WO2010131744A1 - 紫外線吸収膜形成用塗布液および紫外線吸収ガラス物品 - Google Patents
紫外線吸収膜形成用塗布液および紫外線吸収ガラス物品 Download PDFInfo
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- WO2010131744A1 WO2010131744A1 PCT/JP2010/058215 JP2010058215W WO2010131744A1 WO 2010131744 A1 WO2010131744 A1 WO 2010131744A1 JP 2010058215 W JP2010058215 W JP 2010058215W WO 2010131744 A1 WO2010131744 A1 WO 2010131744A1
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- WIPO (PCT)
- Prior art keywords
- compound
- organooxysilane
- ultraviolet absorbing
- absorbing film
- organooxysilane compound
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Classifications
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/74—UV-absorbing coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a coating liquid for forming an ultraviolet absorbing film on the surface of an article such as glass and an ultraviolet absorbing glass article having an ultraviolet absorbing film formed using the coating liquid.
- 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.
- Patent Document 2 uses a coating solution in which a reaction product of a silane compound and an organic compound having an ultraviolet absorbing ability is mixed with a silane compound. An attempt to form a silica-based ultraviolet absorbing film is described. In the silica-based ultraviolet absorbing film described in Patent Document 2, although there is no bleeding out of the ultraviolet absorber from the film, even when the long-wavelength ultraviolet absorption required in the present invention is achieved, this silica-based ultraviolet absorption is particularly applied to glass. When the coating film is formed, there is a problem that the crack resistance and the wear resistance are not sufficient.
- the present invention was made in order to solve the above problems, and has a mechanical durability such as wear resistance and a coating solution for forming an ultraviolet absorbing film with little decrease in ultraviolet absorbing ability due to long-term use
- Another object of the present invention is to provide an ultraviolet-absorbing glass article having an ultraviolet-absorbing film which is formed by using the coating solution and has mechanical durability such as abrasion resistance and a decrease in ultraviolet-absorbing ability due to long-term use.
- the present invention provides a coating solution for forming an ultraviolet absorbing film and an ultraviolet absorbing glass article having the following configuration.
- a coating solution for forming an ultraviolet absorbing film which is a silane compound or a constituent component of one or more partial hydrolysis-condensation products of the organooxysilane compounds (a) to (c).
- “(a) to (c)” will be used hereinafter to include (a), (b) and (c) unless otherwise specified.
- a component derived from the organooxysilane compound (a) in the coating solution derived from an organooxysilane compound (b) that is a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- the component and the content ratio of the component derived from the organooxysilane compound (c) other than (a) and (b) are components derived from the organooxysilane compound (a), a hydroxyl group-containing benzophenone compound and an epoxy group.
- the total solid content of the component derived from the organooxysilane compound (b) which is a reaction product with the containing organooxysilane compound and the component derived from the organooxysilane compound (c) other than the above (a) and (b) To 100 parts by weight of the component derived from the organooxysilane compound (a) 5 to 50 parts by mass, 10 to 50 parts by mass for the component derived from the organooxysilane compound (b), and 40 to 80 parts by mass for the component derived from the organooxysilane compound (c) The coating solution for forming an ultraviolet absorbing film according to [1].
- At least one content selected from the polyepoxides and glycerin is a component derived from the organooxysilane compound (a), a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound 0.1 to about 100 parts by mass of the total solid content of the component derived from the organooxysilane compound (b) and the components derived from the organooxysilane compound (c) other than the above (a) and (b)
- the coating solution for forming an ultraviolet absorbing film according to [3] which is 20 parts by mass.
- An acid having a pKa of the first proton of 1.0 to 5.0 is defined as a molar concentration of 0.005 to 5.0 with respect to the total mass of the proton coating solution when the first proton of the acid is completely dissociated.
- Silica fine particles are derived from an organooxysilane compound (b) which is a reaction product of a component derived from the organooxysilane compound (a), a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- the content of the component derived from the organooxysilane compound (c) is, as the content of SiO 2 when converted to silicon atoms contained in this component to SiO 2, 1 to 10 wt%, [ [1]
- the ultraviolet absorbing glass article according to [8] wherein a transmittance of light having a wavelength of 380 nm to the glass article is 7.0% or less.
- an ultraviolet absorbing film of the present invention By using the coating solution for forming an ultraviolet absorbing film of the present invention, it is possible to form an ultraviolet absorbing film having mechanical durability such as abrasion resistance and little deterioration in ultraviolet absorbing ability due to long-term use.
- the UV-absorbing glass article of the present invention having a film has long-term durability both mechanically and UV-absorbing ability.
- the coating solution for forming an ultraviolet absorbing film of the present invention is an organooxy which is a reaction product of a component derived from an epoxy group-containing organooxysilane compound (a), a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- a component derived from a silane compound (b) hereinafter also referred to as a “silylated benzophenone compound” if necessary
- the organooxysilane compounds (a) to (c) are compounds having two or more organooxy groups bonded to silicon atoms.
- the component derived from the organooxysilane compound includes, for example, the component derived from the organooxysilane compound (a), and includes the organooxysilane compound (a) itself, and the organooxysilane compound.
- the coating solution for forming an ultraviolet absorbing film of the present invention may contain organooxysilane compounds (a) to (c) themselves as components derived from organooxysilane compounds (a) to (c), respectively. Further, it may contain a partial hydrolysis condensate of each of the organooxysilane compounds (a) to (c). Further, the coating solution for forming an ultraviolet absorbing film of the present invention may contain any two types of partial hydrolysis cocondensates in the organooxysilane compounds (a) to (c) and one other type. Good. Further, the coating solution for forming an ultraviolet absorbing film of the present invention may contain three partial hydrolysis cocondensates of organooxysilane compounds (a) to (c). These partial hydrolysis-condensation products and partial hydrolysis-cocondensation products will be described after the description of each organooxysilane compound.
- the organooxysilane compounds (a) to (c) also form the above-mentioned partial hydrolysis condensate or partial hydrolysis cocondensate.
- the structural units of the silane compounds (a) to (c) are considered to be the same cured product structural unit.
- the coating solution for forming an ultraviolet-absorbing film of the present invention is an organooxysilane compound (a) to (c) 3 whether it is an organooxysilane compound itself or a constituent unit in a partially hydrolyzed condensate or partially hydrolyzed cocondensate. It is essential to contain each component derived from the species in combination.
- the epoxy group-containing organooxysilane compound (a) in the present invention is not particularly limited as long as it is an organooxysilane compound in which an organic group containing an epoxy group is bonded to a silicon atom, but preferably the following general formula ( The organooxysilane compound shown by A) can be mentioned.
- the organic group bonded to the silicon atom is an organic group in which the atom bonded to the silicon atom is a carbon atom.
- the epoxy group-containing organooxysilane compound (a) is also referred to as an organooxysilane compound (a).
- R 1 a SiR 2 b (OR 3 ) 4- (a + b) (A)
- R 1 is an organic group containing an epoxy group
- R 2 is an alkyl group or aryl group having 1 to 10 carbon atoms
- R 3 is a hydrogen atom or oxygen having 1 to 10 carbon atoms
- a monovalent hydrocarbon group which may contain an atom a is 1 or 2
- b is 0 or 1
- a + b is 1 or 2.
- R 1 is an organic group containing an epoxy group, and the number of epoxy groups contained in the organic group and the type of the organic group itself are not particularly limited. Alternatively, a linear or branched alkyl group having 1 to 15 carbon atoms and having one epoxy group-containing cycloalkyl group may be used.
- a 3-glycidoxypropyl group represented by the following formula (1-1), a 5,6-epoxyhexyl group represented by the following formula (1-2), -3) a 9,10-epoxydecyl group represented by the formula, a 2- (3,4-epoxycyclohexyl) ethyl group represented by the following formula (1-4) and the like are preferable, from the viewpoint of reactivity with the silane compound:
- a 3-glycidoxypropyl group and a 2- (3,4-epoxycyclohexyl) ethyl group are particularly preferred.
- the number of organic groups R 1 containing an epoxy group bonded to a silicon atom is represented by a.
- the number of a is 1 or 2.
- an epoxy group-containing organooxysilane compound in which a is 1 is preferably used.
- R 2 is an alkyl group or aryl group having 1 to 10 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, a phenyl group, and the like. It is done. Preferred R 2 is an alkyl group having 4 or less carbon atoms.
- R 3 is a hydrogen atom or a monovalent hydrocarbon group which may contain an oxygen atom having 1 to 10 carbon atoms.
- a monovalent hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group or alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an acyl group having 2 to 10 carbon atoms, Examples thereof include an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a phenyl group, an iso group.
- a propenyl group, a methoxyethyl group, an acetyl group, etc. are mentioned.
- the monovalent hydrocarbon group containing an oxygen atom include an alkoxyalkyl group having 2 to 10 carbon atoms, an acyloxyalkyl group, and an alkoxycarbonylalkyl group. Specific examples include a 2-methoxyethyl group.
- an alkyl group having 4 or less carbon atoms such as a methyl group, an ethyl group, and an isopropyl group is particularly preferable from the viewpoint of hydrolysis rate and coating solution stability.
- the number of OR 3 bonded to the silicon atom represented by 4-ab is 3 or 2.
- epoxy group-containing organooxysilane compound represented by the general formula (A) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidide.
- the above organooxysilane compound (a) is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethylmethyldimethoxysilane or the like is used.
- the organooxysilane compound (a) used in the present invention is considered to act as a binder that imparts crack resistance while maintaining desired wear resistance when the film thickness is increased.
- the organooxysilane compound (b) in the present invention that is, the organooxysilane compound (b), which is a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound, is a raw material hydroxyl group-containing benzophenone compound. It is a component which has an ultraviolet absorptivity by the effect
- a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound (also referred to as a silylated benzophenone compound as described above) is a silicon oxide network having a crosslinked structure formed from an organooxysilane compound.
- the residue of the hydroxyl group-containing benzophenone compound is fixed to the network.
- the hydroxyl group-containing benzophenone-based compound does not bleed out, thereby enabling the ultraviolet absorbing film to maintain the ultraviolet absorbing ability over a long period of time.
- the silylated benzophenone compound is regarded as one of the organooxysilane compounds because it has the same organooxysilyl group as the organooxysilane compound (a).
- the benzophenone compound having a hydroxyl group as a raw material of the silylated benzophenone compound may be any compound having a benzophenone skeleton and having a hydroxyl group.
- the following general formula ( A benzophenone compound represented by B) having 2 to 4 hydroxyl groups is preferably used since it has an excellent ultraviolet absorbing ability even after silylation.
- the hydroxyl group-containing benzophenone compound has more preferably 3 or 4 hydroxyl groups.
- 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 above general formula (B) in the present invention, 2,4-dihydroxybenzophenone represented by the following formula (2-1), (2-2) 2,2 ′, 3 (or any of 4, 5, 6) -trihydroxybenzophenone represented by the formula, 2,2 ′, 4,4′-tetrahydroxybenzophenone represented by (2-3), etc. are more preferred, 2,2 ′, 4,4′-tetrahydroxybenzophenone is particularly preferred.
- the hydroxyl group-containing benzophenone compound can be used alone or as a mixture of two or more.
- Examples of the epoxy group-containing organooxysilane compound used in the reaction for silylating such a hydroxyl group-containing benzophenone compound include the same compounds as the organooxysilane compound (a).
- Preferred examples include compounds represented by the general formula (A), and more preferred are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxy.
- Silane 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4 And epoxy (cyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane.
- the epoxy group-containing organooxysilane 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 organooxysilane 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 organooxysilane compound are reacted in the presence of a catalyst as necessary.
- the amount of the epoxy group-containing organooxysilane compound used in the reaction is not particularly limited, but is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.0, with respect to 1 mol of the hydroxyl group-containing benzophenone compound. Is a mole.
- 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 addition amount of the catalyst 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 organooxysilane compound.
- the addition amount is 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 organooxysilane compound, the reaction takes a long time.
- the catalyst may reduce the stability of the coating solution.
- the silylation reaction is carried out in the presence of a catalyst by heating a mixture of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound, preferably in the above ratio, at a temperature range of 50 to 150 ° C. for 4 to 20 hours. be able to.
- This reaction may be carried out in the absence of a solvent or in a solvent that dissolves both the hydroxyl group-containing benzophenone-based compound and the epoxy group-containing organooxysilane compound, but the solvent is easy to control and easy to handle.
- the method using is preferable. 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 organooxysilane compound.
- the silylated benzophenone compound preferably used in the present invention ie, the organooxysilane compound (b), includes one or two hydroxyl groups of a benzophenone compound containing three or more hydroxyl groups, and an epoxy group-containing organooxysilane.
- Me represents a methyl group.
- the organooxysilane compound (c) in the present invention is an organooxysilane compound other than the above (a) and (b), that is, an organooxysilane compound that does not contain an epoxy group or a residue of a hydroxyl group-containing benzophenone compound.
- the organooxysilane compound (c) is not particularly limited as long as it is an organooxysilane compound that does not contain a residue of an epoxy group or a hydroxyl group-containing benzophenone compound, but in the present invention, preferably the following general formula (C) And the silane compounds shown.
- R 4 m SiR 5 n (OR 6 ) 4- (m + n) (C)
- R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms
- R 5 is an alkyl group or aryl group having 1 to 10 carbon atoms
- R 6 is hydrogen.
- a monovalent hydrocarbon group which may contain an atom or an oxygen atom having 1 to 10 carbon atoms
- m and n are 0, 1 or 2
- m + n is 0, 1 or 2.
- R 4 is not an organic group containing an epoxy group, nor is it an organic group having a residue of a hydroxyl group-containing benzophenone compound.
- R 4 is specifically an alkyl group having 1 to 10 carbon atoms, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or a part of hydrogen atoms of these groups
- a substituted monovalent hydrocarbon group substituted with a substituent that does not contain an epoxy group such as a (meth) acryloxy group, a mercapto group, an amino group, or a cyano group.
- R 4 include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
- R 5 is the same group as R 2 in the above formula (A), and R 6 is the same group as R 3 in the above formula (A).
- R 5 is preferably an alkyl group having 4 or less carbon atoms
- R 6 is preferably an alkyl group having 4 or less carbon atoms.
- the number of R 5 bonded to the silicon atom represented by n is 0, 1 or 2. Since m + n is 0, 1 or 2, the number of OR 6 bonded to the silicon atom in the formula (C) represented by 4-mn is 4, 3 or 2. That is, the silane compound represented by the above formula (C) used in the present invention acts as an adhesive binder.
- silane compound represented by the above formula (C) examples include dialkoxysilanes or diacyloxysilanes, trialkoxy or triacyloxysilanes, and tetraalkoxysilanes exemplified below.
- dialkoxysilane or diacyloxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi (2-methoxyethoxy) silane, dimethyldiacetoxysilane, dimethyldipropoxysilane, and dimethyldiisopropenoxysilane.
- Dimethyldibutoxysilane vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldi (2-methoxyethoxy) silane, vinylmethyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane , Phenylmethyldiacetoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldisilane Lopoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, Examples include 3-mercaptopropylmethyld
- trialkoxy or triacyloxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, methyltriacetoxysilane, methyltripropoxysilane, and methyltriisopropenoxysilane.
- tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetra n-butyloxysilane, tetrasec-butyloxysilane, and tetra tert-butyloxysilane. Can be mentioned.
- organooxysilane compound (c) tetraalkoxysilanes having an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms are used. Preferred trialkoxysilanes are preferred. More preferably, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane are used.
- the organooxysilane compound is a hydroxyl group (silanol group) bonded to a silicon atom through hydrolysis of the organooxy group, and then the silanol groups are dehydrated to form a siloxane bond represented by -Si-O-Si-.
- a linear polysiloxane is produced only from the diorganooxysilane compound, but a three-dimensional network (silicon oxide network) of polysiloxane is produced from the triorganooxysilane compound or the tetraorganooxysilane compound.
- a three-dimensional network of polysiloxanes is also formed from a mixture of a diorganooxysilane compound and a triorganooxysilane compound or a tetraorganooxysilane compound.
- the coating solution for forming an ultraviolet absorbing film of the present invention is an organooxysilane compound (a) to (c) because it is for forming an ultraviolet absorbing film having mechanical durability such as abrasion resistance. It is necessary that at least a part of these is a triorganooxysilane compound or a tetraorganooxysilane compound.
- organooxysilane compounds (a) to (c) in the present invention at least the organooxysilane compound (c) is preferably trialkoxysilanes or tetraalkoxysilanes.
- Silane compounds (a) and (b) may be dialkoxysilanes or trialkoxysilanes.
- the organooxysilane compound (c) is more preferably a tetraalkoxysilane. Furthermore, both organooxysilane compounds (a) and (b) are preferably trialkoxysilanes.
- the coating solution for forming an ultraviolet-absorbing film of the present invention is a partially hydrolyzed condensate of each of the organooxysilane compounds (a) to (c) as a component derived from the organooxysilane compounds (a) to (c). May be contained. Further, the coating solution for forming an ultraviolet absorbing film of the present invention may contain any two kinds of partial hydrolysis cocondensates of the organooxysilane compounds (a) to (c) and another one, Three types of partial hydrolysis cocondensates of organooxysilane compounds (a) to (c) may be contained.
- the partial hydrolysis-condensation product is an oligomer (multimer) produced by hydrolysis and dehydration condensation of an organooxysilane compound.
- the partially hydrolyzed condensate is a high molecular weight compound that is usually soluble in a solvent.
- the partially hydrolyzed condensate has an organooxy group and a silanol group, and further has a property of being hydrolyzed and condensed to be a final cured product.
- a partial hydrolysis condensate can be obtained from only one kind of organooxysilane compound, and a partial hydrolysis cocondensate that is a cocondensate thereof can also be obtained from two or more kinds of organooxysilane compounds.
- a partially hydrolyzed cocondensate can be obtained from a mixture of two or more epoxy group-containing organooxysilane compounds as the organooxysilane compound (a).
- those obtained from different types of organooxysilane compounds between the organooxysilane compounds (a) to (c) are referred to as partially hydrolyzed cocondensates, and the organooxysilane compounds (a) to ( What is obtained from 2 or more types belonging to any one of c) is referred to as a partial hydrolysis condensate.
- Examples of the partially hydrolyzed condensate include a partially hydrolyzed condensate obtained only from the organooxysilane compound (a).
- the partially hydrolyzed condensate can also be obtained from the organooxysilane compound (b) and the organooxysilane compound (c).
- Examples of the partially hydrolyzed cocondensate include a partially hydrolyzed cocondensate obtained from a mixture of an organooxysilane compound (a) and an organooxysilane compound (b).
- a partially hydrolyzed cocondensate can be obtained from a mixture of an organooxysilane compound (a) and an organooxysilane compound (c) or from a mixture of an organooxysilane compound (b) and an organooxysilane compound (c). it can. Furthermore, those partially hydrolyzed cocondensates can also be obtained from a three-part mixture of an organooxysilane compound (a), an organooxysilane compound (b), and an organooxysilane compound (c). These partial hydrolysis-condensation products and partial hydrolysis-cocondensation products may contain an organooxysilane compound that is an unreacted raw material.
- partial hydrolysis condensation and partial hydrolysis cocondensation are collectively referred to as partial hydrolysis (co) condensation, and the resulting product is also referred to as partial hydrolysis (co) condensate.
- the partial hydrolysis (co) condensation of the organooxysilane compound can be performed, for example, by adding water to the starting material organooxysilane compound or a lower alcohol solution thereof in the presence of an acid catalyst.
- the lower alcohol include methanol, ethanol, isopropanol, butanol and the like.
- the solvent that can be used in combination with the alcohol include ketones such as acetone and acetylacetone, esters such as ethyl acetate and isobutyl acetate, and ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and diisopropyl ether.
- the amount of the lower alcohol used for the partial hydrolysis (co) condensation of the organooxysilane compound include an amount of about 0 to 1000 parts by mass with respect to 100 parts by mass of the organooxysilane compound.
- the amount of water is preferably 4 to 20 equivalents, preferably 8 to 15 equivalents in terms of a molar ratio with respect to the SiO 2 equivalent of the component derived from the organooxysilane compound (c). The amount is more preferred. If the amount of water is less than 4 equivalents in the above molar ratio, hydrolysis does not proceed and haze increases or the coating solution may be repelled depending on the substrate during coating. Storage may be insufficient.
- the acid catalyst include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, oxalic acid, Examples thereof include carboxylic acids such as malonic acid, succinic acid, maleic acid, phthalic acid, citric acid and malic acid, and sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid.
- inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, oxalic acid
- carboxylic acids such as malonic acid, succinic acid, maleic acid, phthalic acid, citric acid and
- the acid catalyst used for the partial hydrolysis (co) condensation is to maintain a sufficient light resistance in the obtained ultraviolet absorbing film, and in particular from the viewpoint of preventing photodegradation of the ultraviolet absorbing ability, Hereinafter, it is preferably referred to as pKa1).
- the addition amount of the acid can be set without any limitation as long as it can function as a catalyst.
- the first proton of the acid is completely dissociated. It is preferable to contain it at a rate of 0.001 to 0.1 mol / kg as the molar concentration of the proton relative to the total mass of the coating solution, and more preferably at a rate of 0.001 to 0.01 mol / kg. preferable.
- the molar concentration is set to 0. It is preferably contained at a rate of 005 to 5.0 mol / kg, more preferably 0.01 to 3.5 mol / kg.
- the partial hydrolysis (co) condensation of the organooxysilane compound is carried out by adding a reaction solution obtained by adding water to a lower alcohol solution of an organooxysilane compound in the presence of an acid catalyst at 10 to 40 ° C. for 1 to 48. This can be done by stirring for a period of time.
- the coating solution for forming an ultraviolet absorbing film of the present invention is an organooxy which is a reaction product of a component derived from an epoxy group-containing organooxysilane compound (a), a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- a component derived from a silane compound (b) hereinafter also referred to as a “silylated benzophenone compound” if necessary), and a component derived from an organooxysilane compound (c) other than the above (a) and (b) Containing.
- the coating solution for forming an ultraviolet absorbing film of the present invention may contain organooxysilane compounds (a) to (c) themselves as components derived from the organooxysilane compounds (a) to (c). Each of the oxysilane compounds (a) to (c) may contain a partial hydrolysis condensate. Further, the coating solution for forming an ultraviolet absorbing film of the present invention may contain any two types of partial hydrolysis cocondensates in the organooxysilane compounds (a) to (c) and one other type. Good. Further, the coating solution for forming an ultraviolet absorbing film of the present invention may contain three partial hydrolysis cocondensates of organooxysilane compounds (a) to (c).
- the combination of components derived from the organooxysilane compounds (a) to (c) contained in the coating solution for forming an ultraviolet absorbing film of the present invention includes, for example, an organooxysilane compound (a). And a partially hydrolyzed cocondensate of organooxysilane compound (c) and organooxysilane compound (b), or a partially hydrolyzed cocondensate of organooxysilane compound (a) and organooxysilane compound (c) And a combination of a partially hydrolyzed condensate of organooxysilane compound (b) and the like.
- the coating solution for forming an ultraviolet absorbing film of the present invention may contain three partial hydrolysis cocondensates of organooxysilane compounds (a) to (c).
- the coating solution containing the partially hydrolyzed (co) condensate may contain organooxysilane compounds (a) to (c) such as unreacted raw materials.
- the composition ratio of components derived from the organooxysilane compounds (a) to (c) in the coating solution is such that the coating solution is partially hydrolyzed (co-polymerized).
- the amount of each constituent unit of the partially hydrolyzed (co) condensate converted to the raw material organooxysilane compounds (a) to (c) is further added to the coating solution.
- the organooxysilane compounds (a) to (c) themselves are contained in addition to the (co) condensate, the amount of each of the organooxysilane compounds (a) to (c) Represents the total amount.
- the coating solution for forming an ultraviolet absorbing film contains only three partial hydrolysis cocondensates of organooxysilane compounds (a) to (c), the amount of the structural unit is the organooxysilane compound. Expressed as the amount of the organooxysilane compounds (a) to (c) in terms of (a) to (c).
- the coating solution for forming an ultraviolet absorbing film contains three kinds of partially hydrolyzed cocondensates of organooxysilane compounds (a) to (c) and an organooxysilane compound (c)
- the amount of the organooxysilane compound (c) is such that the structural unit derived from the organooxysilane compound (c) in the partially hydrolyzed cocondensate and the organooxysilane compound (c) contained alone in addition to the cocondensate The total amount.
- the content ratio of the component derived from the organooxysilane compound (a) represented by the above definition in the coating solution for forming an ultraviolet absorbing film of the present invention to the component derived from the organooxysilane compound (c) is an organooxysilane compound.
- the component derived from the organooxysilane compound (a) is 5 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the components derived from the organooxysilane compound (c).
- the component derived from b) is 10 to 50 parts by mass, derived from the organooxysilane compound (c).
- the proportion is 40 to 80 parts by mass, more preferably 7 to 35 parts by mass for the component derived from the organooxysilane compound (a), and 15 for the component derived from the organooxysilane compound (b).
- the component derived from the organooxysilane compound (c) is in a proportion of 45 to 70 parts by weight, and particularly preferably about 10 to 30 parts by weight for the component derived from the organooxysilane compound (a)
- the proportion derived from the organooxysilane compound (b) is 20 to 30 parts by mass, and the component derived from the organooxysilane compound (c) is 50 to 65 parts by mass.
- the content ratio of the component derived from the organooxysilane compound (a) with respect to 100 parts by mass of the total solid content of the components derived from the organooxysilane compound (c) other than (b) is more than 50 parts by mass, desired resistance Wearability may not be obtained, and if the amount is less than 5 parts by mass, cracks may occur when a film thickness necessary for expressing the desired ultraviolet absorbing ability is formed.
- the content ratio of the component derived from the organooxysilane compound (b) with respect to 100 parts by mass of the total solid content of the components derived from the organooxysilane compound (c) other than (b) is more than 50 parts by mass, desired resistance Abrasion may not be obtained, and if it is less than 10 parts by mass, a desired ultraviolet absorbing ability may not be obtained.
- the content ratio of the component derived from the organooxysilane compound (c) is more than 80 parts by mass with respect to 100 parts by mass of the total solid content of the components derived from the organooxysilane compound (c) other than (b)
- the film thickness necessary for the UV absorbing ability is formed, cracks may occur.
- the film thickness is less than 40 parts by mass, desired wear resistance may not be obtained.
- the content ratio of the component derived from the organooxysilane compound (a) and the component derived from the organooxysilane compound (b) in the coating solution for forming an ultraviolet absorbing film of the present invention [(a) / (b)] Is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, in terms of mass ratio. If this (a) / (b) is less than 10/90, the desired wearability may not be obtained, and if it is more than 80/20, cracks will occur when the film thickness necessary for the desired UV absorption is formed. Sometimes.
- the content ratio of the component derived from the organooxysilane compound (b) and the component derived from the organooxysilane compound (c) in the coating solution for forming an ultraviolet absorbing film of the present invention [(b) / (c)] Is preferably 20/80 to 40/60 by mass ratio, more preferably 25/75 to 35/65. If this (b) / (c) is smaller than 20/80, cracks may occur when a film thickness necessary for the desired UV absorption ability is formed, and if it is larger than 40/60, the desired wear resistance cannot be obtained. Sometimes.
- the content of the component derived from the organooxysilane compound (c), SiO 2 content when converted to silicon atoms contained in this component to SiO 2 1 to 10% by mass, and more preferably 3 to 8% by mass.
- the total content of the components derived from the organooxysilane compound (c) is less than 1%, it is necessary to increase the coating amount of a coating solution for obtaining an ultraviolet absorbing film having a desired film thickness. As a result, the appearance may be deteriorated, and when it exceeds 10% by mass, there is a risk that cracks may occur in the ultraviolet absorbing film that can be obtained when the coating liquid is applied in a thick state.
- the coating liquid for forming an ultraviolet absorbing film of the present invention contains various optional compounding agents as necessary within the range not impairing the effects of the present invention, in addition to the above-mentioned organooxysilane compound that is an essential component. can do.
- the coating liquid for forming an ultraviolet absorbing film of the present invention for example, by preventing the ultraviolet absorbing ability of the ultraviolet absorbing film from being lowered and the occurrence of cracks caused by light irradiation over a long period of time.
- Examples thereof include a compounding agent for improving light resistance (hereinafter referred to as “light resistance improver” as necessary).
- Such a light resistance improver include polyepoxides and glycerin.
- polyepoxides are preferable.
- Polyepoxides are a general term for compounds having a plurality of epoxy groups. That is, the average number of epoxy groups in the polyepoxides is 2 or more, but in the present invention, a polyepoxide having an average number of epoxy groups of 2 to 10 is 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. These are compounds having two or more epoxy groups.
- 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 that a higher effect can be exerted with respect to an improvement in light resistance.
- These alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.
- ethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl 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.
- three or more hydroxyl groups such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether are used.
- a polyglycidyl ether of an aliphatic polyol having an average molecular weight one having an average number of glycidyl groups (epoxy groups) exceeding 2 per molecule is preferred.
- the blending amount of the light resistance improver is not particularly limited as long as it is an amount capable of preventing photodegradation of the mechanical strength and ultraviolet absorbing ability of the ultraviolet absorbing film without impairing the effects of the present invention.
- polyepoxides and glycerin As a content in the case of using one kind selected from the group consisting of components derived from the organooxysilane compound (a) in the coating solution for forming an ultraviolet absorbing film, a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound, To 100 parts by mass of the total solid content of the component derived from the organooxysilane compound (b), which is the reaction product of the above, and the component derived from the organooxysilane compound (c) other than the above (a) and (b) The amount of 0.1 to 20 parts by mass is preferable, and the amount of 1.0 to 10 parts by mass is more preferable.
- the blending amount of the light resistance improver is less than 0.1 parts by mass, the light deterioration of the ultraviolet absorbing ability may not be sufficiently prevented, and if it exceeds 20 parts by mass, the mechanical strength of the ultraviolet absorbing film deteriorates. There is a fear.
- the coating liquid for forming an ultraviolet absorbing film of the present invention may further contain a light stabilizer for the purpose of improving light resistance.
- the light stabilizer is preferably a hindered amine light stabilizer (HALS).
- HALS hindered amine light stabilizer
- the blending amount of the light stabilizer is a reaction product of a component derived from the organooxysilane compound (a) in the coating solution for forming an ultraviolet absorbing film, a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- it is 0.001 with respect to 100 mass parts of total solid content of the component derived from the organooxysilane compound (b) and the components derived from the organooxysilane compound (c) other than the above (a) and (b).
- the amount is from 0.015 parts by mass, more preferably from 0.002 to 0.009 parts by mass.
- silica fine particles blended for further improving the wear resistance of the ultraviolet absorbing film can be mentioned.
- silica fine particles are blended in a coating solution for forming an ultraviolet absorbing film, it is preferable to blend 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.
- colloidal silica can be appropriately blended to produce a coating solution for forming an ultraviolet absorbing film containing silica fine particles.
- colloidal silica is mix
- silica fine particles are blended as an optional component in the coating solution for forming an ultraviolet absorbing film of the present invention, it is preferable to blend silica fine particles having an average particle diameter (BET method) of 1 to 100 nm.
- BET method average particle diameter
- the average particle diameter exceeds 100 nm, the particles diffusely reflect light, so that the value of the haze value of the obtained ultraviolet absorbing film increases, which may be undesirable in terms of optical quality.
- the average particle size is particularly preferably 5 to 40 nm. This is for imparting abrasion resistance to the ultraviolet absorbing film and maintaining the transparency of the ultraviolet absorbing film.
- 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.
- distributed in acidic aqueous solution it is preferable to use the colloidal silica disperse
- the colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titania sol, and ceria sol.
- the blending amount is derived from the organooxysilane compound (a) in the coating liquid for forming an ultraviolet absorbing film.
- a component derived from an organooxysilane compound (b) which is a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound, and an organooxysilane compound other than the above (a) and (b) An amount of 0.5 to 50 parts by mass is preferable and an amount of 10 to 30 parts by mass is more preferable with respect to 100 parts by mass of the total solid content of the components derived from (c).
- the range of the above blending amount maintains the film forming property of the ultraviolet absorbing film while ensuring sufficient wear resistance, and cracks. This is the range of the amount of silica fine particles that can prevent the occurrence of UV light and the transparency of the ultraviolet absorbing film due to the aggregation of the silica fine particles.
- the coating solution for forming an ultraviolet absorbing film of the present invention may further contain functional fine particles such as indium tin oxide fine particles and antimony tin oxide fine particles and an organic dye for the purpose of imparting functionality.
- a surfactant may be included as an additive for the purpose of improving the coating property to the substrate and the smoothness of the resulting coating film.
- the coating solution for forming an ultraviolet absorbing film of the present invention may further contain additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coating property to the substrate, and improving the adhesion to the substrate.
- additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coating property to the substrate, and improving the adhesion to the substrate.
- an additive such as an adhesion-imparting agent may be included.
- the compounding amount of these additives is a reaction product of a component derived from the organooxysilane compound (a) in the coating solution for forming an ultraviolet absorbing film, a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound.
- An amount of 0.01 to 2 parts by mass is preferred every time.
- the coating liquid for forming an ultraviolet absorbing film of the present invention may contain a dye, a pigment, a filler and the like as long as the object of the present invention is not impaired.
- Examples of an optional compounding agent that can be contained in the coating solution for forming an ultraviolet absorbing film of the present invention include a compounding agent that imparts flexibility to the ultraviolet absorbing film.
- Examples of the compounding agent that imparts flexibility include various organic resins such as silicone resin, acrylic resin, polyvinyl butyral (PVB) resin, polyester resin, polyurethane resin, and epoxy resin.
- organic resins such as silicone resin, acrylic resin, polyvinyl butyral (PVB) resin, polyester resin, polyurethane resin, and epoxy resin.
- the component derived from the organooxysilane compound (a) contained therein, the component derived from the organooxysilane compound (b), and derived from the organooxysilane compound (c) An ultraviolet absorbing film is formed by curing a curing component such as a component to be cured as described below.
- the coating solution for forming an ultraviolet absorbing film of the present invention preferably contains an acid catalyst that promotes the above curing.
- the acid catalyst include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, oxalic acid, malonic acid, Examples thereof include carboxylic acids such as succinic acid, maleic acid, phthalic acid, citric acid and malic acid, and sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid.
- inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, oxalic acid, malonic acid
- carboxylic acids such as succinic acid, maleic acid, phthalic acid, citric acid and
- an ultraviolet absorbing film of the present invention from the viewpoint of improving light resistance, in particular, preventing light deterioration of ultraviolet absorbing ability, together with a light resistance improving agent such as the above polyepoxides and glycerin, It is preferable to use an acid having a pKa of 1.0 to 5.0.
- the amount of acid added can be set without any limitation as long as it can function as a catalyst. Specifically, when an acid having a pKa1 of less than 1.0 is used, the first proton of the acid is completely dissociated.
- the molar concentration of protons with respect to the total mass of the coating solution is preferably 0.001 to 0.1 mol / kg, preferably 0.001 to 0.01 mol / kg. Is more preferable.
- concentration of the acid used is less than 0.001 mol / kg, the function as a catalyst may not be sufficiently achieved, and when it exceeds 0.1 mol / kg, the ultraviolet absorbing film may be yellowed.
- an acid having a pKa1 of 1.0 to 5.0 from the viewpoint of maintaining sufficient light resistance in the obtained ultraviolet absorbing film and preventing photodegradation of ultraviolet absorbing ability.
- the molar concentration is preferably 0.005 to 5.0 mol / kg, more preferably 0.01 to 3.5 mol / kg. If the concentration of the acid used is less than 0.005 mol / kg, hydrolysis does not proceed and the haze increases at the time of coating, and the coating solution may be repelled depending on the substrate. There is a possibility that the speed is increased and long-term storage is not sufficient.
- the coating solution for forming an ultraviolet absorbing film of the present invention may contain a curing catalyst in addition to the acid catalyst.
- Curing catalysts include aliphatic carboxylic acids, for example, lithium salts such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt; benzyltrimethylammonium salt, tetramethylammonium salt Quaternary ammonium salts such as salts and tetraethylammonium salts; metal alkoxides and chelates such as aluminum, titanium and cerium; ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and their salts, ammonium trifluoromethylsulfonate, Bis (tolufluoromethylsulfonyl) bromomethylammonium and the like can be mentioned.
- the pH adjustment method include a method of adjusting the content of the acid catalyst within the above preferable range and adjusting the content of the curing catalyst.
- the coating solution for forming an ultraviolet absorbing film of the present invention usually hydrolyzes the organooxysilane compound and the like together with a predetermined amount of the organooxysilane compound as an essential component and various additives as optional ingredients.
- the amount of water contained in the coating solution for forming an ultraviolet absorbing film of the present invention is not particularly limited as long as it is sufficient to hydrolyze / condensate the organooxysilane compound and the like.
- the amount of the component derived from (c) is preferably 4 to 20 equivalents, more preferably 8 to 15 equivalents, with respect to the SiO 2 equivalent of the component. If the amount of water is less than 4 equivalents in the above molar ratio, hydrolysis does not proceed and the haze increases at the time of coating, or the coating solution may be repelled depending on the substrate at the time of coating. There is a possibility that it becomes fast and long-term storage property is not sufficient.
- the ultraviolet absorbing film formed using the coating liquid for forming an ultraviolet absorbing film of the present invention has a hardness that can withstand normal use, but the light absorbing property of the resulting ultraviolet absorbing film is improved, in particular, the light deterioration of the ultraviolet absorbing ability.
- a decrease in hardness for example, scratch resistance may be observed.
- the coating liquid for forming an ultraviolet absorbing film of the present invention has a pKa of 1.0 to 5.
- silica fine particles When 0 acid is used, it is preferable to add silica fine particles and further increase the amount of water added to hydrolyze / condensate the organooxysilane compound and the like.
- silica fine particles to be used include the same silica fine particles as described above. The preferred embodiment is also the same.
- the blending amount of the silica fine particles and water specifically, for the silica fine particles, the reaction product of the component derived from the organooxysilane compound (a), the hydroxyl group-containing benzophenone compound and the epoxy group-containing organooxysilane compound.
- the blending amount of 0.5 to 50 parts by mass, more preferably 1.0 to 10 parts by mass, with respect to water, is a molar ratio with respect to the SiO 2 equivalent of the component derived from the organooxysilane compound (c).
- the amount is preferably 8 to 20 equivalents, more preferably 12.5 to 17.5 equivalents.
- the scratch resistance may be lowered.
- silica fine particles are blended in excess of the above upper limit, it may affect the film-forming property of the ultraviolet absorbing film, and if water is blended in excess of the above upper limit, the hydrolysis rate will increase and long-term storage will not be sufficient. There is.
- the coating solution for forming an ultraviolet-absorbing film of the present invention is usually dissolved and dispersed in an arbitrary amount of a predetermined amount of the organooxysilane compound as an essential component and various additives as an optional compounding agent in an arbitrary amount. Prepared in the form. It is necessary that all the non-volatile components in the coating liquid for forming an ultraviolet absorbing film are stably dissolved and dispersed in a solvent.
- the solvent contains at least 20% by mass, preferably 50% by mass or more of alcohol. .
- alcohols used in such solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, and 2-ethoxyethanol. 4-methyl-2-pentanol, 2-butoxyethanol and the like are preferable.
- the component derived from the organooxysilane compound (a), a hydroxyl group-containing benzophenone compound and an epoxy group-containing organooxysilane compound The components derived from the organooxysilane compound (b) which is a reaction product with the above and the components derived from the organooxysilane compound (c) other than the above (a) and (b) have good solubility, group Alcohol with a boiling point of 80-160 ° C is used because of its good coating properties. Masui.
- 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.
- a solvent used in the coating solution for forming an ultraviolet absorbing film of the present invention when the coating solution contains a partially hydrolyzed (co) condensate, a raw material organooxysilane compound (for example, an alkyltrisilane) is produced during the production process.
- a lower alcohol generated by hydrolysis of (alkoxysilane) or colloidal silica dispersed in an organic solvent is used, the dispersed organic solvent is also included.
- solvents other than alcohol that can be mixed with water / alcohol may be used in combination.
- examples include ketones such as acetone and 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 used in the coating solution for forming an ultraviolet absorbing film of the present invention is preferably 100 to 1900 parts by weight, and preferably 250 to 900 parts per 100 parts by weight of all nonvolatile components in the coating solution for forming an ultraviolet absorbing film. More preferably, it is part by mass.
- the coating solution for forming an ultraviolet absorbing film of the present invention contains organooxysilane compounds (a) to (c) themselves as components derived from the organooxysilane compounds (a) to (c), respectively. May be subjected to a partial hydrolysis (co) condensation treatment in order to stabilize the coating solution during storage or the like.
- the partial hydrolysis cocondensation is preferably performed in the presence of an acid catalyst under the same reaction conditions as described above.
- the purpose can be achieved by mixing the organooxysilane compounds (a) to (c) and then stirring them for a predetermined time at room temperature in the presence of an acid catalyst.
- the ultraviolet-absorbing glass article of the present invention has a glass substrate and an ultraviolet-absorbing film formed on the surface of at least a part of the glass substrate using the coating liquid for forming an ultraviolet-absorbing film of the present invention.
- the material of the glass substrate used in the ultraviolet absorbing glass article of the present invention is not particularly limited, and examples thereof include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Moreover, it is also possible to use the glass base material which absorbs an ultraviolet-ray and infrared rays as a glass base material of the ultraviolet-absorption glass article of this invention.
- UV-absorbing glass article of the present invention is preferably applied in applications where wear resistance is particularly required, specifically for automobile windows, particularly for windshields and sliding windows.
- the ultraviolet-absorbing glass article of the present invention has an ultraviolet-absorbing film formed as described later using the coating liquid for forming an ultraviolet-absorbing film of the present invention having the above-described configuration, and is derived from the organooxysilane compound (b).
- the transmittance of light at a wavelength of 380 nm measured using a spectrophotometer (manufactured by Hitachi, Ltd .: U-3500) is 7.0%, preferably 4 due to the ultraviolet absorption ability of the hydroxyl group-containing cibenzophenone compound residue of the component. 0.0%, more preferably 1.0% or less.
- the hydroxyl group-containing benzophenone compound residue which is an ultraviolet absorbing component
- the silicon oxide network constituting the ultraviolet absorbing film there is little bleed out due to long-term use, and the ultraviolet absorbing glass article of the present invention is converted into an ultraviolet ray.
- the absorption capacity is excellent in long-term storage stability.
- the component derived from the organooxysilane compound (a) and the component derived from the organooxysilane compound (c) act as a binder component to form the organooxysilane compound (b).
- a light absorption improver such as polyepoxides or glycerin and / or an acid having a pKa1 of 1.0 to 5.0 as an acid catalyst, preferably containing both
- the ultraviolet absorbing film formed using the coating liquid for film formation prevents the optical deterioration of the mechanical strength and ultraviolet absorbing ability of the ultraviolet absorbing film and has durability against light irradiation over a long period of time, that is, light resistance. It is.
- the ultraviolet absorbing glass article of the present invention has an ultraviolet absorbing film mainly composed of a silicon oxide network formed from the coating liquid for forming an ultraviolet absorbing film of the present invention.
- JIS-R3212 (1998) makes it possible to reduce the increase in the haze after the test with respect to the CS-10F wear wheel by the CS-10F wear wheel to 5.0% or less after the test. .
- the ultraviolet absorbing film-forming coating solution of the present invention As a specific method for forming the ultraviolet absorbing film-forming coating solution of the present invention on the glass substrate, (A) a step of coating the coating solution on the glass substrate to form a coating film, and (B) Removing the organic solvent from the coating film and curing three components derived from the organooxysilane compounds (a) to (c) (hereinafter referred to as “organooxysilane compounds”) to obtain a cured product And a method including a step of forming an ultraviolet absorbing film.
- the film formed here is a film containing the said solvent.
- the coating method of the coating solution on the glass substrate is not particularly limited as long as it is a method of uniform coating, and is a flow coating method, a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen printing method.
- Well-known methods such as 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 ultraviolet absorbing film.
- step (B) a step of removing the solvent from the coating film of the coating solution on the glass substrate and curing the organooxysilane compound or the like to form an ultraviolet absorbing film is performed.
- the volatile components are first removed by evaporation after the coating film is formed with the coating solution.
- This removal of volatile components is preferably carried out by heating and / or drying under reduced pressure.
- the volatile components are vaporized and removed in parallel with this, so the operation of removing the volatile components is included in the temporary drying.
- the temporary drying time that is, the operation time for removing the volatile components, is preferably about 3 seconds to 2 hours, although it depends on the coating solution used for film formation.
- the volatile component is sufficiently removed, but it may not be completely removed. That is, an organic solvent or the like can remain in the ultraviolet absorbing film as long as the performance of the ultraviolet absorbing film is not affected.
- heating for the production of the silicon oxide compound, which is performed as necessary, and heating for removing the volatile component, that is, temporary Drying may be performed continuously.
- the organooxysilane compound and the like are cured.
- This reaction can be carried out at room temperature or under heating.
- the upper limit of the heating temperature is preferably 200 ° C., and particularly preferably 190 ° C., because the cured product contains an organic component. Since the cured product can be generated even at normal temperature, the lower limit of the heating temperature is not particularly limited. However, when the promotion of the reaction by heating is intended, the lower limit of the heating temperature is preferably 60 ° C, more preferably 80 ° C. Therefore, the heating temperature is preferably 60 to 200 ° C, more preferably 80 to 190 ° C.
- the heating time is preferably from several minutes to several hours, although it depends on the coating solution used for film formation.
- the film thickness of the ultraviolet absorbing film of the ultraviolet absorbing glass article having the ultraviolet absorbing film thus formed using the coating liquid for forming an ultraviolet absorbing film of the present invention is 1.0 to 8.0 ⁇ m.
- the thickness is preferably 1.5 to 7.0 ⁇ m.
- the film thickness of the ultraviolet absorbing film is less than 1.0 ⁇ m, the ultraviolet absorbing effect may be insufficient.
- the film thickness of the ultraviolet absorbing film exceeds 8.0 ⁇ m, cracks may occur when desired wear resistance is exhibited.
- Examples 1 to 18 described below are examples, and examples 19 to 21 are comparative examples.
- the constituent compounds of drugs described by trade names in each example are shown below.
- SR-SEP manufactured by Sakamoto Pharmaceutical Co., Ltd., sorbitol-based polyglycidyl ether ⁇ Others>
- Methanol silica sol manufactured by Nissan Chemical Industries, Ltd., silica fine particles having an average primary particle size of 10 to 20 nm Colloidal silica with a solid content of 30% by mass dispersed in methanol
- UV absorber silylation synthesis example 2,2 ', 4,4'-tetrahydroxybenzophenone (BASF) 49.2g, 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical) 47.3g, benzyltriethylammonium chloride (Junsei) ) 0.8 g and 100 g of butyl acetate (manufactured by Junsei Kagaku Co., Ltd.), heated to 60 ° C. with stirring, dissolved, heated to 120 ° C. and reacted for 4 hours to give a silylation with a solid content of 49% by mass A UV absorber solution was obtained.
- BASF 4,4'-tetrahydroxybenzophenone
- Example 1 41.9 g of ethanol, 17.3 g of tetramethoxysilane, 5.8 g of 3-glycidoxypropyltrimethoxysilane, 15.0 g of the silylated ultraviolet absorber solution obtained in the above synthesis example, 15.8 g of pure water, 1% An aqueous nitric acid solution 4.2 g was charged and stirred for 1 hour to obtain a coating solution 1 for forming an ultraviolet absorbing film. Thereafter, a high heat ray absorbing green glass (Tv: 75.2%, Tuv: 9.5%, light transmittance at a wavelength of 380 nm: 38.5%, length 10 cm, width 10 cm, thickness 3.5 cm) with a clean surface.
- Tv 75.2%
- Tuv 9.5%
- UVFL Asahi Glass Co., Ltd., commonly called UVFL
- Spectral characteristics were measured using a spectrophotometer (manufactured by Hitachi, Ltd .: U-3500), and judged by the light transmittance at a wavelength of 380 nm, the visible light transmittance and the ultraviolet transmittance calculated according to JIS-R3106. .
- Abrasion resistance Using a Taber type abrasion resistance tester, a wear test of 1000 revolutions with a CS-10F wear wheel was performed by the method described in JIS-R3212 (1998), and the degree of scratches before and after the test was clouded The haze value was measured, and the haze value was increased by [%]. 5) Humidity resistance test: The specimen is put into a constant temperature and humidity chamber at 80 ° C. and 95 RH%, and after 1000 hours, the transmittance of light with a wavelength of 380 nm is measured with respect to the specimen. Judgment was made.
- Accelerated weather resistance test (light resistance evaluation): A specimen is placed on a super xenon weather meter (Suga test machine: SX75), the illumination intensity is 150 W / m 2 (300-400 nm), the black panel temperature is 83 ° C., and the humidity is 50 RH%. After 1000 hours had passed after the specimen was exposed to the above conditions, the transmittance of light having a wavelength of 380 nm to the specimen was measured, and cracks were determined by the same method as in 2) above.
- Scratch test (scratch resistance / hardness evaluation): A ball pencil was pressed against a UV absorbing film on a glass plate by a human hand and scratched for 2 cm, and the scratch mark was determined visually to make a scratch test. The case where the film had scratches that could be observed with the naked eye was evaluated as x, and the film that had no or almost no scratches that could be observed with the naked eye was rated as ⁇ .
- Example 2 A glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the film thickness was changed. The characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 3 42.6 g of ethanol, 18.1 g of tetramethoxysilane, 4.6 g of 3-glycidoxypropyltrimethoxysilane, 14.8 g of the silylated ultraviolet absorber solution obtained in the above synthesis example, 15.8 g of pure water, 1%
- An aqueous nitric acid solution 4.2 g was charged and stirred for 1 hour to obtain a coating solution 2 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating solution 2 was used instead of the coating solution 1.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 4 41.9 g of ethanol, 15.4 g of tetramethoxysilane, 8.0 g of 3-glycidoxypropyltrimethoxysilane, 15.2 g of the silylated ultraviolet absorber solution obtained in the above synthesis example, 15.4 g of pure water, 1%
- An aqueous nitric acid solution (4.2 g) was charged and stirred for 1 hour to obtain a coating solution 3 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating solution 3 was used in place of the coating solution 1.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 5 46.2 g of ethanol, 16.6 g of tetramethoxysilane, 2.8 g of 3-glycidoxypropyltrimethoxysilane, 17.0 g of the silylated UV absorber solution obtained in the above synthesis example, 13.8 g of pure water, 1%
- An aqueous nitric acid solution (3.6 g) was charged and stirred for 1 hour to obtain a coating solution 4 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating solution 4 was used instead of the coating solution 1.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 6 38.8 g of ethanol, 16.4 g of tetramethoxysilane, 9.8 g of 3-glycidoxypropyltrimethoxysilane, 13.4 g of the silylated UV absorber solution obtained in the above synthesis example, 17.1 g of pure water, 1% An aqueous nitric acid solution (4.5 g) was charged and stirred for 1 hour to obtain a coating solution 5 for forming an ultraviolet absorbing film. A glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating solution 5 was used instead of the coating solution 1. The characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 7 21.2 g of Solmix AP-1, 15.0 g of tetramethoxysilane, 5.1 g of 3-glycidoxypropyltrimethoxysilane, 14.6 g of the silylated UV absorber solution obtained in the above synthesis example, 1.2 g of SR-SEP as polyepoxide, 2.1 g of methanol silica sol as colloidal silica, 14.2 g of acetic acid, and 26.6 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 6 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 1 except that the above coating solution 6 was used instead of the coating solution 1 and the drying conditions were 180 ° C. and 30 minutes.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1 except that the temperature of the moisture resistance test was changed to 50 ° C. The evaluation results are shown in Table 2.
- Example 8 A glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the film thickness was changed. The characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 9 14.0 g of Solmix AP-1, 16.5 g of tetramethoxysilane, 5.2 g of 3-glycidoxypropyltrimethoxysilane, 15.0 g of the silylated UV absorber solution obtained in the above synthesis example, As a polyepoxide, 0.3 g of SR-SEP, 4.2 g of methanol silica sol as colloidal silica, 15.6 g of acetic acid, and 29.2 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 7 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 7 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 10 20.5 g of Solmix AP-1, 14.5 g of tetramethoxysilane, 5.3 g of 3-glycidoxypropyltrimethoxysilane, 15.0 g of the silylated UV absorber solution obtained in the above synthesis example, 1.1 g of SR-SEP as polyepoxide, 4.2 g of methanol silica sol as colloidal silica, 13.7 g of acetic acid, and 25.7 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 8 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 8 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 11 49.5 g of Solmix AP-1, 15.5 g of tetramethoxysilane, 4.9 g of 3-glycidoxypropyltrimethoxysilane, 14.1 g of the silylated UV absorber solution obtained in the above synthesis example.
- SR-SEP 3.1 g of 1% nitric acid aqueous solution
- 11.6 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 9 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 9 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 12 34.9 g of Solmix AP-1, 15.5 g of tetramethoxysilane, 4.9 g of 3-glycidoxypropyltrimethoxysilane, 14.1 g of the silylated UV absorber solution obtained in the above synthesis example, As a polyepoxide, 1.3 g of SR-SEP, 14.6 g of acetic acid, and 14.6 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 10 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 7 except that the coating solution 10 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 13 33.9 g of Solmix AP-1, 15.8 g of tetramethoxysilane, 5.0 g of 3-glycidoxypropyltrimethoxysilane, 14.4 g of the silylated UV absorber solution obtained in the above synthesis example, 1.0 g of glycerin (manufactured by Junsei Chemical Co., Ltd.), 14.9 g of acetic acid and 14.9 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 11 for forming an ultraviolet absorbing film.
- glycerin manufactured by Junsei Chemical Co., Ltd.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 11 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 14 50.3 g of Solmix AP-1, 12.1 g of tetramethoxysilane, 3.8 g of 3-glycidoxypropyltrimethoxysilane, 11.0 g of the silylated UV absorber solution obtained in the above synthesis example, 11.4 g of acetic acid and 11.4 of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 12 for forming an ultraviolet absorbing film. A glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 12 was used instead of the coating solution 6. The characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1 except for the moisture resistance test. The evaluation results are shown in Table 2.
- Example 15 52.2 g of Solmix AP-1, 12.1 g of tetramethoxysilane, 3.8 g of 3-glycidoxypropyltrimethoxysilane, 11.0 g of the silylated UV absorber solution obtained in the above synthesis example, 9.5 g of lactic acid and 11.4 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 13 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 7 except that the coating solution 13 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1 except for the moisture resistance test. The evaluation results are shown in Table 2.
- Example 16 61.5 g of Solmix AP-1, 12.1 g of tetramethoxysilane, 3.8 g of 3-glycidoxypropyltrimethoxysilane, 11.0 g of the silylated UV absorber solution obtained in the above synthesis example, 0.2 g of malonic acid and 11.4 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 14 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 7 except that the coating solution 14 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1 except for the moisture resistance test. The evaluation results are shown in Table 2.
- Example 17 17.8 g of Solmix AP-1, 16.5 g of tetramethoxysilane, 5.3 g of 3-glycidoxypropyltrimethoxysilane, 15.1 g of the silylated UV absorber solution obtained in the above synthesis example, As a polyepoxide, 0.3 g of SR-SEP, 15.6 g of acetic acid, and 29.3 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 15 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 7 except that the coating solution 15 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 18 30.4 g of Solmix AP-1, 15.5 g of tetramethoxysilane, 4.9 g of 3-glycidoxypropyltrimethoxysilane, 14.2 g of the silylated UV absorber solution obtained in the above synthesis example, As a polyepoxide, 1.2 g of SR-SEP, 4.3 g of methanol silica sol as colloidal silica, 14.7 g of acetic acid, and 14.7 g of ion-exchanged water were charged and stirred for 1 hour. Thereafter, 4.94 g of Solmix AP-1 was added and stirred to obtain a coating solution 16 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 7 except that the coating solution 16 was used instead of the coating solution 6.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.
- Example 19 Charge 43.3 g of ethanol, 21.8 g of tetramethoxysilane, 14.2 g of the silylated UV absorber solution obtained in the above synthesis example, 16.4 g of pure water, 4.3 g of 1% nitric acid aqueous solution, and stir for 1 hour.
- a coating solution 17 for forming an ultraviolet absorbing film was obtained.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating solution 17 was used instead of the coating solution 1.
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 20 47.0 g of ethanol, 15.1 g of tetramethoxysilane, 5.1 g of methyltrimethoxysilane, 13.1 g of the silylated UV absorber solution obtained in the above synthesis example, 15.6 g of pure water, 4.1 g of 1% nitric acid aqueous solution And stirred for 1 hour to obtain a coating solution 18 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was produced in the same manner as in Example 1 except that the coating liquid 18 was used instead of the coating liquid 1 and the film thickness of the ultraviolet absorbing film after drying was changed as shown in Table 2. .
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Example 21 49.6 g of ethanol, 17.3 g of tetramethoxysilane, 9.6 g of 3-glycidoxypropyltrimethoxysilane, 3.6 g of 2,2 ′, 4,4′-tetrahydroxybenzophenone, 15.8 g of pure water, 1%
- An aqueous nitric acid solution 4.2 g was charged and stirred for 1 hour to obtain a coating solution 19 for forming an ultraviolet absorbing film.
- a glass plate with an ultraviolet absorbing film was prepared in the same manner as in Example 1 except that the coating liquid 19 was used instead of the coating liquid 1 and the film thickness of the ultraviolet absorbing film after drying was changed as shown in Table 2. .
- the characteristics of the obtained glass plate with an ultraviolet absorbing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
- Table 1 summarizes the compositions of the coating solutions for forming an ultraviolet absorbing film obtained in Examples 1 to 21.
- the abbreviations of the compounds used indicate the following compounds.
- TMOS Tetramethoxysilane
- MTMS Methyltrimethoxysilane
- GPTMS 3-Glycidoxypropyltrimethoxysilane
- Si-THBP Silylated UV absorber THBP obtained in the synthesis example: 2,2 ', 4,4'-tetra Hydroxybenzophenone
- the ultraviolet absorbing films produced in Comparative Examples 19 to 21 have an ultraviolet absorbing ability but have cracks and insufficient mechanical properties.
- the ultraviolet absorbing films prepared in Examples 1 to 18 as examples are excellent in ultraviolet absorbing ability and in mechanical properties such as wear resistance and crack resistance.
- the ultraviolet absorbing films prepared in Examples 7 to 18 contain polyepoxides and glycerin in the coating composition that is a film forming material and / or a weak acid having a pKa1 of 1.0 to 5.0 as an acid catalyst. It is an ultraviolet absorbing film excellent in light resistance in which generation of cracks after the accelerated weathering test and reduction in ultraviolet absorbing ability are suppressed. Further, the ultraviolet absorbing films prepared in Examples 1 to 11 use strong acid (nitric acid) as an acid, or contain a polyepoxide or glycerin in a coating composition that is a film forming material, and in addition, as an acid catalyst. A weak acid (acetic acid) is used, and silica fine particles and water are mixed in an appropriate amount.
- strong acid acetic acid
- the UV-absorbing glass article of the present invention has excellent UV-absorbing property and mechanical durability, and mechanical durability such as wear resistance and crack resistance such as automotive door glass plates is highly required. It is also possible to apply to the part to be applied.
- the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-118259 filed on May 15, 2009 are incorporated herein as the disclosure of the present invention.
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Abstract
Description
[1]エポキシ基含有オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分、の3成分の組合せを含有し、前記3成分のそれぞれは、前記(a)~(c)のオルガノオキシシラン化合物であるか、または前記(a)~(c)のオルガノオキシシラン化合物の1種以上の部分加水分解縮合物の構成成分である、ことを特徴とする紫外線吸収膜形成用塗布液。(なお、本明細書において、「(a)~(c)」とは、以下、特段の定めがない限り、上記(a)、(b)および(c)を含む意味で使用される。)
[2]前記塗布液における前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の含有割合が、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100重量部に対して、前記オルガノオキシシラン化合物(a)に由来する成分については5~50質量部、前記オルガノオキシシラン化合物(b)に由来する成分については10~50質量部、前記オルガノオキシシラン化合物(c)に由来する成分については40~80質量部となる割合である、[1]に記載の紫外線吸収膜形成用塗布液。
[3]ポリエポキシド類およびグリセリンから選ばれる少なくとも1種を含有する[1]または[2]に記載の紫外線吸収膜形成用塗布液。
[4]前記ポリエポキシド類およびグリセリンから選ばれる少なくとも1種の含有量が、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100質量部に対して0.1~20質量部である[3]に記載の紫外線吸収膜形成用塗布液。
[5]第一プロトンのpKaが1.0~5.0の酸を、該酸の第一プロトンが完全に解離したときのプロトンの塗布液全質量に対するモル濃度として0.005~5.0モル/kgとなる割合で含有する[1]~[4]のいずれかに記載の紫外線吸収膜形成用塗布液。
[6]シリカ微粒子を、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100質量部に対して0.5~50質量部の割合で含有し、水を、前記オルガノオキシシラン化合物(c)に由来する成分のSiO2換算量に対してモル比で8~20当量の割合で含有する[1]~[5]のいずれかに記載の紫外線吸収膜形成用塗布液。
[7]前記オルガノオキシシラン化合物(c)に由来する成分の含有量が、この成分に含まれるケイ素原子をSiO2に換算したときのSiO2含有量として、1~10質量%である、[1]~[6]のいずれかに記載の紫外線吸収膜形成用塗布液。
[8]ガラス基材と、前記ガラス基材の少なくとも一部の表面に[1]~[7]のいずれかに記載の紫外線吸収膜形成用塗布液を用いて形成された紫外線吸収膜とを有する紫外線吸収ガラス物品。
[9]前記ガラス物品に対する波長380nmの光の透過率が7.0%以下である、[8]に記載の紫外線吸収ガラス物品。
[10]前記紫外線吸収膜の表面に対して、JIS-R3212(1998年)によるCS-10F摩耗ホイールでの1000回転摩耗試験を行ったときの、試験前に対する試験後の曇価の増加量が5.0%以下である、[8]または[9]に記載の紫外線吸収ガラス物品。
[本発明の紫外線吸収膜形成用塗布液]
本発明の紫外線吸収膜形成用塗布液は、エポキシ基含有オルガノオキシシラン化合物(a)に由来する成分と、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)(以下、必要に応じて「シリル化ベンゾフェノン系化合物」ともいう)に由来する成分および、前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分とを含有する。なお、上記オルガノオキシシラン化合物(a)~(c)は、それぞれ、ケイ素原子に結合したオルガノオキシ基を2以上有する化合物である。
したがって、本発明の紫外線吸収膜形成用塗布液は、オルガノオキシシラン化合物(a)~(c)にそれぞれ由来する成分として、オルガノオキシシラン化合物(a)~(c)自体を含有してもよく、オルガノオキシシラン化合物(a)~(c)それぞれの部分加水分解縮合物を含有していてもよい。さらに、本発明の紫外線吸収膜形成用塗布液は、オルガノオキシシラン化合物(a)~(c)中の任意の2種の部分加水分解共縮合物と他の1種とを含有していてもよい。さらに、本発明の紫外線吸収膜形成用塗布液は、オルガノオキシシラン化合物(a)~(c)の3種の部分加水分解共縮合物を含有していてもよい。これらの部分加水分解縮合物や部分加水分解共縮合物については、各オルガノオキシシラン化合物の説明の後に説明する。
本発明におけるエポキシ基含有オルガノオキシシラン化合物(a)は、エポキシ基を含有する有機基がケイ素原子に結合しているオルガノオキシシラン化合物であれば、特に限定されないが、好ましくは、下記一般式(A)で示されるオルガノオキシシラン化合物を挙げることができる。なお、上記ケイ素原子に結合している有機基とはケイ素原子に結合する原子が炭素原子である有機基をいう。また、以下、エポキシ基含有オルガノオキシシラン化合物(a)をオルガノオキシシラン化合物(a)ともいう。
ここで、式(A)中、R1はエポキシ基を含有する有機基であり、R2は炭素数1~10のアルキル基またはアリール基、R3は水素原子または炭素数1~10の酸素原子を含んでもよい1価炭化水素基であり、aは1または2、bは0または1であり、a+bは1または2である。
なお、上記式(A)中、a+bは1または2であることから、4-a-bで示されるケイ素原子に結合するOR3の数は、3または2である。
本発明に用いられるオルガノオキシシラン化合物(a)は、厚膜化したときに所望の耐摩耗性を維持しつつ、耐クラック性を付与するバインダーとして作用すると考えられる。
本発明におけるオルガノオキシシラン化合物(b)、すなわち、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)は、原料である水酸基含有ベンゾフェノン系化合物の作用により紫外線吸収能を有する成分である。水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物(前記のように、シリル化ベンゾフェノン系化合物ともいう)は、オルガノオキシシラン化合物から形成される架橋構造を有する酸化ケイ素系ネットワーク内に組み込まれることで、水酸基含有ベンゾフェノン系化合物の残基がネットワークに固定される。これにより、水酸基含有ベンゾフェノン系化合物がブリードアウトすることがなく、これにより紫外線吸収膜が長期にわたって紫外線吸収能を保持することを可能としている。なお、シリル化ベンゾフェノン系化合物はオルガノオキシシラン化合物(a)と同様のオルガノオキシシシリル基を有することより、オルガノオキシシラン化合物の1種とみなす。
本発明におけるオルガノオキシシラン化合物(c)は、前記(a)、(b)以外のオルガノオキシシラン化合物、すなわち、エポキシ基や水酸基含有ベンゾフェノン系化合物の残基を含有しないオルガノオキシシラン化合物である。オルガノオキシシラン化合物(c)としては、エポキシ基や水酸基含有ベンゾフェノン系化合物の残基を含有しないオルガノオキシシラン化合物であれば、特に限定されないが、本発明において好ましくは、下記一般式(C)で示されるシラン化合物が挙げられる。
ここで、式(C)中R4は、炭素数1~10の置換または非置換の1価炭化水素基であり、R5は炭素数1~10のアルキル基またはアリール基、R6は水素原子または炭素数1~10の酸素原子を含んでもよい1価炭化水素基であり、mおよびnは0、1または2であり、m+nは0、1または2である。ただし、上記R4は、エポキシ基を含有する有機基ではなく、また水酸基含有ベンゾフェノン系化合物の残基を有する有機基でもない。
本発明の紫外線吸収膜形成用塗布液は、オルガノオキシシラン化合物(a)~(c)にそれぞれ由来する成分として、上記オルガノオキシシラン化合物(a)~(c)のそれぞれの部分加水分解縮合物を含有していてもよい。また、本発明の紫外線吸収膜形成用塗布液は、オルガノオキシシラン化合物(a)~(c)の任意の2種の部分加水分解共縮合物と他の1種を含有していてもよく、オルガノオキシシラン化合物(a)~(c)の3種の部分加水分解共縮合物を含有してもよい。
本発明において上記部分加水分解(共)縮合に用いる酸触媒は、得られる紫外線吸収膜に十分な耐光性を保持させる、特に紫外線吸収能の光劣化を防止する観点から、第一プロトンのpKa(以下、pKa1と記載する。)が1.0~5.0の酸を用いることが好ましい。このような酸として、具体的には、酢酸(pKa1=4.76)、乳酸(pKa1=3.64)、マレイン酸(pKa1=1.84)、マロン酸(pKa1=2.65)、シュウ酸(pKa1=1.04)等が挙げられる。
本発明の紫外線吸収膜形成用塗布液は、エポキシ基含有オルガノオキシシラン化合物(a)に由来する成分と、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)(以下、必要に応じて「シリル化ベンゾフェノン系化合物」ともいう)に由来する成分および、前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分とを含有する。
ポリエポキシド類とは、複数のエポキシ基を有する化合物の総称である。すなわち、ポリエポキシド類の平均エポキシ基数は2以上であるが、本発明においては平均エポキシ基数が2~10のポリエポキシドが好ましい。
なお、本発明の紫外線吸収膜形成用塗布液においては、耐光性の向上、特に紫外線吸収能の光劣化を防止する観点から、上記ポリエポキシド類やグリセリン等の耐光性向上剤とともに、第一プロトンのpKaが1.0~5.0の酸を用いることが好ましい。
なお、上記シリカ微粒子として水分散型コロイダルシリカを用いた場合には、その水も紫外線吸収膜形成用塗布液に含まれる水として扱われる。
本発明の紫外線吸収ガラス物品は、ガラス基材と、前記ガラス基材の少なくとも一部の表面に上記本発明の紫外線吸収膜形成用塗布液を用いて形成された紫外線吸収膜とを有する。
SR-SEP:阪本薬品工業社製、ソルビトール系ポリグリシジルエーテル
<その他>
ソルミックスAP-1:日本アルコール販売社製、エタノール:イソプロピルアルコール:メタノール=85:10:5(質量比)の混合溶媒
メタノールシリカゾル:日産化学工業社製、平均一次粒径10~20nmのシリカ微粒子を固形分濃度30質量%でメタノールに分散させたコロイダルシリカ
2,2’,4,4’-テトラヒドロキシベンゾフェノン(BASF社製)49.2g、3-グリシドキシプロピルトリメトキシシラン(信越化学社製)47.3g、塩化ベンジルトリエチルアンモニウム(純正化学社製)0.8g、酢酸ブチル(純正化学社製)100gを仕込み攪拌しながら60℃に昇温し、溶解させ、120℃まで加熱し4時間反応させることにより、固形分濃度49質量%のシリル化紫外線吸収剤溶液を得た。
エタノール41.9g、テトラメトキシシラン17.3g、3-グリシドキシプロピルトリメトキシシラン5.8g、上記合成例で得られたシリル化紫外線吸収剤溶液15.0g、純水15.8g、1%硝酸水溶液4.2gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液1を得た。その後、表面を清浄した高熱線吸収グリーンガラス(Tv:75.2%、Tuv:9.5%、波長380nmの光の透過率:38.5%、縦10cm、横10cm、厚さ3.5cm、旭硝子社製、通称UVFL)上にスピンコート法によって塗布し、大気中、150℃で30分間乾燥させた後、紫外線吸収膜付きガラス板を得た。得られた紫外線吸収膜付きガラス板の特性を以下のとおり評価した。評価結果を表2に示す。
1)膜厚:走査型電子顕微鏡(日立製作所製:S-800)によって紫外線吸収膜の断面観察を行い、得られた観察像より膜厚[nm]を得た。
5)耐湿試験:80℃、95RH%の恒温恒湿槽に検体を投入し、1000時間経過後、検体に対する波長380nmの光の透過率を測定するとともに、上記2)と同様の方法でクラックの判定を行った。
7)スクラッチ試験(耐傷付き性/硬度評価):ガラス板上の紫外線吸収膜に人の手によりボールペンシルを押し当て2cm引掻いた後、傷の跡を目視により判断してスクラッチ試験とした。膜に肉眼で観察できる傷があるものを×、肉眼で観察できる傷が全くない・ほとんどないものを○とした。
膜厚を変更した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
エタノール42.6g、テトラメトキシシラン18.1g、3-グリシドキシプロピルトリメトキシシラン4.6g、上記合成例で得られたシリル化紫外線吸収剤溶液14.8g、純水15.8g、1%硝酸水溶液4.2gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液2を得た。塗布液1に代えて上記塗布液2を使用した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
エタノール41.9g、テトラメトキシシラン15.4g、3-グリシドキシプロピルトリメトキシシラン8.0g、上記合成例で得られたシリル化紫外線吸収剤溶液15.2g、純水15.4g、1%硝酸水溶液4.2gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液3を得た。塗布液1に代えて上記塗布液3を使用した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
エタノール46.2g、テトラメトキシシラン16.6g、3-グリシドキシプロピルトリメトキシシラン2.8g、上記合成例で得られたシリル化紫外線吸収剤溶液17.0g、純水13.8g、1%硝酸水溶液3.6gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液4を得た。塗布液1に代えて上記塗布液4を使用した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
エタノール38.8g、テトラメトキシシラン16.4g、3-グリシドキシプロピルトリメトキシシラン9.8g、上記合成例で得られたシリル化紫外線吸収剤溶液13.4g、純水17.1g、1%硝酸水溶液4.5gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液5を得た。塗布液1に代えて上記塗布液5を使用した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の21.2g、テトラメトキシシランの15.0g、3-グリシドキシプロピルトリメトキシシランの5.1g、上記合成例で得られたシリル化紫外線吸収剤溶液の14.6g、ポリエポキシドとしてSR-SEPの1.2g、コロイダルシリカとしてメタノールシリカゾルの2.1g、酢酸の14.2g、イオン交換水の26.6gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液6を得た。塗布液1に代えて上記塗布液6を使用し、乾燥条件を180℃、30分間とした以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を、耐湿試験の温度を50℃に変更した以外は例1と同様に評価した。評価結果を表2に示す。
膜厚を変更した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の14.0g、テトラメトキシシランの16.5g、3-グリシドキシプロピルトリメトキシシランの5.2g、上記合成例で得られたシリル化紫外線吸収剤溶液の15.0g、ポリエポキシドとしてSR-SEPの0.3g、コロイダルシリカとしてメタノールシリカゾルの4.2g、酢酸の15.6g、イオン交換水の29.2gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液7を得た。塗布液6に代えて上記塗布液7を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の20.5g、テトラメトキシシランの14.5g、3-グリシドキシプロピルトリメトキシシランの5.3g、上記合成例で得られたシリル化紫外線吸収剤溶液の15.0g、ポリエポキシドとしてSR-SEPの1.1g、コロイダルシリカとしてメタノールシリカゾルの4.2g、酢酸の13.7g、イオン交換水の25.7gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液8を得た。塗布液6に代えて上記塗布液8を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の49.5g、テトラメトキシシランの15.5g、3-グリシドキシプロピルトリメトキシシランの4.9g、上記合成例で得られたシリル化紫外線吸収剤溶液の14.1g、ポリエポキシドとしてSR-SEPの1.3g、硝酸1%水溶液の3.1g、イオン交換水の11.6gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して紫外線吸収膜形成用塗布液9を得た。塗布液6に代えて上記塗布液9を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の34.9g、テトラメトキシシランの15.5g、3-グリシドキシプロピルトリメトキシシランの4.9g、上記合成例で得られたシリル化紫外線吸収剤溶液の14.1g、ポリエポキシドとしてSR-SEPの1.3g、酢酸の14.6g、イオン交換水の14.6gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液10を得た。塗布液6に代えて上記塗布液10を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の33.9g、テトラメトキシシランの15.8g、3-グリシドキシプロピルトリメトキシシランの5.0g、上記合成例で得られたシリル化紫外線吸収剤溶液の14.4g、グリセリン(純正化学社製)の1.0g、酢酸の14.9g、イオン交換水の14.9gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌し紫外線吸収膜形成用塗布液11を得た。塗布液6に代えて上記塗布液11を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の50.3g、テトラメトキシシランの12.1g、3-グリシドキシプロピルトリメトキシシランの3.8g、上記合成例で得られたシリル化紫外線吸収剤溶液の11.0g、酢酸の11.4g、イオン交換水の11.4を仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液12を得た。塗布液6に代えて上記塗布液12を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を、耐湿試験を除いて例1と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の52.2g、テトラメトキシシランの12.1g、3-グリシドキシプロピルトリメトキシシランの3.8g、上記合成例で得られたシリル化紫外線吸収剤溶液の11.0g、乳酸の9.5g、イオン交換水の11.4gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液13を得た。塗布液6に代えて上記塗布液13を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を、耐湿試験を除いて例1と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の61.5g、テトラメトキシシランの12.1g、3-グリシドキシプロピルトリメトキシシランの3.8g、上記合成例で得られたシリル化紫外線吸収剤溶液の11.0g、マロン酸の0.2g、イオン交換水の11.4gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液14を得た。塗布液6に代えて上記塗布液14を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を、耐湿試験を除いて例1と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の17.8g、テトラメトキシシランの16.5g、3-グリシドキシプロピルトリメトキシシランの5.3g、上記合成例で得られたシリル化紫外線吸収剤溶液の15.1g、ポリエポキシドとしてSR-SEPの0.3g、酢酸の15.6g、イオン交換水の29.3gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌し紫外線吸収膜形成用塗布液15を得た。塗布液6に代えて上記塗布液15を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
ソルミックスAP-1の30.4g、テトラメトキシシランの15.5g、3-グリシドキシプロピルトリメトキシシランの4.9g、上記合成例で得られたシリル化紫外線吸収剤溶液の14.2g、ポリエポキシドとしてSR-SEPの1.2g、コロイダルシリカとしてメタノールシリカゾルの4.3g、酢酸の14.7g、イオン交換水の14.7gを仕込み、一時間攪拌した。その後、ソルミックスAP-1の4.94gを添加し攪拌して、紫外線吸収膜形成用塗布液16を得た。塗布液6に代えて上記塗布液16を使用した以外は例7と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例7と同様に評価した。評価結果を表2に示す。
エタノール43.3g、テトラメトキシシラン21.8g、上記合成例で得られたシリル化紫外線吸収剤溶液14.2g、純水16.4g、1%硝酸水溶液4.3gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液17を得た。塗布液1に代えて上記塗布液17を使用した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す
エタノール47.0g、テトラメトキシシラン15.1g、メチルトリメトキシシラン5.1g、上記合成例で得られたシリル化紫外線吸収剤溶液13.1g、純水15.6g、1%硝酸水溶液4.1gを仕込み、一時間攪拌して紫外線吸収膜形成用塗布液18を得た。塗布液1に代えて上記塗布液18を使用し、乾燥後の紫外線吸収膜の膜厚を表2に示すように変更した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す
エタノール49.6g、テトラメトキシシラン17.3g、3-グリシドキシプロピルトリメトキシシラン9.6g、2,2’,4,4’-テトラヒドロキシベンゾフェノン3.6g、純水15.8g、1%硝酸水溶液4.2gを仕込み、一時間攪拌して、紫外線吸収膜形成用塗布液19を得た。塗布液1に代えて上記塗布液19を使用し、乾燥後の紫外線吸収膜の膜厚を表2に示すように変更した以外は例1と同様にして、紫外線吸収膜付きガラス板を作製した。得られた紫外線吸収膜付きガラス板の特性を例1と同様に評価した。評価結果を表2に示す。
TMOS:テトラメトキシシラン
MTMS:メチルトリメトキシシラン
GPTMS:3-グリシドキシプロピルトリメトキシシラン
Si-THBP:合成例で得られたシリル化紫外線吸収剤
THBP:2,2’,4,4’-テトラヒドロキシベンゾフェノン
なお、2009年5月15日に出願された日本特許出願2009-118259号の明細書、特許請求の範囲及び要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
Claims (10)
- エポキシ基含有オルガノオキシシラン化合物(a)に由来する成分、
水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および
前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分、
の3成分の組合せを含有し、
前記3成分のそれぞれは、前記(a)~(c)のオルガノオキシシラン化合物であるか、または前記(a)~(c)のオルガノオキシシラン化合物の1種以上の部分加水分解縮合物の構成成分である、
ことを特徴とする紫外線吸収膜形成用塗布液。 - 前記塗布液における前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の含有割合が、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100重量部に対して、前記オルガノオキシシラン化合物(a)に由来する成分については5~50質量部、前記オルガノオキシシラン化合物(b)に由来する成分については10~50質量部、前記オルガノオキシシラン化合物(c)に由来する成分については40~80質量部となる割合である、請求項1に記載の紫外線吸収膜形成用塗布液。
- ポリエポキシド類およびグリセリンから選ばれる少なくとも1種を含有する請求項1または2に記載の紫外線吸収膜形成用塗布液。
- 前記ポリエポキシド類およびグリセリンから選ばれる少なくとも1種の含有量が、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100質量部に対して0.1~20質量部である請求項3に記載の紫外線吸収膜形成用塗布液。
- 第一プロトンのpKaが1.0~5.0の酸を、該酸の第一プロトンが完全に解離したときのプロトンの塗布液全質量に対するモル濃度として0.005~5.0モル/kgとなる割合で含有する請求項1~4のいずれか1項に記載の紫外線吸収膜形成用塗布液。
- シリカ微粒子を、前記オルガノオキシシラン化合物(a)に由来する成分、水酸基含有ベンゾフェノン系化合物とエポキシ基含有オルガノオキシシラン化合物との反応生成物であるオルガノオキシシラン化合物(b)に由来する成分、および前記(a)、(b)以外のオルガノオキシシラン化合物(c)に由来する成分の合計固形分量100質量部に対して0.5~50質量部の割合で含有し、水を、前記オルガノオキシシラン化合物(c)に由来する成分のSiO2換算量に対してモル比で8~20当量の割合で含有する請求項1~5に記載の紫外線吸収膜形成用塗布液。
- 前記オルガノオキシシラン化合物(c)に由来する成分の含有量が、この成分に含まれるケイ素原子をSiO2に換算したときのSiO2含有量として、1~10質量%である、請求項1~6のいずれか1項に記載の紫外線吸収膜形成用塗布液。
- ガラス基材と、前記ガラス基材の少なくとも一部の表面に請求項1~7のいずれか1項に記載の紫外線吸収膜形成用塗布液を用いて形成された紫外線吸収膜とを有する紫外線吸収ガラス物品。
- 前記ガラス物品に対する波長380nmの光の透過率が7.0%以下である、請求項8に記載の紫外線吸収ガラス物品。
- 前記紫外線吸収膜の表面に対して、JIS-R3212(1998年)によるCS-10F摩耗ホイールでの1000回転摩耗試験を行ったときの、試験前に対する試験後の曇価の増加量が5.0%以下である、請求項8または9に記載の紫外線吸収ガラス物品。
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Also Published As
Publication number | Publication date |
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US20160046522A1 (en) | 2016-02-18 |
JP2015214483A (ja) | 2015-12-03 |
JPWO2010131744A1 (ja) | 2012-11-08 |
CN102421862A (zh) | 2012-04-18 |
EP2431433B1 (en) | 2020-12-30 |
EP2431433A1 (en) | 2012-03-21 |
EP2431433A4 (en) | 2015-03-04 |
JP6010299B2 (ja) | 2016-10-19 |
BRPI1013097A2 (pt) | 2016-04-05 |
CN102421862B (zh) | 2014-11-12 |
US20120038976A1 (en) | 2012-02-16 |
JP6004054B2 (ja) | 2016-10-05 |
US10450223B2 (en) | 2019-10-22 |
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