferable.
  • the solubility of the silicon oxide matrix raw material component is good, and the coating property to the substrate is good Therefore, alcohol having a boiling point of 80 to 160 ° C. is preferable.
  • ethanol 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4-methyl-2- Pentanol and 2-butoxyethanol are preferred.
  • an organic solvent used for a liquid composition for example, when a partially hydrolyzed (co) condensate of a hydrolyzable silane compound is included, a raw material hydrolyzable silane compound (for example, an alkoxy group) is produced during the production process.
  • the lower alcohol generated by hydrolyzing the silanes having a hydrolyzate or the alcohol used as a solvent may be included as it is.
  • an organic solvent other than the above an organic solvent other than the alcohol miscible with water / alcohol may be used in combination.
  • Ketones such as acetylacetone; esters such as ethyl acetate and isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.
  • the amount of the solvent (d) contained in the liquid composition is preferably such that the total solid concentration in the liquid composition comprising the solvent (d) and the total solid content is 3.5 to 50% by mass, and 9 to 30% by mass. % Is more preferred. Workability
  • the liquid composition of the present invention may optionally contain a functional component other than the ultraviolet absorber (a), such as an infrared absorber (e), or a component that improves the film formability of the coating, such as a flexible component ( f) may be included.
  • a functional component other than the ultraviolet absorber (a) such as an infrared absorber (e)
  • e infrared absorber
  • a component that improves the film formability of the coating such as a flexible component ( f) may be included.
  • the infrared absorbent (e) is not particularly limited as long as it is a compound having a function of absorbing light in the infrared wavelength region.
  • Specific examples of the infrared absorber (e) include one or more selected from composite tungsten oxide, antimony-doped tin oxide (ATO), and tin-doped indium oxide (ITO). These infrared absorbers (e) are used in the form of fine particles.
  • the composite tungsten oxide a general formula: M x W y O z (wherein M element is Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn) 1 or more elements selected from the following: W is tungsten; O is oxygen; 0.001 ⁇ x / y ⁇ 1.0; 2.2 ⁇ z / y ⁇ 3.0) Can be mentioned.
  • the composite tungsten oxide represented by the above general formula functions effectively as an infrared absorber because a sufficient amount of free electrons are generated.
  • the fine particles of the composite tungsten oxide represented by the general formula: M x W y O z have excellent durability when having a hexagonal, tetragonal, or cubic crystal structure. It preferably includes one or more crystal structures selected from crystal and cubic.
  • the amount (x) of the added M element is 0.001 or more and 1.0 or less in terms of the molar ratio with respect to the amount (y) of tungsten, and the value of x / y.
  • the abundance (z) is 2.2 or more and 3.0 or less in terms of a molar ratio to the amount (y) of tungsten and a value of z / y.
  • the value of x / y is preferably about 0.33. This is because the x / y value theoretically calculated from the hexagonal crystal structure is 0.33, and the composite tungsten is contained by containing the M element in such an amount that the x / y value is around this value. This is because the oxide fine particles exhibit preferable optical characteristics.
  • Specific examples of such composite tungsten oxide include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like.
  • the composite tungsten oxide used in the present invention is not limited to these, and has useful infrared absorption characteristics as long as the values of x / y and z / y are in the above ranges.
  • Such a composite tungsten oxide is known to have a maximum value in the wavelength range of 400 to 700 nm and a minimum value in the wavelength range of 700 to 1800 nm in the film in which the fine particles are uniformly dispersed. It is an infrared absorber.
  • the fine particles of the composite tungsten oxide represented by the general formula: M x W y O z can be produced by a conventionally known method. For example, using an ammonium tungstate aqueous solution or a tungsten compound starting material in which a tungsten hexachloride solution and an aqueous solution of an element M chloride salt, nitrate, sulfate, oxalate, oxide, etc. are mixed at a predetermined ratio, these are used.
  • Composite tungsten oxide fine particles can be obtained by heat treatment in an inert gas atmosphere or a reducing gas atmosphere.
  • the surface of the composite tungsten oxide fine particles is preferably coated with a metal oxide selected from Si, Ti, Zr, Al and the like from the viewpoint of improving weather resistance.
  • a metal oxide selected from Si, Ti, Zr, Al and the like from the viewpoint of improving weather resistance.
  • the coating method is not particularly limited, it is possible to coat the surface of the composite tungsten oxide fine particles by adding the metal alkoxide to the solution in which the composite tungsten oxide fine particles are dispersed.
  • the ATO fine particles and the ITO fine particles are obtained by various conventionally known preparation methods, for example, a physical method obtained by pulverizing metal powder by a mechanochemical method or the like; CVD method, vapor deposition method, sputtering method, thermal plasma method, laser method Chemical dry methods such as: pyrolysis method, chemical reduction method, electrolysis method, ultrasonic method, laser ablation method, supercritical fluid method, method called chemical wet method by microwave synthesis method, etc.
  • the prepared one can be used without particular limitation.
  • the crystal system of these fine particles is not limited to a normal cubic crystal, and depending on the type of the hydrolyzable silane compound (c), for example, hexagonal ITO having a relatively low infrared absorbing ability can be used as necessary. .
  • the composite tungsten oxide fine particles, ATO fine particles, and ITO fine particles may be used alone as an infrared absorber (e), or two or more kinds may be mixed and used.
  • ITO fine particles are preferably used from the viewpoint of transmittance loss and environmental safety.
  • at least one selected from the above-mentioned composite tungsten oxide fine particles, ATO fine particles, and ITO fine particles may be used in combination with other infrared-absorbing fine particles as the infrared absorbent (e).
  • the average primary particle diameter in the fine particles of the infrared absorber (e) is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less.
  • the fine particles of the infrared absorbent (e) may be aggregated to some extent in the liquid composition, but the average dispersed particle diameter is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less. is there.
  • the average primary particle diameter and average dispersed particle diameter are preferably set in terms of maintaining transparency.
  • the lower limit of the average primary particle diameter is not particularly limited, but infrared absorber (e) fine particles of about 2 nm that can be produced by the current technology can also be used.
  • the average primary particle diameter of the fine particles refers to that measured from an observation image with a transmission electron microscope.
  • the lower limit of the average dispersed particle size is not particularly limited.
  • the average dispersed particle size refers to that measured by a dynamic scattering method using a particle size distribution measuring device (Microtrac 150: Nanotrac 150).
  • the content of the infrared absorbent (e) in the liquid composition is such that the obtained coating film has sufficient infrared absorption ability and the mechanical strength of the coating film is ensured, so that the hydrolyzable silane compound (c) is 100 masses. 1 part by weight or when the liquid composition contains the flexible component (f), the total amount of hydrolyzable silane compound (c) and flexible component (f) is 100 parts by weight. It is preferably ⁇ 80 parts by mass, more preferably 5 to 60 parts by mass, and particularly preferably 5 to 40 parts by mass.
  • the inorganic fine particles used as the infrared absorber (e) are prepared in the form of a dispersion liquid prepared by dispersing inorganic fine particles in a dispersion medium in advance. It is preferable to mix
  • the agglomerated state of the infrared absorbent (e) fine particles in the resulting coating reflects the agglomerated state in the liquid composition and further in the raw material dispersion. Therefore, in order to maintain the transparency of the coating, infrared absorption is required.
  • the fine particles of the agent (e) are preferably highly dispersed in the dispersion. From the viewpoint of dispersibility, the dispersion liquid in which the fine particles of the infrared absorber (e) are dispersed is preferably a dispersion liquid dispersed using a dispersant described later.
  • the dispersion medium in the dispersion of the infrared absorbent (e) fine particles constitutes a part of the organic solvent contained in the composition in the resulting composition.
  • a compound having compatibility with an organic solvent is preferably used as a dispersion medium.
  • the liquid composition contains the infrared absorbent (e) in addition to the ultraviolet absorbent (a), the complex is further formed with the infrared absorbent (e) for the following reason, It is preferable to contain a chelating agent that does not substantially absorb light having a visible light wavelength.
  • “Substantially no absorption” means, for example, a liquid composition obtained by adding 50 parts by mass of a chelating agent to 100 parts by mass of the infrared absorber (e), and the infrared absorber (e) is on the substrate.
  • the maximum absorption wavelength of light in the UV-absorbing organic compound contained in the UV absorber (a) is in the range of 325 to 425 nm, and is generally in the range of 325 to 390 nm.
  • these compounds have the said infrared absorber ( It is considered that the inorganic fine particles constituting e) are chelate-bonded to easily develop a yellow color. Therefore, together with the ultraviolet absorber (a) and the infrared absorber (e), a complex is formed with the infrared absorber (e) in the liquid composition, and the complex substantially absorbs light of visible light wavelength. If a chelating agent not shown is contained, the chelate bond between the ultraviolet absorber (a) and the infrared absorber (e) can be suppressed, and yellow color development can be prevented while maintaining the ultraviolet absorbing ability.
  • the dispersing agent is a dispersion medium (becomes a part of the organic solvent in the liquid composition) from at least the part of the molecule that adsorbs to the surface of the fine particle and the part that adsorbs to the fine particle.
  • a chelating agent is a compound that can be coordinated to a plurality of positions on the surface of a fine particle with one molecule, has little steric hindrance after adsorption to the fine particle due to the molecular structure, and is stable in dispersion of the fine particle. It is a generic term for compounds that do not have the function of increasing the properties. Although the dispersant and the chelating agent are both adsorbed on the surface of the fine particles, the dispersing agent has a function of increasing the dispersion stability, whereas the chelating agent is different in that it does not have the function.
  • the molecular weight of the chelating agent is preferably 1,000 to 100,000.
  • the molecular weight is more preferably 1,500 to 100,000, and particularly preferably 2,000 to 100,000. If the molecular weight of the chelating agent is within the above range, it is adsorbed and coordinated with the surface of the infrared absorbent (e) fine particles together with the dispersant, and the ultraviolet absorbent (a) is chelate-bonded to the fine particles of the infrared absorbent (e).
  • the chelating agent bleeds out from the film after the film is formed, The adsorption point with respect to the molecule is reduced, and further, the hardness of the film is hardly lowered.
  • the dispersant has a portion that adsorbs to the surface of the fine particles of the infrared absorber (e) and a portion that extends into the dispersion medium (which becomes a part of the organic solvent) and ensures dispersion stability. And the suitable quantity by which the dispersion stability of the microparticles
  • An appropriate amount of such a dispersant may not be an amount sufficient to sufficiently cover the surface of the fine particles of the infrared absorber (e) and suppress chelate bonds of the ultraviolet absorber (a).
  • the chelating agent and the dispersing agent together can sufficiently cover the surface of the fine particles of the infrared absorbing agent (e), and the infrared ray of the ultraviolet absorbing agent (a).
  • the chelate bond to the absorbent (e) fine particles can be sufficiently suppressed.
  • the content of the chelating agent in the liquid composition is preferably 1 to 13 parts by mass with respect to 100 parts by mass of the infrared absorber (e), and is appropriately adjusted within the above range according to the content of the dispersant. do it.
  • the content of the chelating agent is sufficient to cause the ultraviolet absorbent (a) to chelate bond to the fine particles of the infrared absorbent (e) in the liquid composition when the molecular weight chelating agent is used together with the dispersant.
  • the chelating agent may be contained in a dispersion containing fine particles of the infrared absorber (e), a dispersant, and a dispersion medium (which becomes a part of the solvent (d)).
  • the prepared ultraviolet absorber (a), silicon compound (b), hydrolyzable silane compound (c) and the like are contained in a solution in which the solvent (d) is dissolved. It is preferable from the point which suppresses the chelate bond of an agent (a) efficiently.
  • the chelating agent is appropriately selected depending on the type of the solvent (d). Since the liquid composition contains water and preferably alcohol as the solvent (d) as described above, a chelating agent soluble in these polar solvents is preferable.
  • a chelating agent specifically, a polymer having one or more selected from maleic acid, acrylic acid and methacrylic acid as a monomer, preferably a polymer having the above molecular weight range, and the like can be mentioned.
  • the polymer may be a homopolymer or a copolymer.
  • polymaleic acid and polyacrylic acid are preferably used. These may be used alone or in combination of two or more.
  • a commercially available product can be used as the chelating agent.
  • Commercially available products include, for example, non-pole PMA-50W (trade name, manufactured by NOF Corporation, molecular weight: 1,200, aqueous solution having a solid content of 40 to 48% by mass) as polymaleic acid, and aqualic HL as polyacrylic acid. (Trade name, manufactured by Nippon Shokubai Co., Ltd., molecular weight: 10,000, aqueous solution having a solid content of 45.5% by mass) and the like.
  • the flexible component (f) can contribute to the suppression of crack generation in the film obtained from the liquid composition.
  • the hydrolyzable silane compound (c) is composed only of a tetrafunctional hydrolyzable silane compound
  • the film may not have sufficient flexibility. If the liquid composition contains the flexible component (f) together with the tetrafunctional hydrolyzable silane compound, a film excellent in both mechanical strength and crack resistance can be easily produced.
  • the flexible component (f) examples include silicone resins, acrylic resins, polyester resins, polyurethane resins, hydrophilic organic resins containing polyoxyalkylene groups, various organic resins such as epoxy resins, and organic compounds such as glycerin. be able to.
  • the form is preferably liquid, fine particles or the like.
  • the organic resin may also be a curable resin that cures as the hydrolyzable silane compound (c) is cured by heating when a film is formed using a liquid composition containing the organic resin. In this case, a part of the hydrolyzable silane compound (c) and the curable resin that is the flexible component (f) may partially react to crosslink within a range that does not impair the properties of the resulting film. .
  • the silicone resin is preferably a silicone oil containing various modified silicone oils (excluding the compound (b3)), and the terminal is a hydrolyzable silyl group or a polymerizable group-containing organic group.
  • examples thereof include silicone rubber in which the diorganosilicone contained is partially or wholly crosslinked.
  • hydrophilic organic resin containing a polyoxyalkylene group examples include polyethylene glycol (PEG) and polyether phosphate ester polymers.
  • the polyurethane resin is polyurethane rubber or the like
  • the acrylic resin is acrylonitrile rubber, a homopolymer of (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester and a copolymer capable of copolymerizing with the (meth) acrylic acid alkyl ester.
  • Preferred examples include copolymers with a monomer.
  • the monomer copolymerizable with the (meth) acrylic acid alkyl ester has a partial structure of a hydroxyalkyl ester of (meth) acrylic acid, a (meth) acrylic acid ester having a polyoxyalkylene group, or an ultraviolet absorber.
  • a (meth) acrylic acid ester, a (meth) acrylic acid ester having a silicon atom, or the like can be used.
  • polyepoxides are a general term for compounds having a plurality of epoxy groups. That is, the average number of epoxy groups of the polyepoxides is 2 or more, but in the present invention, polyepoxides having an average number of epoxy groups of 2 to 10 are preferred.
  • Such polyepoxides are preferably polyglycidyl compounds such as polyglycidyl ether compounds, polyglycidyl ester compounds, and polyglycidyl amine compounds.
  • the polyepoxides may be either aliphatic polyepoxides or aromatic polyepoxides, and aliphatic polyepoxides are preferred.
  • polyglycidyl ether compounds are preferred, and aliphatic polyglycidyl ether compounds are particularly preferred.
  • a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is particularly preferable from the viewpoint of improving light resistance.
  • These alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.
  • polyglycidyl ether compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol poly Examples thereof include glycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. These may use only 1 type and may use 2 or more types together.
  • a poly of an aliphatic polyol having three or more hydroxyl groups such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.
  • Glycidyl ether one having an average number of glycidyl groups (epoxy groups) exceeding 2 per molecule is preferred. These may be used alone or in combination of two or more.
  • epoxy resins particularly polyepoxides, PEG, glycerin and the like can impart sufficient flexibility to the resulting coating while maintaining mechanical strength. It is preferable from the point.
  • the above epoxy resins, particularly polyepoxides, PEG, glycerin, etc. in addition to the function of preventing the occurrence of cracks due to light irradiation over a long period of time, while ensuring the colorless transparency of the resulting coating, A film provided with various functions such as infrared absorption has a function of suppressing a decrease in the function.
  • polyepoxides are particularly preferable among these.
  • the content of the flexible component (f) in the liquid composition is not particularly limited as long as it is an amount capable of imparting flexibility to the resulting coating and improving crack resistance without impairing the effects of the present invention.
  • An amount of 0.1 to 100 parts by mass is preferable with respect to 100 parts by mass of the hydrolyzable silane compound (c), and an amount of 1.0 to 50 parts by mass is more preferable.
  • the liquid composition includes the ultraviolet absorber (a), silicon compound (b), hydrolyzable silane compound (c), and solvent (d) as essential components, and an infrared absorber (e) as an optional component, flexible
  • the component (f), the dispersing agent, the chelating agent and the like are contained in a content appropriately adjusted within the above range.
  • the liquid composition can further contain various optional compounding agents as necessary within a range not impairing the effects of the present invention.
  • an additive such as a surface conditioner, an antifoaming agent or a viscosity conditioner may be included for the purpose of improving the coatability on the surface to be formed, usually the substrate surface, and to the substrate surface.
  • an additive such as an adhesion-imparting agent may be included.
  • the amount of these additives is preferably 0.01 to 2 parts by mass for each additive component with respect to 100 parts by mass of the total of the components (c) and (f).
  • the liquid composition may contain a dye, a pigment, a filler and the like as long as the effects of the present invention are not impaired.
  • silica fine particles are preferable.
  • silica fine particles are blended in the liquid composition, it is preferably blended as colloidal silica.
  • Colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.
  • Silica fine particles preferably have an average particle size (BET method) of 1 to 100 nm. If the average particle diameter exceeds 100 nm, the particles diffusely reflect light, and thus the haze value (haze value) of the resulting film increases, which may be undesirable in terms of optical quality. Further, the average particle size is particularly preferably 5 to 40 nm. This is for imparting abrasion resistance to the coating and maintaining the transparency of the coating.
  • colloidal silica can use both a water dispersion type and an organic solvent dispersion type, it is preferable to use an organic solvent dispersion type.
  • the content of the silica fine particles is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the hydrolyzable silicon compound (c).
  • the content range described above maintains the film formability of the film while ensuring sufficient wear resistance. This is the range of the content of silica fine particles that can prevent the decrease in transparency of the coating due to aggregation.
  • the liquid composition can be prepared by uniformly mixing the above components.
  • the mixing method is not particularly limited, but when the liquid composition contains the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound (b2) as the silicon compound (b), the hydrolyzable silane compound (c It is preferable to mix on the conditions on which partial hydrolysis cocondensation with this is performed.
  • a method may be used in which the silicon compound (b) and the hydrolyzable silane compound (c) are partially hydrolyzed and co-condensed in the solvent (d), and other components such as an ultraviolet absorber (a) are added to the resulting solution.
  • the silicon compound (b) and the hydrolyzable silane compound (c) are partially hydrolyzed and co-condensed, and then a dispersion of the infrared absorber (e) is blended. There may be.
  • ultraviolet absorber (a), silicon compound (b), hydrolyzable silane compound (c), solvent (d), infrared absorber (e), flexible component (f), dispersant, chelating agent can be prepared by a method including the following step (1) and step (2).
  • Step (1) Dispersion preparing step for obtaining a dispersion by mixing the infrared absorbent (e), the dispersant, and a dispersion medium (corresponding to part or all of the organic solvent)
  • Step (2) Step ( 1), the ultraviolet absorbent (a), the chelating agent, the silicon compound (b), the hydrolyzable silane compound (c), the flexible component (f), water, an acid catalyst,
  • the mixing method is not particularly limited as long as it can be uniformly mixed. Specific examples include a mixing method using a magnetic stirrer or the like.
  • the liquid composition of the present invention contains the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound (b2) or the hydrolyzable silicon compound (c) as a monomer, it is preserved.
  • a treatment for partially hydrolyzing and co-condensing them may be performed.
  • This partial hydrolysis cocondensation is preferably performed in the presence of the same acid catalyst as described above under the same reaction conditions as described above.
  • the object can be achieved by mixing at least one hydrolyzable silicon compound as required, followed by stirring in the presence of an acid catalyst at 10 to 70 ° C. for a predetermined time.
  • a liquid composition for forming a silicon oxide-based cured film by the sol-gel method of the present invention is obtained.
  • the liquid composition for forming a film of the present invention is applied to the surface of a substrate on which a film is formed, heated and cured to form a silicon oxide-based cured film by a sol-gel method.
  • a cured film is excellent in ultraviolet-absorbing ability by containing a ultraviolet absorber (a).
  • the silicon compound (b) having a surface tension of 17.5 to 30 mN / m moves to the upper surface of the film in the course of film formation, and in particular, the hydrolyzable silane compound (b1) and / or the hydrolyzable silane compound (b2 In the case of), it is sufficiently immobilized on the upper surface of the coating.
  • the film obtained thereby has excellent antifouling properties and sufficient durability.
  • the material of the substrate to which the liquid composition for film formation of the present invention is applied is not particularly limited, and basically includes transparent glass, resin, and the like.
  • the substrate is glass
  • examples of the material include ordinary soda lime glass, borosilicate glass, alkali-free glass, and quartz glass.
  • the glass substrate it is also possible to use a glass substrate that absorbs ultraviolet rays or infrared rays.
  • the substrate is a resin
  • examples of the material include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and the like.
  • the shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature.
  • the thickness of the substrate can be appropriately selected depending on the application, but generally it is preferably 1 to 10 mm.
  • the visible light transmittance of the substrate tends to decrease as the mixing ratio of the infrared absorber (e) in the coating increases.
  • the transmittance is preferably 72% or more, more preferably 74% or more, as the visible light transmittance measured according to JIS R3212 (1998).
  • a glass substrate is preferable from the viewpoint of the weather resistance of the substrate and the adhesion between the coating and the substrate.
  • the glass article which has the film formed on the glass base material using the liquid composition of this invention is demonstrated.
  • the glass article of the present invention has a glass substrate and a film formed on the surface of at least a part of the glass substrate using the liquid composition of the present invention.
  • the surface on which the film is formed is appropriately selected according to the application. Usually, although it forms in any one of the main surfaces of a plate-shaped glass base material, it is not limited to this.
  • a specific method for forming a film on the surface of the glass substrate using the liquid composition of the present invention is as follows: (I) Liquid composition on the film-forming surface of the glass substrate And (II) removing volatile components such as an organic solvent, water, and acid from the obtained coating film as necessary, and adding a hydrolyzable silane compound (c) as a main component. And a step of curing the coating film by heating to a temperature at which the decomposable silane compound is cured.
  • the liquid composition is applied to the film-forming surface of the glass substrate to form a coating film of the liquid composition.
  • the coating film formed here is a coating film containing volatile components, such as the said organic solvent and water normally.
  • the application method of the liquid composition on the glass substrate is not particularly limited as long as it is a method of uniform application, and a flow coating method, a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen printing method. Known methods such as a method, a gravure printing method, a roll coating method, a meniscus coating method, and a die coating method can be used.
  • the thickness of the coating film of the coating solution is determined in consideration of the thickness of the finally obtained film.
  • the (II) step to be carried out is carried out by appropriately selecting conditions according to the hydrolyzable silane compound (c) to be used. That is, in the step (II), volatile components such as an organic solvent and water are removed from the coating film of the liquid composition on the glass substrate as necessary, and a hydrolyzable silicon compound and other curing components are included. In some cases, the cured component is heated and cured to form a coating.
  • the removal of volatile components from the coating film in the step (II) is preferably performed by heating and / or drying under reduced pressure.
  • After forming the coating film on the glass substrate it is preferable to perform temporary drying at a temperature of about room temperature to 120 ° C. from the viewpoint of improving the leveling property of the coating film.
  • temporary drying it is preferable to perform temporary drying at a temperature of about room temperature to 120 ° C. from the viewpoint of improving the leveling property of the coating film.
  • volatile components are vaporized and removed in parallel with this operation, so it can be said that the operation of removing volatile components is included in the temporary drying.
  • the silicon compound (b) having a surface tension of 17.5 to 30 mN / m in the liquid composition moves to the vicinity of the surface of the coating film.
  • the temporary drying time that is, the operation time for removing volatile components, is preferably about 3 seconds to 2 hours, although it depends on the liquid composition used for film formation.
  • the volatile component is sufficiently removed, but it may not be completely removed. That is, a part of the volatile component can remain in the film as long as the performance of the finally obtained film is not affected.
  • heating for removing the volatile component that is, generally temporary drying, and then hydrolyzable silicon compound and When other curing components are included, heating for curing the curing components may be continuously performed.
  • the coating is obtained by curing the curing component such as the hydrolyzable silicon compound by heating.
  • the upper limit of the heating temperature in this case is preferably 230 ° C. from the viewpoint of economic efficiency and in many cases the coating film contains an organic substance.
  • the lower limit of the heating temperature is preferably 80 ° C, and more preferably 150 ° C. Accordingly, the heating temperature is preferably in the range of 80 to 230 ° C, more preferably in the range of 150 to 230 ° C.
  • the heating time is preferably from several minutes to several hours, although it depends on the composition of the liquid composition used for film formation.
  • the thickness of the coating is preferably 1.0 to 7.0 ⁇ m, more preferably 1.5 to 5.5 ⁇ m.
  • the film thickness is less than 1.0 ⁇ m, the function of absorbing ultraviolet rays or absorbing infrared rays may not be sufficiently exhibited. Further, cracks may occur when the film thickness exceeds 7.0 ⁇ m.
  • the glass article of the present invention having the coating has ultraviolet shielding properties.
  • the ultraviolet transmittance of the glass article of the present invention measured using a spectrophotometer is 3.0% or less as the ultraviolet transmittance measured according to ISO-9050 (1990). Is preferably 1.0% or less, and particularly preferably 0.5% or less.
  • the glass article of the present invention having the coating has antifouling properties.
  • the antifouling property of the coating can be evaluated by, for example, water repellency or oil repellency. Specifically, water repellency can be evaluated using a contact angle with water as an index, and oil repellency can be evaluated using a contact angle with oleic acid as an index.
  • the water contact angle measured on the coating surface is preferably 70 degrees or more, more preferably 90 degrees or more.
  • the oleic acid contact angle measured on the coating surface is preferably 35 degrees or more, and more preferably 43 degrees or more.
  • the liquid composition for forming the coating film has good compatibility between the silicon compound (b) having a surface tension of 17.5 to 30 mN / m and the hydrolyzable silane compound (c). It is possible to keep the haze value of a glass article obtained by using an object at a low level.
  • the haze value is preferably 1% or less, and more preferably 0.5% or less.
  • the film having a single layer structure is provided with both functions of absorbing ultraviolet rays and antifouling.
  • the antifouling property can be sustained over a long period of time as compared with the case where the ultraviolet absorbing film and the antifouling film are laminated. It also has excellent wear resistance.
  • the solar transmittance in the glass article of the present invention is the solar transmittance measured according to JIS R3106 (1998) is preferably 48.0% or less, more preferably 46.0% or less, and particularly preferably 44.0% or less. preferable.
  • the transmittance of light having a wavelength of 1500 nm is preferably 35% or less, and more preferably 30% or less.
  • the visible light transmittance in the glass article of the invention is preferably 50% or more, more preferably 70% or more, and more preferably 72% or more as the visible light transmittance measured according to JIS R3212 (1998). It is particularly preferred that
  • the liquid composition for forming the film contains, for example, an ultraviolet absorber (a) and an infrared absorber (e), YI, which is a yellowish index calculated according to JIS K7105 (1981), is preferably 15 or less, and more preferably 11 or less.
  • a glass article formed with a film using the liquid composition of the present invention is a glass article having an excellent ultraviolet shielding property, a low haze value and an excellent antifouling property, and an outdoor glass article.
  • the present invention can be applied to window glass for vehicles such as automobiles and window glass for building materials attached to buildings such as houses and buildings.
  • Examples 1 to 6 are examples, and examples 7 to 9 are comparative examples.
  • the surface tension of the silicon compound (b) was measured by blowing air at a temperature of 22 ° C. using a surface tension meter (manufactured by Eiko Seiki Co., Ltd .: Science line t60).
  • the surface tension of the silicon compound (bx) of Example 9 was measured in the same manner.
  • Nonpol PMA-50W 44.0% by mass aqueous solution of polymaleic acid having a molecular weight of 1,200 manufactured by NOF Corporation.
  • Flexible component (f) SR-SEP: Sakamoto Pharmaceutical Co., Ltd., sorbitol polyglycidyl ether (filler) SiO 2 fine particle dispersion: Colloidal silica in which silica fine particles having an average primary particle size of 10 to 20 nm are dispersed in methanol, manufactured by Nissan Chemical Industries, Ltd.
  • ⁇ Preparation example of silylated UV absorber solution > 2,2 ′, 4,4′-tetrahydroxybenzophenone (BASF) 49.2 g, 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co.) 123.2 g, benzyltriethylammonium chloride (Pure Chemical Co., Ltd.) ) 0.8g, butyl acetate (manufactured by Junsei Chemical Co., Ltd.) 100g, heated to 60 ° C while stirring, dissolved, heated to 120 ° C and reacted for 4 hours, silylation with a solid content concentration of 63% by mass A UV absorber (a2) solution was obtained.
  • BASF 4,4′-tetrahydroxybenzophenone
  • ITO dispersion 11.9 g of ITO ultrafine particles, 3.0 g of DISPERBYK-190, and 24.2 g of Solmix AP-1 were dispersed for 48 hours using a ball mill, and then Solmix AP-1 was added and ITO solid content was added. It diluted so that a density
  • Example 1 11.7 g of silylated UV absorber (a2) solution, 0.014 g of TSL8257, 14.0 g of tetraethoxysilane, 48.1 g of Solmix AP-1, 18.1 g of pure water, 1 of SR-SEP 0.02 g of maleic acid and 0.081 g of non-pole PMA-50W were charged and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 1 having a solid content of 14% by mass.
  • silylated UV absorber (a2) solution 0.014 g of TSL8257, 14.0 g of tetraethoxysilane, 48.1 g of Solmix AP-1, 18.1 g of pure water, 1 of SR-SEP 0.02 g of maleic acid and 0.081 g of non-pole PMA-50W were charged and stirred at 50 ° C. for 2 hours. Thereafter, 7.0
  • the liquid composition 1 was applied by spin coating on high-heat-absorption green glass (manufactured by Asahi Glass Co., Ltd., size: 10 ⁇ 10 mm, thickness: 3.5 mm) whose surface had been cleaned. It was made to dry for minutes and the glass plate 1 with a film was obtained. The characteristic of the obtained glass plate 1 with a film was evaluated as follows. The evaluation results are shown in Table 1 together with the composition of the liquid composition 1.
  • the mass% of (a) component in solid content composition (mass%) shown in Table 1 shows the mass% of the part except the trimethoxysilyl group of silylated ultraviolet absorber (a2) with respect to solid content whole quantity.
  • the trimethoxysilyl group part of silylated ultraviolet absorber (a2) computed the mass% as (c) component combining with tetraethoxysilane.
  • the film thickness [ ⁇ m] of the coating was measured using a stylus type surface shape measuring instrument (ULVAC: Dektak 150).
  • Example 2 11.7 g of silylated UV absorber (a2) solution, 0.14 g of TSL8257, 14.0 g of tetraethoxysilane, 48.0 g of Solmix AP-1, 18.1 g of pure water, 1 SR-SEP 0.0 g, maleic acid 0.012 g and non-pole PMA-50W 0.081 g were charged and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 2 having a solid concentration of 14% by mass. Then, the glass plate 2 with a film was obtained like Example 1. The characteristics of the obtained coated glass plate 2 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 2.
  • Example 3 10.6 g of the silylated ultraviolet absorber (a2) solution, 1.3 g of TSL8257, 12.7 g of tetraethoxysilane, 51.5 g of Solmix AP-1, 16.5 g of pure water, 1 SR-SEP 0.0 g, maleic acid 0.012 g and non-pole PMA-50W 0.081 g were charged and stirred at 50 ° C. for 2 hours. Thereafter, 6.4 g of the ITO fine particle dispersion was added to obtain a liquid composition 3 having a solid content of 14% by mass. Then, the glass plate 3 with a film was obtained like Example 1. The characteristics of the obtained coated glass plate 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 3.
  • Example 4 11.7 g of silylated UV absorber (a2) solution, 0.14 g of KBM-7103, 14.0 g of tetraethoxysilane, 48.0 g of Solmix AP-1, 18.1 g of pure water, SR-SEP 1.0 g of maleic acid, 0.012 g of maleic acid, and 0.081 g of non-pole PMA-50W were added and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 4 having a solid content of 14% by mass. Then, the glass plate 4 with a film was obtained like Example 1. The characteristics of the obtained coated glass plate 4 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 4.
  • Example 5 11.7 g of silylated ultraviolet absorber (a2) solution, 0.14 g of BYK-307, 14.0 g of tetraethoxysilane, 48.0 g of Solmix AP-1, 18.1 g of pure water, SR-SEP 1.0 g of maleic acid, 0.012 g of maleic acid, and 0.081 g of non-pole PMA-50W were added and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 5 having a solid content concentration of 14% by mass. Thereafter, a coated glass plate 5 was obtained in the same manner as in Example 1. The characteristics of the obtained coated glass plate 5 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 5.
  • Example 6 12.0 g of silylated UV absorber (a2) solution, 0.14 g of TSL8257, 14.3 g of tetraethoxysilane, 50.6 g of Solmix AP-1, 18.5 g of pure water, SiO 2 fine particle dispersion 3.3 g of SR, 1.1 g of SR-SEP and 0.012 g of maleic acid were added and stirred at 50 ° C. for 2 hours to obtain a liquid composition 6 having a solid concentration of 14% by mass. Then, the glass plate 6 with a film was obtained like Example 1. The characteristics of the obtained coated glass plate 6 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 6.
  • Example 7 11.7 g of silylated ultraviolet absorber (a2) solution, 14.0 g of tetraethoxysilane, 48.1 g of Solmix AP-1, 18.1 g of pure water, 1.0 g of SR-SEP, maleic acid 0.012 g and 0.081 g of non-pole PMA-50W were charged and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 7 having a solid concentration of 14% by mass. Thereafter, a coated glass plate 7 was obtained in the same manner as in Example 1. The characteristics of the obtained coated glass plate 7 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 7.
  • Example 8 11.7 g of silylated ultraviolet absorber (a2) solution, 14.0 g of tetraethoxysilane, 48.1 g of Solmix AP-1, 18.1 g of pure water, 1.0 g of SR-SEP, maleic acid 0.012 g and 0.081 g of non-pole PMA-50W were charged and stirred at 50 ° C. for 2 hours. Thereafter, 7.0 g of the ITO fine particle dispersion was added to obtain a liquid composition 8-1 having a solid concentration of 14% by mass. Further, 88.0 g of IPA, 9.4 g of TSL8257, and 2.6 g of 1% by mass nitric acid were charged and stirred at 25 ° C. for 3 hours to obtain a liquid composition 8-2 for overcoat.
  • silylated ultraviolet absorber (a2) solution 14.0 g of tetraethoxysilane, 48.1 g of Solmix AP-1, 18.1 g of pure water, 1.0 g of
  • the liquid composition 8-1 was applied by spin coating on high heat ray absorbing green glass (manufactured by Asahi Glass Co., Ltd., size: 10 ⁇ 10 mm, thickness: 3.5 mm) whose surface was cleaned. After drying at 30 ° C. for 30 minutes and cooling to room temperature, the liquid composition 8-2 is further applied by a squeegee coating method and dried in the atmosphere at 200 ° C. for 30 minutes to form a film having an overcoat layer on the ultraviolet absorbing film The attached glass plate 8 was obtained. The characteristics of the obtained coated glass plate 8 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 8-1.
  • the film thickness of the coated glass plate 8 shown in Table 1 is the total film thickness of the ultraviolet absorbing film and the overcoat layer.
  • the abrasion resistance of the water contact angle is low in a two-layer film such as a film of the glass plate 8 with a film. Moreover, it is disadvantageous in terms of work efficiency for obtaining the coating.
  • a silicon compound (bx) having a surface tension outside the scope of the present invention was produced as follows to produce a liquid composition.
  • the compound obtained by the following synthesis examples was used, respectively.
  • the abbreviations of the compounds used in the synthesis examples indicate the following compounds.
  • R F2 —CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 CF 3
  • R-113 CCl 2 FCClF 2
  • a 300 mL eggplant flask charged with a stirrer chip was thoroughly purged with nitrogen.
  • 40 g of ethanol, 5.6 g of NaF, and R-225 (50 g) were placed.
  • 43.5 g of CF 3 O (CF 2 CF 2 O) a CF 2 CF 2 OC (O) —R F2 was dropped, and then vigorously stirred while bubbling at room temperature.
  • the eggplant flask outlet was sealed with nitrogen.
  • a vacuum pump was installed in the cooling pipe to keep the system at a reduced pressure, and excess ethanol and CH 3 CH 2 OC (O) —R F2 generated by exchange were distilled off.
  • Example 1 Thereafter, a coated glass plate 9 was obtained in the same manner as in Example 1. The characteristics of the obtained coated glass plate 9 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the liquid composition 9.
  • Table 1 the classification of the silicon compound (bx) is (b) ′.
  • a glass article formed with a film using the liquid composition of the present invention is a glass article having a coating excellent in ultraviolet shielding properties, having a low haze value and excellent in antifouling properties, and is an outdoor glass article such as an automobile.
  • the present invention can be applied to window glass for vehicles such as vehicles, window glass for building materials attached to buildings such as houses and buildings.

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Abstract

L'invention fournit une composition liquide qui permet de former à la surface d'un composant en verre, ou similaire, un film d'absorption de rayons ultraviolets qui tout en combinant une capacité d'absorption de rayons ultraviolets et des propriétés antisalissures élevées, se révèle excellent en termes de résistance à l'usure. L'invention fournit également un composant en verre qui possède un tel film d'absorption de rayons ultraviolets qui tout en combinant une capacité d'absorption de rayons ultraviolets et des propriétés antisalissure élevées, se révèle excellent en termes de résistance à l'usure, et qui est formé par mise en œuvre cette composition liquide. La composition liquide comprend : un agent d'absorption de rayons ultraviolets (a) prédéfini ; un composé silicium (b) de tension superficielle comprise entre 17,5 et 30mN/m ; un composé silane hydrolysable (c) (composé silicium (b) excépté) représenté par la formule (1) ; et un solvant (d). RH1 n1SiX1 4-n1…(1) (Dans la formule, n1 représente un nombre entier de 0 à 3, RH1 représente un groupe hydrocarbure de 1 à 20 atomes de carbone substitué ou non sans atome de fluor, et X1 représente un groupe hydrolysable. En cas de présence d'une pluralité de RH1 et X1, ceux-ci peuvent être différents ou identiques.)
PCT/JP2015/062285 2014-04-28 2015-04-22 Composition liquide, et composant en verre Ceased WO2015166863A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671950A (zh) * 2016-02-03 2016-06-15 陕西省石油化工研究设计院 一种纺织品用反应性防紫外线整理剂
WO2019095468A1 (fr) * 2017-11-16 2019-05-23 刘展标 Récipient en verre/céramique et procédé de fabrication associé
CN110804390A (zh) * 2019-10-16 2020-02-18 中国科学院上海硅酸盐研究所 一种高效隔热玻璃涂料及其制备方法
CN116507684A (zh) * 2020-10-12 2023-07-28 默克专利股份有限公司 组合物
WO2025154746A1 (fr) * 2024-01-16 2025-07-24 ダウ・東レ株式会社 Silicone co-modifiée

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JP2006306008A (ja) * 2005-03-31 2006-11-09 Jsr Corp 帯電防止用積層体
JP2008094971A (ja) * 2006-10-12 2008-04-24 Soft99 Corporation 自動車ガラス用撥水性コーティング剤
JP2009269969A (ja) * 2008-05-02 2009-11-19 Sekisui Chem Co Ltd コーティング用組成物及びこれを用いた粘着フィルム
JP2009542891A (ja) * 2006-07-10 2009-12-03 エルジー・ケム・リミテッド 汚れ除去が容易な反射防止コーティング組成物、これを用いて製造された反射防止コーティングフィルム及びその製造方法
WO2010131744A1 (fr) * 2009-05-15 2010-11-18 旭硝子株式会社 Fluide de revetement servant a former un film absorbant les ultraviolets et article en verre absorbant les ultraviolets
WO2011142463A1 (fr) * 2010-05-14 2011-11-17 旭硝子株式会社 Liquide à appliquer pour former un film absorbant les ultraviolets, et article de verre absorbant les ultraviolets

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Publication number Priority date Publication date Assignee Title
JP2006306008A (ja) * 2005-03-31 2006-11-09 Jsr Corp 帯電防止用積層体
JP2009542891A (ja) * 2006-07-10 2009-12-03 エルジー・ケム・リミテッド 汚れ除去が容易な反射防止コーティング組成物、これを用いて製造された反射防止コーティングフィルム及びその製造方法
JP2008094971A (ja) * 2006-10-12 2008-04-24 Soft99 Corporation 自動車ガラス用撥水性コーティング剤
JP2009269969A (ja) * 2008-05-02 2009-11-19 Sekisui Chem Co Ltd コーティング用組成物及びこれを用いた粘着フィルム
WO2010131744A1 (fr) * 2009-05-15 2010-11-18 旭硝子株式会社 Fluide de revetement servant a former un film absorbant les ultraviolets et article en verre absorbant les ultraviolets
WO2011142463A1 (fr) * 2010-05-14 2011-11-17 旭硝子株式会社 Liquide à appliquer pour former un film absorbant les ultraviolets, et article de verre absorbant les ultraviolets

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671950A (zh) * 2016-02-03 2016-06-15 陕西省石油化工研究设计院 一种纺织品用反应性防紫外线整理剂
CN105671950B (zh) * 2016-02-03 2018-09-18 陕西省石油化工研究设计院 一种纺织品用反应性防紫外线整理剂
WO2019095468A1 (fr) * 2017-11-16 2019-05-23 刘展标 Récipient en verre/céramique et procédé de fabrication associé
CN110804390A (zh) * 2019-10-16 2020-02-18 中国科学院上海硅酸盐研究所 一种高效隔热玻璃涂料及其制备方法
CN110804390B (zh) * 2019-10-16 2021-05-25 中国科学院上海硅酸盐研究所 一种高效隔热玻璃涂料及其制备方法
CN116507684A (zh) * 2020-10-12 2023-07-28 默克专利股份有限公司 组合物
WO2025154746A1 (fr) * 2024-01-16 2025-07-24 ダウ・東レ株式会社 Silicone co-modifiée

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