JP2013136482A - Ultraviolet-absorbing glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-absorbing glass article, having an ultraviolet-absorbing film, excellent in cracking resistance and ultraviolet-absorbing ability at initial stage, hardly deteriorating in the ultraviolet-absorbing ability after long-term light exposure.SOLUTION: The ultraviolet-absorbing glass article contains a glass substrate and an ultraviolet-absorbing film formed on at least one part of the surface of the substrate by using a composition for forming an ultraviolet-absorbing film. The composition for forming an ultraviolet-absorbing film contains at least 50 mass% of a tetrafunctional hydrolyzable silicon compound in the whole amount of the solid, 50-93 mass% of silicon oxide based matrix raw component in terms of SiO, 5-30 mass% of a hydrophilic organic polymer, and 2-20 mass% of a fluorescent brightening agent with respective amount proportions. The film thickness of the ultraviolet-absorbing film is at most 5.0 μm and the ultraviolet ray transmittance in the formed area of the ultraviolet-absorbing film of the glass article in the initial stage defined in JIS-R3106 is at most 0.2%.

Description

  The present invention relates to an ultraviolet absorbing glass article.

  In recent years, 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.

  In order to obtain a UV-absorbing film having the above high wear resistance and UV-absorbing ability, it has been attempted to form a silica-based UV-absorbing film on a substrate using a composition in which an organic UV-absorbing agent is mixed with a silane compound. Has been made. For example, in Patent Document 1, a composition containing a silicon alkoxide and a water-soluble organic polymer such as polyethylene glycol, and further containing an ultraviolet absorber or an organic dye is applied on a glass plate and cured to form an organic-inorganic composite. It is described that an ultraviolet absorbing film made of a film is obtained.

  Here, it is known that the ultraviolet absorbers and organic dyes used in the ultraviolet absorbing film generally have a reduced ultraviolet absorbing ability when exposed to light for a long time. Therefore, the total amount of ultraviolet absorbers and the like in the ultraviolet absorbing film is required to be a certain amount or more, and this has been dealt with by increasing the film thickness. However, such a silica-based ultraviolet absorbing film has a problem that, when the film thickness is increased, cracks are generated immediately after the film formation or when the film is used for a long time in a high temperature and high humidity environment. Therefore, there has been a demand for an ultraviolet absorbing film that is excellent in crack resistance, particularly crack resistance in long-term use under high temperature and high humidity, and initial ultraviolet absorption ability, and is less deteriorated in ultraviolet absorption ability due to long-time exposure.

International Publication No. 2006/137454 Pamphlet

  The present invention has been made to solve the above-mentioned problems, and is excellent in crack resistance, particularly crack resistance in long-term use under high temperature and high humidity and initial ultraviolet absorption ability, and UV absorption by long-time exposure. An object of the present invention is to provide an ultraviolet-absorbing glass article having an ultraviolet-absorbing film with little deterioration in performance.

The present invention provides an ultraviolet absorbing glass article having the following configuration.
[1] An ultraviolet-absorbing glass article having a glass substrate and an ultraviolet-absorbing film formed on the surface of at least a part of the glass substrate using the ultraviolet-absorbing film-forming composition,
The composition for forming an ultraviolet absorbing film is a silicon oxide matrix raw material component composed of hydrolyzable silicon compounds containing a tetrafunctional hydrolyzable silicon compound in terms of SiO ₂ with respect to the total solid content in the composition. 50 to 93% by mass, 5 to 30% by mass of a hydrophilic organic polymer, and 2 to 20% by mass of an optical brightener, and the content of the tetrafunctional hydrolyzable silicon compound with respect to the total solid content The proportion is at least 50% by mass in terms of SiO ₂ ,
The ultraviolet absorbing film has a thickness of 5.0 μm or less,
And the ultraviolet absorption glass article whose initial ultraviolet transmittance defined by JIS-R3106 in the ultraviolet absorption film formation field of the glass article is 0.2% or less.

[2] The ultraviolet absorbing glass article according to [1], wherein the tetrafunctional hydrolyzable silicon compound is selected from tetramethoxysilane and / or tetraethoxysilane.
[3] The ultraviolet absorbing glass article according to [1] or [2], wherein the hydrophilic organic polymer contains a polyoxyalkylene group.
[4] The ultraviolet absorbing glass article according to any one of [1] to [3], wherein the optical brightener is soluble in a polar solvent.
[5] The ultraviolet absorbing glass article according to any one of [1] to [4], wherein the composition for forming an ultraviolet absorbing film further contains an ultraviolet absorber.

  According to the present invention, it has an ultraviolet-absorbing film which is excellent in crack resistance, particularly crack resistance in long-term use under high temperature and high humidity and initial ultraviolet absorption ability, and has little deterioration in ultraviolet absorption ability even after long exposure. An ultraviolet absorbing glass article can be provided.

Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
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 an ultraviolet-absorbing film-forming composition having the following specific composition: An ultraviolet absorbing glass article having an ultraviolet absorbing film thickness of 5.0 μm or less and an initial ultraviolet transmittance determined by JIS-R3106 in the ultraviolet absorbing film forming region of the glass article of 0.2% or less. It is.

The composition for forming an ultraviolet absorbing film used in the present invention contains the following components (1) to (3) in the following proportions with respect to 100% by mass of the total solid content in the composition.
(1) 50 to 93% by mass of a silicon oxide matrix raw material component composed of hydrolyzable silicon compounds containing a tetrafunctional hydrolyzable silicon compound in terms of SiO ₂ . However, the ratio with respect to 100 mass% of the total solid content in the composition of the tetrafunctional hydrolyzable silicon compound is at least 50 mass% in terms of SiO ₂ .
(2) 5-30 mass% of hydrophilic organic polymer.
(3) 2 to 20% by mass of optical brightener.

The film thickness of the ultraviolet absorbing film of the ultraviolet absorbing glass article of the present invention is 5.0 μm or less, and the initial ultraviolet transmittance determined by JIS-R3106 in the ultraviolet absorbing film forming region is 0.2% or less. Hereinafter, in this specification, the ultraviolet transmittance defined by JIS-R3106 is simply referred to as ultraviolet transmittance or Tuv.
Here, the “ultraviolet absorbing ability” of the ultraviolet absorbing glass article indicates an ultraviolet absorbing ability obtained by combining the ultraviolet absorbing ability of the ultraviolet absorbing film and the ultraviolet absorbing ability of the glass substrate. The high ultraviolet absorbing ability of the ultraviolet absorbing glass article is attributed to the high ultraviolet absorbing ability of the ultraviolet absorbing film.

  The fluorescent whitening agent used in the present invention is a compound that absorbs light of 360 to 400 nm and converts it to fluorescence of around 430 nm, and has an excellent ultraviolet absorbing ability. However, the fluorescent whitening agent has been used as an auxiliary agent for the ultraviolet absorber until now because the fluorescence generated by the fluorescent whitening agent becomes a problem when used in a large amount. UV absorbers have a lower UV absorption capacity than fluorescent brighteners, so it is necessary to increase the film thickness in order to increase the total amount. There was a problem. For this reason, the types of hydrolyzable silicon compounds constituting the flexible component and the silicon oxide matrix raw material component have been studied, but there was a problem in terms of wear resistance.

  The ultraviolet absorbing film according to the present invention contains a fluorescent brightening agent, a silicon oxide-based matrix raw material component, and a hydrophilic organic polymer in the above proportion in the ultraviolet absorbing film forming composition for forming the ultraviolet absorbing film, While avoiding the problem of crack generation at a thickness of 5.0 μm or less, it was possible to exhibit an excellent ultraviolet absorbing ability of an initial ultraviolet transmittance of 0.2% or less. Further, if the ultraviolet transmittance is 0.2% or less in the initial stage, the necessary ultraviolet transmittance can be maintained even by the long-time exposure. Furthermore, according to the composition of the ultraviolet absorbing film forming composition, the composition can maintain a sufficient level of wear resistance.

In addition, when the ultraviolet-absorbing glass article of the present invention is used for window glass for vehicles such as automobiles and window glass for building materials attached to buildings such as houses and buildings, it is usually a large area glass substrate. In addition, an ultraviolet absorbing film is formed on a large area, for example, one main surface. Even in such a case, the ultraviolet absorbing film formed using the composition for forming an ultraviolet absorbing film having the composition according to the present invention has a thickness of 5.0 μm or less over the entire film, and the film Uniform formation is possible so that the ultraviolet transmittance is 0.2% or less over the entire glass substrate in the region where is formed.
Hereinafter, the member which comprises the ultraviolet absorption glass article of this invention is demonstrated.

[Glass substrate]
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, alkali-free 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. Moreover, the laminated glass laminated | stacked using the resin intermediate film can also be used.

  Moreover, as a glass substrate used for the ultraviolet-absorbing glass article of the present invention, the transmittance of light with a wavelength of 400 nm is preferably 5% or more, and in order to further exhibit the effect of the ultraviolet-absorbing film, the light with a wavelength of 400 nm is used. More preferably, the transmittance is 20% or more. Furthermore, the transmittance of light having a wavelength of 400 nm is preferably 80% or less, and more preferably 65% or less. Further, the solar transmittance of JIS-R3106 (1998) of the glass substrate is preferably 75% or less, and more preferably 65% or less. Furthermore, the visible light transmittance is preferably 50% or more, and more preferably 70% or more.

  The shape, size, and thickness of the glass substrate used for the ultraviolet absorbing glass article of the present invention are not particularly limited. The shape of the glass substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. About the thickness of a glass base material, when using for the window for motor vehicles, or the window for construction, the thickness of about 0.5-10 mm is mentioned, for example.

  In the glass substrate used for the ultraviolet absorbing glass article of the present invention, for example, as a glass substrate capable of exhibiting the ultraviolet absorbing ability of the ultraviolet absorbing glass article, the light transmittance at a wavelength of 400 nm is 5 to 80%, JIS-R3106 ( 1998) is preferably a glass substrate having a solar transmittance of 65% or less and a visible light transmittance of 70% or more. Specifically, as such a glass substrate material, a green glass material containing metal ions such as titanium ions, cerium ions, and iron ions in a soda lime glass substrate is preferably used. When such a glass substrate is used, there is an advantage that not only higher ultraviolet absorption ability can be provided, but also the near infrared region near 1 μm can be shielded, and thus heat insulation can be provided.

  Further, a tempered glass obtained by heating a glass plate made of an inorganic glass material to a temperature close to 650 to 700 ° C. in the atmosphere, quenching it, and performing a tempering treatment can be used as a glass substrate. Further, a bent glass substrate is obtained by bending the glass substrate in this heat treatment. By using a glass substrate that has been subjected to such processing, a processed glass plate having an ultraviolet absorbing film with high durability is obtained, which is particularly useful as a window material for automobiles and buildings. .

  Note that the ultraviolet absorbing glass article of the present invention is preferably used for applications in which abrasion resistance is particularly required since the ultraviolet absorbing film is excellent in abrasion resistance. For windshields and sliding windows. Therefore, as the glass substrate, a glass substrate having a material, size and shape usually used for such applications is suitably used.

[Ultraviolet absorbing film]
In the ultraviolet-absorbing glass article of the present invention, the ultraviolet-absorbing film uses a composition for forming an ultraviolet-absorbing film that contains each of the components (1) to (3) in the above-mentioned proportion in the total solid content of the composition. Formed.
Hereinafter, each component contained in the composition for forming an ultraviolet absorbing film used in the present invention will be described.

(1) Silicon oxide matrix raw material component The silicon oxide matrix raw material component contained in the composition for forming an ultraviolet absorbing film used in the present invention is composed of hydrolyzable silicon compounds including a tetrafunctional hydrolyzable silicon compound. In the present specification, the hydrolyzable silicon compounds are a silane compound group in which at least one hydrolyzable group is bonded to a silicon atom, and one or two or more partial hydrolysiss of such a silane compound group ( Used as a generic term for condensates. The number of functionalities of the hydrolyzable silicon compound refers to the number of hydrolyzable groups bonded to the silicon atom.

  Hydrolyzable silicon compounds are hydrolyzed in the presence of water to generate hydroxyl groups (silanol groups) bonded to silicon atoms, and then the silanol groups are dehydrated and condensed to form —Si—O—. A siloxane bond represented by Si- is generated to increase the molecular weight. A linear polysiloxane is formed only from a bifunctional hydrolyzable silicon compound, but a three-dimensional network of polysiloxane is formed from a trifunctional hydrolyzable silicon compound or a tetrafunctional hydrolyzable silicon compound. As a result, a silicon oxide matrix is formed. Also, a three-dimensional network of polysiloxane is formed from a mixture of a bifunctional hydrolyzable silicon compound and a trifunctional hydrolyzable silicon compound or a tetrafunctional hydrolyzable silicon compound to form a silicon oxide matrix. Is done.

  The composition for forming an ultraviolet absorbing film used in the present invention may contain a partial hydrolysis condensate as a main component of the silicon oxide matrix raw material component, or may be a partial hydrolysis condensate. Contains a functional hydrolyzable silicon compound. Hereinafter, the tetrafunctional hydrolyzable silicon compound refers to a tetrafunctional hydrolyzable silicon compound and / or a partially hydrolyzed condensate thereof. The same applies to the trifunctional hydrolyzable silicon compound and the bifunctional hydrolyzable silicon compound.

The content of the silicon oxide-based matrix raw material component in the composition for forming an ultraviolet absorbing film is 50 to 93% by mass in terms of SiO _{2 with} respect to 100% by mass of the total solid content in the composition, and is a tetrafunctional hydrolyzable silicon compound The ratio of the total solid content in the composition to 100% by mass is at least 50% by mass in terms of SiO ₂ . The content of the silicon oxide-based matrix material component relative to the total solid content 100 wt% of the ultraviolet absorbing film forming composition and 50 to 93 mass% in terms of SiO _2, and the tetrafunctional hydrolyzable silicon compound in terms of SiO ₂ By setting the amount to 50% by mass or more, the obtained ultraviolet absorbing film has abrasion resistance, and has sufficient crack resistance within the range of the film thickness of the ultraviolet absorbing film of the ultraviolet absorbing glass article of the present invention and absorbs ultraviolet rays. The film formability of the film forming composition is also improved.

Content of the silicon oxide matrix raw material component with respect to 100% by mass of the total solid content of the composition for forming an ultraviolet absorbing film is 50 to 93% by mass in terms of SiO ₂ , and preferably 65 to 90% by mass. The tetrafunctional hydrolyzable silicon compound is 50% by mass or more, preferably 65% by mass or more, based on 100% by mass of the total solid content of the composition for forming an ultraviolet absorbing film.

  As long as the content of the tetrafunctional hydrolyzable silicon compound in the composition for forming an ultraviolet absorbing film can be ensured, the silicon oxide matrix raw material component is otherwise trifunctional hydrolyzable silicon compound and / or bifunctional hydrolyzed compound. A decomposable silicon compound may be included. In this case, a trifunctional hydrolyzable silicon compound is preferably used as the tetrafunctional hydrolyzable silicon compound.

The content ratio of the tetrafunctional hydrolyzable silicon compound, the trifunctional hydrolyzable silicon compound and / or the bifunctional hydrolyzable silicon compound in the silicon oxide matrix raw material component is 4 by mass ratio in terms of SiO _2. Functional hydrolyzable silicon compound: Other hydrolyzable silicon compounds are preferably 60-100: 40-0, more preferably 70-100: 30-0. However, even in this case, the ratio of the tetrafunctional hydrolyzable silicon compound with respect to 100% by mass of the total solid content of the composition for forming an ultraviolet absorbing film is 50% by mass or more. Moreover, it is preferable that the compounding quantity of the bifunctional hydrolyzable silicon compound in a silicon oxide matrix raw material component shall be the quantity of 10 mass% or less with respect to this component whole quantity.

  When the silicon oxide-based matrix raw material component contains a trifunctional hydrolyzable silicon compound and a bifunctional hydrolyzable silicon compound in addition to the tetrafunctional hydrolyzable silicon compound, these are as described above. You may mix | blend, may be mix | blended as each partial hydrolysis-condensation product, and may be mix | blended as 2 or more types of these partial hydrolysis-condensation products. Hereinafter, the partially hydrolyzed condensate and the partially hydrolyzed cocondensate are collectively referred to as a partially hydrolyzed (co) condensate.

  In the present specification, the partially hydrolyzed (co) condensate refers to an oligomer (multimer) produced by hydrolysis of a hydrolyzable silicon compound followed by dehydration condensation. The partially hydrolyzed (co) condensate is a high molecular weight compound that is usually soluble in a solvent. The partially hydrolyzed (co) condensate has a hydrolyzable group and a silanol group, and further has a property of being hydrolyzed (co) condensed to be a final cured product. A partial hydrolysis condensate can be obtained only from one kind of hydrolyzable silicon compound, and a partial hydrolysis cocondensate that is a cocondensate thereof can be obtained from two or more kinds of hydrolyzable silicon compounds. it can.

The partial hydrolysis (co) condensation of the hydrolyzable silicon compound is performed, for example, by adding a reaction solution obtained by adding water to a lower alcohol solution of the hydrolyzable silicon compound in the presence of an acid catalyst at 10 to 40 ° C. It can be performed by stirring for ˜48 hours.
Here, when the silicon oxide matrix raw material component contains such a partially hydrolyzed cocondensate, the mixing ratio of each hydrolyzable silicon compound is calculated as the amount of the raw material hydrolyzable silicon compound in terms of SiO _2. Is done.

  Specific examples of the hydrolyzable group possessed by each hydrolyzable silicon compound constituting the silicon oxide matrix raw material component include alkoxy groups (including substituted alkoxy groups such as alkoxy-substituted alkoxy groups), alkenyloxy groups, and acyl groups. Acyloxy group, oxime group, amide group, amino group, iminoxy group, aminoxy group, alkyl-substituted amino group, isocyanate group, chlorine atom and the like. Among these, the hydrolyzable group is preferably an organooxy group such as an alkoxy group, an alkenyloxy group, an acyloxy group, an iminoxy group, an aminoxy group, and particularly preferably an alkoxy group. As the alkoxy group, an alkoxy group having 4 or less carbon atoms and an alkoxy-substituted alkoxy group having 4 or less carbon atoms (such as a 2-methoxyethoxy group) are preferable, and a methoxy group and an ethoxy group are particularly preferable.

  The tetrafunctional hydrolyzable silicon compound used as the main component of the silicon oxide matrix raw material component is a compound in which four hydrolyzable groups are bonded to a silicon atom, and the four hydrolyzable groups are identical to each other. It may or may not be. The hydrolyzable group is preferably an alkoxy group, more preferably an alkoxy group having 4 or less carbon atoms, and still more preferably a methoxy group and an ethoxy group. Specific examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. In the present invention, tetraethoxysilane is preferable. Silane, tetramethoxysilane, etc. are used. These may be used alone or in combination of two or more.

  The trifunctional hydrolyzable silicon compound optionally contained in the silicon oxide matrix raw material component is a compound in which three hydrolyzable groups and one non-hydrolyzable group are bonded to a silicon atom. Three of the hydrolyzable groups may be the same as or different from each other. The hydrolyzable group is preferably an alkoxy group, more preferably an alkoxy group having 4 or less carbon atoms, and still more preferably a methoxy group and an ethoxy group.

  The non-hydrolyzable group is preferably a monovalent organic group having a non-hydrolyzable functional group or no functional group, and preferably a non-hydrolyzable monovalent organic group having a functional group. More preferred. The non-hydrolyzable monovalent organic group refers to an organic group in which the organic group and a silicon atom are bonded by a carbon-silicon bond, and a bond terminal atom is a carbon atom.

  Here, the functional group used in this specification is a term comprehensively indicating a reactive group, which is distinguished from a mere substituent, and includes, for example, a non-reactive group such as a saturated hydrocarbon group. Is not included in this. An addition polymerizable unsaturated double bond (ethylenic double bond) that is not involved in the formation of the main chain of the polymer compound that the monomer has in the side chain is one kind of functional group. Further, the term “(meth) acryl ...” such as (meth) acrylic acid ester used in the present specification is a term meaning both “acryl” and “methacryl”.

  Among the non-hydrolyzable monovalent organic groups, the non-hydrolyzable monovalent organic group having no functional group does not have an addition polymerizable unsaturated double bond such as an alkyl group or an aryl group. A halogenated hydrocarbon group having no addition polymerizable unsaturated double bond such as a hydrocarbon group or a halogenated alkyl group is preferred. The non-hydrolyzable monovalent organic group having no functional group has particularly preferably 20 or less carbon atoms, more preferably 10 or less. As this monovalent organic group, an alkyl group having 4 or less carbon atoms is preferable.

  Specific examples of the trifunctional hydrolyzable silicon compound having a non-hydrolyzable monovalent organic group having no functional group include methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, Examples include methyltriacetoxysilane, methyltripropoxysilane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltriacetoxysilane. . These may be used alone or in combination of two or more.

  Examples of the functional group in the non-hydrolyzable monovalent organic group having the functional group include an epoxy group, a (meth) acryloxy group, a primary or secondary amino group, an oxetanyl group, a vinyl group, a styryl group, a ureido group, Examples include a mercapto group, an isocyanate group, a cyano group, and a halogen atom, and an epoxy group, a (meth) acryloxy group, a primary or secondary amino group, an oxetanyl group, a vinyl group, a ureido group, a mercapto group, and the like are preferable. In particular, an epoxy group, a primary or secondary amino group, and a (meth) acryloxy group are preferable. The monovalent organic group having an epoxy group is preferably a monovalent organic group having a glycidoxy group or a 3,4-epoxycyclohexyl group, and the organic group having a primary or secondary amino group is an amino group or a monoalkyl group. Monovalent organic groups having an amino group, a phenylamino group, an N- (aminoalkyl) amino group, and the like are preferable.

  Two or more functional groups in the monovalent organic group may exist, but a monovalent organic group having one functional group is preferable except for a primary or secondary amino group. In the case of a primary or secondary amino group, it may have two or more amino groups, in which case a monovalent organic group having one primary amino group and one secondary amino group For example, N- (2-aminoethyl) -3-aminopropyl group and 3-ureidopropyl group are preferable. The total carbon number of the monovalent organic group having these functional groups is preferably 20 or less, and more preferably 10 or less.

Specific examples of the trifunctional hydrolyzable silicon compound having a non-hydrolyzable monovalent organic group having a functional group include the following compounds.
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropenoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-A Nopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, di- (3-methacryloxy) propyltri Ethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3- Examples include mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 2-cyanoethyltrimethoxysilane.

  Among these, preferable compounds include a glycidoxy group, a 2,3-epoxycyclohexyl group, an amino group, an alkylamino group (the alkyl group has 4 or less carbon atoms), phenyl at the terminal of the alkyl group having 2 or 3 carbon atoms. One monovalent organic group having any one functional group of an amino group, an N- (aminoalkyl) amino group (the alkyl group has 4 or less carbon atoms), and a (meth) acryloxy group, and 4 or less carbon atoms A trifunctional hydrolyzable silicon compound in which three of the alkoxy groups are bonded to a silicon atom.

  Specific examples of such a compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, di- (3-methacryloxy) propyltriethoxysilane and the like. From the viewpoint of reactivity with silane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane and the like are particularly preferred. These may be used alone or in combination of two or more.

  The bifunctional hydrolyzable silicon compound optionally contained in the silicon oxide matrix raw material component is a compound in which two hydrolyzable groups and two non-hydrolyzable groups are bonded to a silicon atom. Two of the hydrolyzable groups may be the same as or different from each other. The hydrolyzable group is preferably an alkoxy group, more preferably an alkoxy group having 4 or less carbon atoms, and still more preferably a methoxy group and an ethoxy group.

  The non-hydrolyzable group is preferably a non-hydrolyzable monovalent organic group. The non-hydrolyzable monovalent organic group may have a functional group similar to that of the trifunctional hydrolyzable silicon compound as necessary.

  Specific examples of the bifunctional hydrolyzable silicon compound 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-chloropropylmethyldipropoxysilane, , 3,3-trifluoropropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercapto Examples include propylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 2-cyanoethylmethyldimethoxysilane. These may be used alone or in combination of two or more.

Further, in the composition for forming an ultraviolet absorbing film of the present invention, the content of the silicon oxide matrix raw material component relative to the total mass of the composition is obtained when silicon atoms contained in the silicon oxide matrix raw material component are converted to SiO _2. The SiO ₂ content is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. When the content of the silicon oxide matrix raw material component with respect to the total mass of the composition is less than 1% by mass, it is necessary to increase the coating amount of the composition for obtaining an ultraviolet absorbing film having a desired film thickness. As a result, the appearance may be deteriorated, and when it exceeds 20% by mass, there is a risk that cracks may occur in the ultraviolet absorbing film that can be obtained when the composition is applied.

(2) Hydrophilic organic polymer The composition for forming an ultraviolet absorbing film used in the present invention contains a hydrophilic organic polymer in a proportion of 5 to 30% by mass with respect to 100% by mass of the total solid content in the composition.
The generation of cracks, which may be caused by the evaporation of the liquid component contained in the composition, occurs when the hydrophilic organic polymer forms an ultraviolet absorbing film by the method described later using the composition for forming an ultraviolet absorbing film. It has a function to suppress.

  The ultraviolet absorbing film is formed by forming a silicon oxide matrix by generating a three-dimensional network of polysiloxane from a silicon oxide matrix raw material component mainly contained in the composition for forming an ultraviolet absorbing film. Since the silicon oxide matrix raw material component according to the present invention consists of a tetrafunctional hydrolyzable silicon compound alone or contains a high content thereof, the resulting silicon oxide matrix has a rigid structure and is cured during film formation. There is a concern that cracks may not occur due to the shrinkage. When such a composition for forming an ultraviolet absorbing film contains a hydrophilic organic polymer, the film is formed in such a manner that the hydrophilic organic polymer is taken into the silicon oxide matrix. As a result, it becomes possible for the entire film to flexibly follow the structural change in curing shrinkage during film formation, and the stress in the film is considered to be relaxed.

  By setting the content of the hydrophilic organic polymer in the composition for forming an ultraviolet absorbing film within the above range, cracks can be sufficiently suppressed during film formation, and the mechanical strength of the resulting ultraviolet absorbing film can be maintained. Abrasion and the like can be made sufficient.

  The content rate of the hydrophilic organic polymer with respect to 100 mass% of total solid content in the composition for ultraviolet absorption film formation is 5-30 mass%, and 10-30 mass% is preferable.

Specific examples of the hydrophilic organic polymer include polymers containing a hydrophilic group such as a hydroxyl group or a carboxylic acid group, a polyoxyalkylene group having an etheric oxygen atom between alkylene groups, and the like. In the present invention, a hydrophilic organic polymer containing a polyoxyalkylene group is preferable. Examples of the hydrophilic organic polymer containing a polyoxyalkylene group include polyethylene glycol (PEG) and polyether phosphate ester polymers.
The molecular weight of polyethylene glycol (PEG) is preferably 100 to 40000, more preferably 200 to 4000.

Examples of the polyether phosphate ester polymer include polyether phosphate ester surfactants, and the preferred molecular weight thereof is the same as that of polyethylene glycol (PEG). Specific examples of polyether phosphate ester surfactants include Solsperse 41000 (trade name, manufactured by Nippon Lubrizol Corporation), Disparon DA-375 (trade name, manufactured by Enomoto Kasei Co., Ltd.) and the like as commercially available products. .
In the present invention, these hydrophilic organic polymers can be used alone or in combination of two or more.

(3) Fluorescent brightener The composition for forming an ultraviolet absorbing film used in the present invention contains a fluorescent brightener in a proportion of 2 to 20% by mass with respect to 100% by mass of the total solid content in the composition.

The fluorescent whitening agent is a compound that absorbs light of 360 to 400 nm and converts it into fluorescence of around 430 nm. In the present invention, compounds classified as fluorescent whitening agents can be used without particular limitation. Since the fluorescent whitening agent has a high extinction coefficient with respect to light in the ultraviolet region of the above wavelength, even if the amount of the composition for forming an ultraviolet absorbing film is within the above range, the resulting ultraviolet absorbing film is obtained. When the thickness is 5.0 μm or less, the Tuv of the glass substrate in the region where the film is formed can be 0.2% or less.
The content ratio of the fluorescent whitening agent with respect to 100% by mass of the total solid content in the composition for forming an ultraviolet absorbing film is 2 to 20% by mass, and preferably 3 to 15% by mass.

  Specific examples of the fluorescent brightener used in the present invention include thiophene fluorescent brightener, stilbene fluorescent brightener, coumarin fluorescent brightener, naphthalene fluorescent brightener, benzimidazole fluorescent brightener. Agents and the like.

Specific examples of the thiophene fluorescent brightening agent include 2,5-bis (5-t-butyl-2-benzoxazolyl) thiophene.
Specific examples of stilbene-based optical brighteners include 4,4′-bis (2-benzoxazolyl) stilbene and 4- (2H-naphtho [1,2-d] triazol-2-yl) stilbene-2. Sodium sulfonate, 4,4′-bis [(1,4-dihydro-4-oxo-6-phenylamino-1,3,5-triazin-2-yl) amino] stilbene-2,2′-disulfone Disodium acid, 2,2 ′-(1,2-ethenediyl) bis [5- (3-phenylureido) benzenesulfonate sodium], 2,2 ′-(1,2-ethenediyl) bis [5-[( 4-amino-6-chloro-1,3,5-triazin-2-yl) amino] sodium benzenesulfonate], 4,4′-bis [[4-anilino-6- [bis (2-hydroxyethyl)] Amino] -1,3,5 -Triazin-2-yl] amino] stilbene-2,2'-disulfonic acid disodium, 2,2 '-[1,2-ethenediylbis (3-sodiosulfo-4,1-phenylene)] bis (2H-naphtho [ 1,2-d] sodium triazole-6-sulfonate), 2,2 ′-(1,2-ethenediyl) bis [5-[(2,4-dimethoxybenzoyl) amino] benzenesulfonate sodium], 2, 2 '-(1,2-ethenediyl) bis [5-[[4-methoxy-6- [phenylamino] -1,3,5-triazin-2-yl] amino] benzenesulfonic acid] disodium, 4, 4′-bis [(6-amino-1,4-dihydro-oxo-1,3,5-triazin-2-yl) amino] stilbene-2,2′-disulfonic acid sodium salt, 2,2 ′-([ 1,1'- Phenyl] -4,4' Jiirujibiniren) bis (benzene sulfonate) sodium di, and the like.

  Specific examples of naphthalene fluorescent whitening agents include 1,4-bis (2-benzoxazolyl) naphthalene. Specific examples of the benzimidazole fluorescent whitening agent include HOSTALUUX ACK LIQ (trade name, manufactured by Clariant Japan).

In addition to the above, as a fluorescent whitening agent usable in the present invention, TW-2 (trade name, manufactured by Showa Chemical Industry Co., Ltd.), Hakkol P (trade name, manufactured by Showa Chemical Industry Co., Ltd.), Kayight B ( Trade name, manufactured by Nippon Kayaku Co., Ltd.), TINOPAL NFW LIQ (trade name, manufactured by BASF), Hakkol KIP (trade name, manufactured by Showa Chemical Industry Co., Ltd.), and the like.
In the present invention, these fluorescent brighteners can be used alone or in combination of two or more.

  The fluorescent whitening agent is preferably soluble in a polar solvent from the viewpoint of solubility in the composition for forming an ultraviolet absorbing film. The composition for forming an ultraviolet absorbing film used in the present invention usually contains a solvent such as water and alcohol as liquid components as described later. Note that the fluorescent whitening agent is soluble in a polar solvent means that a predetermined amount of the above-mentioned fluorescent whitening agent with respect to a predetermined amount of water and an alcohol or other polar solvent blended in the composition for forming an ultraviolet absorbing film. Is soluble.

As a specific measure, if the solubility in water at 25 ° C. is 3 g / 100 g or more, it can be said that the fluorescent brightener is soluble in a polar solvent.
As fluorescent brighteners soluble in such polar solvents, Hakkol P (trade name, manufactured by Showa Chemical Industry Co., Ltd.), TINOPAL NFW LIQ (trade name, manufactured by BASF Corp.), Hakkol KIP (trade name, Showa Chemical Industry Co., Ltd.) Manufactured) and the like.

(4) Other components In addition to the above components (1) to (3), the composition for forming an ultraviolet absorbing film used in the present invention is usually a curing catalyst such as an acid which is a curing catalyst for the component (1), It contains water for decomposition and a solvent that dissolves or disperses solid components and enables application on a glass substrate. In addition, as an optional component, various functional components such as an ultraviolet absorber, a flexible component, silica fine particles, an infrared absorber, and a light stabilizer, and a film-formability improving component such as a leveling agent are impaired. It can contain in the range which is not.

(Curing catalyst)
The composition for forming an ultraviolet absorbing film may further contain a curing catalyst as component (1). Curing catalysts include aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid, etc.), alkali metal salts such as lithium salt, sodium salt, 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.

Furthermore, in the present invention, it is preferable to adjust the pH of the composition for forming an ultraviolet absorbing film to 1.0 to 5.0 in order to impart desired abrasion resistance to the obtained ultraviolet absorbing film. It is more preferable to adjust to 0-4.5. Examples of the pH adjustment method include addition of an acid and adjustment of the content of the curing catalyst. Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene Examples include organic acids such as sulfonic acid.
In the present invention, these curing catalysts, preferably acids, can be used alone or in combination of two or more.

The content of the curing catalyst such as the acid in the composition for forming an ultraviolet absorbing film is 0.1 to 20.0% by mass relative to the SiO ₂ equivalent of the silicon oxide matrix raw material component (1). Is preferable, and 0.5-10.0 mass% is more preferable.

(water)
The composition for forming an ultraviolet absorbing film used in the present invention contains water for hydrolyzing and polycondensing the hydrolyzable silicon compounds constituting the silicon oxide matrix raw material component which is the component (1).

The amount of water contained in the composition for forming an ultraviolet absorbing film is not particularly limited as long as it is a sufficient amount for hydrolyzing and polycondensing the hydrolyzable silicon compounds, but is the component (1). The amount of 1 to 20 equivalents by molar ratio with respect to the SiO ₂ equivalent of the silicon oxide matrix raw material component is preferable, and the amount of 4 to 16 equivalents is more preferable. When the amount of water is less than 1 equivalent in the above molar ratio, hydrolysis does not proceed easily, and when the composition is applied to the surface of the glass substrate, the composition may be repelled or haze may increase. When the equivalent is exceeded, the hydrolysis rate is increased, and long-term storage may not be sufficient.

In addition, for the purpose of improving the hardness in the ultraviolet absorbing film such as wear resistance and scratch resistance as described later, particularly when blending silica fine particles, the amount of water contained in the composition for forming an ultraviolet absorbing film is: An amount of 2 to 20 equivalents in terms of molar ratio to the amount of SiO ₂ equivalent of the silicon oxide matrix raw material component is preferred, and an amount of 4 to 17.5 equivalents is more preferred. If the amount of water is less than 2 equivalents in the above molar ratio, the hardness of the ultraviolet absorbing film may be reduced, and if it exceeds 20 equivalents, the hydrolysis rate is increased and long-term storage properties may not be sufficient.
Further, when water-dispersed colloidal silica, which will be described later, is used as the silica fine particles, or when a fluorescent brightening agent or an ultraviolet absorber, which will be described later, is used as the aqueous dispersion, these waters are also used for forming an ultraviolet-absorbing film. Treated as water.

(solvent)
The composition for forming an ultraviolet absorbing film used in the present invention usually contains a predetermined amount of each of the above components (1) to (3), an acid and water, and various optional components that are optionally added. Prepared in dissolved and dispersed form. It is necessary that the total solid content in the composition for forming an ultraviolet-absorbing film is stably dissolved and dispersed in a solvent. For this purpose, the solvent contains at least 20% by mass, preferably 50% by mass or more alcohol. .

  Examples of the alcohol used in such a solvent 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. Among these, the solubility of the silicon oxide matrix raw material component is good, and the coating property to the base material is good. Therefore, an alcohol having a boiling point of 80 to 160 ° C. is preferable. Specifically, 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.

  Moreover, as a solvent used for the composition for forming an ultraviolet absorbing film, when the composition contains a partially hydrolyzed (co) condensate of a hydrolyzable silicon compound, the raw material hydrolyzable silicon When a compound (for example, alkyltrialkoxysilane) is hydrolyzed, a lower alcohol, etc., colloidal silica in an organic solvent dispersion system, and various components are mixed with an organic solvent. It is.

  Further, in the composition for forming an ultraviolet absorbing film, a solvent other than the above may be used in combination with a solvent other than alcohol that can be mixed with water / alcohol. Examples of such a solvent include acetone, acetylacetone. Ketones such as ethyl acetate and esters such as isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.

  The amount of the solvent used in the composition for forming an ultraviolet absorbing film used in the present invention is preferably 20 to 1000% by weight with respect to 100% by weight of the total solid content in the composition for forming an ultraviolet absorbing film. More preferably, it is 500 mass%.

(UV absorber)
The composition for forming an ultraviolet absorbing film used in the present invention may optionally contain an ultraviolet absorber. Many ultraviolet absorbers exhibit absorption in the range of, for example, 325 to 390 nm, which has a relatively shorter wavelength than the fluorescent whitening agent. Therefore, by using the ultraviolet absorber together with the fluorescent brightening agent within the range not impairing the effect of the present invention, the ultraviolet absorbing ability becomes a UV absorbing film in a relatively wide wavelength region. In addition, the use of an ultraviolet absorber is preferable because the content of the fluorescent whitening agent in the composition for forming an ultraviolet absorbing film can be suppressed to a low range, and the amount of fluorescence emitted can be suppressed.

  Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzophenones, triazines, benzotriazoles, cyanoacrylates, azomethines, indoles, salicylates, and anthracenes. These UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, azomethine UV absorbers, indole UV absorbers, and salicylate UV absorbers. Agents, anthracene ultraviolet absorbers and the like, and aqueous dispersions and emulsions prepared using these compounds, as well as complexes of these compounds with metals.

  As the above benzotriazole-based ultraviolet absorber, specifically, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (commercially available products include: TINUVIN 326 (trade name, manufactured by BASF), etc., octyl-3- [3-tert-4-hydroxy-5- [5-chloro-2H-benzotriazol-2-yl] propionate, 2- (2H-benzo Triazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6) -Tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzene Nzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxy Phenyl) propionate, 2- (2H-benzothiazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6 (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol and the like.

  Specifically, the triazine-based ultraviolet absorber is 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-bis-butoxyphenyl) -1,3,5-triazine 2- (2-hydroxy-4- [1-octylcarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, TINUVIN477 (trade name, manufactured by BASF)) etc And the like.

  Specific examples of the cyanoacrylate-based ultraviolet absorber include UVINUL3008 (trade name, manufactured by BASF), and specific examples of the salicylate-based ultraviolet absorber include pt-butylphenyl salicylate and p-octylphenyl. Salicylates and the like are anthracene ultraviolet absorbers, specifically, anthracene and anthracene derivatives, etc., and indole ultraviolet absorbers are BONASORB UA-3911, BONASORB UA-3912 (both trade names, both manufactured by Orient Chemical Co., Ltd.), etc. However, examples of the azomethine UV absorber include BONASORB UA-3701 (trade name, manufactured by Orient Chemical Co., Ltd.).

  Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2,2 ′, 3 (or any of 4, 5, and 6) -trihydroxybenzophenone, 2,2 ′, 4,4. Examples include '-tetrahydroxybenzophenone, 2,4-dihydroxy-2', 4'-dimethoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone.

  In the present invention, these ultraviolet absorbers can be used alone or in combination of two or more. Of these ultraviolet absorbers, in the present invention, benzophenone ultraviolet absorbers are preferably used from the viewpoint of solubility.

  5-30 mass% is preferable with respect to 100 mass% of total solid content in a composition, and, as for content of the ultraviolet absorber in the composition for ultraviolet absorption film formation, 10-20 mass% is more preferable.

(Flexibility imparting component)
In the composition for forming an ultraviolet absorbing film used in the present invention, in addition to the hydrophilic organic polymer, a component for imparting flexibility to a silicon oxide matrix obtained by curing a silicon oxide matrix raw material component (hereinafter referred to as “ It is possible to mix | blend "the flexibility provision component" in the range which does not impair the effect of this invention. Other flexibility-imparting components can act together with the hydrophilic organic polymer and contribute to the prevention of cracks in the ultraviolet absorbing film.

Examples of the flexibility-imparting component include organic compounds such as various organic resins such as silicone resin, acrylic resin, polyester resin, polyurethane resin, and epoxy resin.
When an organic resin is used as the flexibility-imparting component, its form is preferably liquid or fine particles. The organic resin may also be blended in the composition for forming an ultraviolet absorbing film as a raw material component of a resin that crosslinks and cures when the silicon oxide matrix raw material component is cured and dried. In this case, as long as the characteristics of the silicon oxide matrix are not hindered, a part of the silicon oxide matrix raw material component and the organic resin raw material component or organic resin which is a flexibility-imparting component partially react to crosslink. Also good.

  Of the flexibility-imparting components, the silicone resin is preferably a silicone oil containing various modified silicone oils, and a diorganosilicone containing a hydrolyzable silyl group or a polymerizable group-containing organic group at the end is partially or fully crosslinked. Examples include silicone rubber.

  Polyurethane rubber, etc. can be used as the polyurethane resin, and acrylonitrile rubber, homopolymer of alkyl acrylate ester, homopolymer of alkyl methacrylate ester, alkyl acrylate ester and its alkyl acrylate copolymer can be copolymerized. Preferred examples include a copolymer with a monomer, a copolymer of an alkyl methacrylate and a monomer copolymerizable with the alkyl methacrylate, and the like. Examples of the monomer copolymerizable with the (meth) acrylic acid alkyl ester include a hydroxyalkyl ester of (meth) acrylic acid, a (meth) acrylic acid ester having a polyoxyalkylene group, and a partial structure of an ultraviolet absorber (meta ) Acrylic acid ester, (meth) acrylic acid ester having a silicon atom, and the like can be used.

  When an epoxy resin is blended in the composition for forming an ultraviolet absorbing film as a flexibility-imparting component, it is preferable to blend a combination of a polyepoxide and a curing agent, which are raw material components of the epoxy resin, or a polyepoxide alone. Polyepoxides are a general term for compounds having a plurality of epoxy groups. That is, the average number of epoxy groups of the polyepoxides is 2 or more, but in the present invention, 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.

  Among these, polyglycidyl ether compounds are preferable, and aliphatic polyglycidyl ether compounds are particularly preferable. As the polyglycidyl ether compound, a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is particularly preferable from the viewpoint of improving light resistance. These alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.

  Specifically, 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.

  Among these, from the point that light resistance can be particularly improved, a poly of an aliphatic polyol having three or more hydroxyl groups such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether. Glycidyl ether (one having an average number of glycidyl groups (epoxy groups) exceeding 2 per molecule) is preferred. These may be used alone or in combination of two or more.

  The blending amount of the flexibility-imparting component is particularly an amount that can work with the hydrophilic organic polymer to impart flexibility to the ultraviolet absorbing film and improve crack resistance without impairing the effects of the present invention. Not limited. Specifically, 3 to 20% by mass is preferable with respect to 100% by mass of the total solid content in the composition for forming an ultraviolet absorbing film, and 5 to 10% by mass is more preferable.

(Silica fine particles)
The composition for forming an ultraviolet absorbing film used in the present invention may contain silica fine particles as necessary in order to improve the wear resistance of the ultraviolet absorbing film. When silica fine particles are blended in the composition for forming an ultraviolet absorbing film, it is preferred 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. When preparing a composition for forming an ultraviolet absorbing film, colloidal silica can be appropriately blended to form a composition for forming an ultraviolet absorbing film containing silica fine particles. Further, when producing a partially hydrolyzed (co) condensate of a hydrolyzable silicon compound, colloidal silica is blended with the raw material hydrolyzable silicon compound to perform partial hydrolyzate (co) condensation, and silica fine particle-containing partial hydrolyzate is produced. A decomposition (co) condensate can be obtained, and it can be used as a composition for forming an ultraviolet absorbing film containing silica fine particles.

  The average particle diameter (BET method) of the silica fine particles used in the composition for forming an ultraviolet absorbing film is preferably 1 to 100 nm. When 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. Furthermore, 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 colorless transparency of the ultraviolet absorbing film. Moreover, although 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. Further, 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 of the silica fine particles is not particularly limited as long as it is an amount capable of improving the wear resistance of the ultraviolet absorbing film without impairing the effects of the present invention. Specifically, 3 to 50% by mass is preferable and 5 to 30% by mass is more preferable with respect to 100% by mass of the total solid content in the composition for forming an ultraviolet absorbing film.

(Other optional ingredients)
The composition for forming an ultraviolet absorbing film used in 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). The blending amount of the light stabilizer is preferably 0.001 to 0.015% by mass and more preferably 0.002 to 0.009% by mass with respect to 100% by mass of the total solid content in the composition for forming an ultraviolet absorbing film. .

  The composition for forming an ultraviolet absorbing film may further contain functional fine particles such as indium tin oxide fine particles and antimony tin oxide fine particles and organic dyes for the purpose of imparting infrared shielding properties.

  Moreover, the composition for ultraviolet absorption film formation may contain surfactant as an additive for the purpose of improving the coating property to a glass base material, and the smoothness of the coating film obtained.

  The composition for forming an ultraviolet absorbing film used in 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 glass substrate. For the purpose of improving the adhesion, an additive such as an adhesion imparting agent may be included. The amount of these additives is preferably 0.01 to 2% by mass for each additive component with respect to 100% by mass of the total solid content in the composition for forming an ultraviolet absorbing film. Moreover, the composition for ultraviolet absorption film formation may contain dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.

(Preparation of UV-absorbing film forming composition)
The composition for forming an ultraviolet absorbing film used in the present invention comprises (1) a silicon oxide matrix raw material component, (2) a hydrophilic organic polymer, (3) a predetermined amount of a fluorescent brightening agent, and curing of the component (1). The catalyst, water for hydrolysis, a solvent for dissolving or dispersing the solid component, and any amount of various optional components added as necessary can be prepared by mixing in a usual manner. In addition, about the time which adds each component, it can select suitably.

  Here, when the composition for forming an ultraviolet absorbing film used in the present invention contains the hydrolyzable silicon compound itself as the silicon oxide matrix raw material component, in order to stabilize the composition during storage, You may perform the process which carries out partial hydrolysis (co) condensation of these.

  As in the above, this partial hydrolysis cocondensation is preferably performed in the presence of the same acid catalyst as described above under the same reaction conditions as described above. Usually, the object can be achieved by mixing one or more hydrolyzable silicon compounds as required, and then stirring the mixture for a predetermined time at room temperature in the presence of an acid catalyst. The optional compounding agent may be added before the partial hydrolysis cocondensation or after the partial hydrolysis cocondensation. It is preferable to add the catalyst and adjust the pH after the partial hydrolysis cocondensation.

[Ultraviolet absorbing glass article of the present invention]
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 composition for forming an ultraviolet absorbing film. In addition, it is preferable that formation of the ultraviolet absorption film in a glass base material is formed in the whole surface of one main surface of a glass base material, or the whole area | region except an edge part.

  As a specific method of forming the composition for forming an ultraviolet absorbing film on the glass substrate, (A) a step of applying the composition on the glass substrate to form a coating film, and (B) the coating film And a method including a step of forming an ultraviolet-absorbing film by removing the solvent and curing the silicon oxide matrix raw material component to obtain a cured product.

First, in the step (A), a composition for forming an ultraviolet absorbing film is applied on a glass substrate to form a coating film using the composition. In addition, the coating film formed here is a coating film containing the said solvent. The method for applying the UV-absorbing film-forming composition on the glass substrate is not particularly limited as long as it is a uniformly applied method. Flow coating method, dip coating method, spin coating method, spray coating method, flexographic printing Known methods such as a method, a screen printing method, a gravure printing method, a roll coating method, a meniscus coating method, and a die coating method can be used. The thickness of the coating film by the composition for forming an ultraviolet absorbing film is determined in consideration of the thickness of the finally obtained ultraviolet absorbing film.
In addition, as a method for uniformly forming a coating film on a glass substrate having a large area or curvature, a dip coating method, a spin coating method, a spray coating method, a roll coating method, or the like is preferable.

  Next, the step (B): removing the solvent from the coating film of the composition for forming an ultraviolet absorbing film on the glass substrate and curing the silicon oxide matrix raw material component comprising the hydrolyzable silicon compounds to absorb ultraviolet rays. A step of forming a film is performed.

  Since the coating film of the composition for forming an ultraviolet absorbing film contains a volatile organic solvent or the like, the volatile component is first removed by evaporation after the coating film is formed by the composition. This removal of volatile components is preferably carried out by heating and / or drying under reduced pressure. After forming a coating film of the composition for forming an ultraviolet absorbing film on a glass substrate, it is preferable to perform temporary drying at a temperature of about room temperature to 120 ° C. from the viewpoint of improving the leveling property of the coating film. Usually, during this temporary drying operation, 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 time for temporary drying, that is, the operation time for removing the volatile component, is preferably about 3 seconds to 2 hours, although it depends on the ultraviolet absorbing film forming composition to be used.

  At this time, it is preferable that 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. In addition, when heating is performed to remove the volatile components, heating for forming a silicon oxide matrix, which is performed as necessary, and heating for removing the volatile components, that is, general Specifically, the temporary drying may be performed continuously.

  After removing the volatile component from the coating film as described above, the silicon oxide matrix raw material component is cured. This reaction can be carried out at room temperature or under heating. When a cured product (silicon oxide matrix) is produced 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, this heating temperature is preferably 60 to 200 ° C, more preferably 80 to 190 ° C. The heating time depends on the composition used for film formation, but is preferably 10 minutes to 2 hours.

  In the ultraviolet absorbing glass article of the present invention, the film thickness of the ultraviolet absorbing film formed on the glass substrate as described above using the composition for forming an ultraviolet absorbing film is 5.0 μm or less over the entire film. The initial ultraviolet transmittance (Tuv) is 0.2% or less over the entire glass substrate in the region where the film is formed. When the film thickness is 5.0 μm or less, an ultraviolet absorbing film having excellent crack resistance can be obtained. Further, when Tuv is 0.2% or less, an ultraviolet absorbing film having excellent initial ultraviolet absorbing ability and less deterioration of ultraviolet absorbing ability even after long exposure can be obtained. A preferred initial Tuv is 0.1% or less.

If the initial Tuv is in the above range, a light resistance test, for example, a specimen is placed on a sunshine carbon weather meter (Suga tester: WEL-SUN-HCH), and the illumination intensity is 78.5 W / m ² (300-400 nm), The amount of change from the initial Tuv (ΔTuv) can be reduced to 1.0% or less in the Tuv after 1000 hours have passed after the specimen is exposed to the conditions of a black panel temperature of 83 ° C. and a humidity of 50 to 60 RH%. Therefore, it can be said that the ultraviolet absorbing film has little deterioration of the ultraviolet absorbing ability.

  On the other hand, the lower limit of the film thickness is not particularly limited as long as Tuv can be in the above range, but considering the mechanical strength and wear resistance of the ultraviolet absorbing film, the lower limit is preferably 0.5 μm. The lower limit is more preferably 1.0 μm.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 3 are examples, and examples 4 to 8 are comparative examples.

(Example 1)
2. 27.8 g of ethanol, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., expressed as “TEOS” in Table 1) 36.4 g, PEG 4000 as polyethylene glycol (trade name, manufactured by Kanto Chemical Co., Ltd., molecular weight: 4000) 0g, TINOPAL NFW LIQ (trade name, manufactured by BASF, solid content 20% by mass) 7.5g, pure water 25.2g, concentrated hydrochloric acid (manufactured by Kanto Chemical Co., 35% by mass) 0.1g as an optical brightener The mixture was charged and stirred for 1 hour to obtain a composition 1 for forming an ultraviolet absorbing film. After that, one of the main components of the high-heat-absorption green glass plate (Tv: 75.2%, Tuv: 9.5%, length 10 cm, width 10 cm, thickness 3.5 mm, manufactured by Asahi Glass Co., Ltd., commonly known as UVFL) whose surface was cleaned The ultraviolet absorbing film forming composition 1 obtained as described above was applied to the entire surface of the surface by a spin coating method and dried in the atmosphere at 180 ° C. for 30 minutes to obtain an ultraviolet absorbing glass article 1. The characteristics of the obtained ultraviolet absorbing glass article 1 were evaluated as follows. The evaluation results are shown in Table 1. The film thickness shown in Table 1 is the maximum film thickness [μm]. Here, in the ultraviolet absorbing glass article 1, the ultraviolet absorbing film had a substantially uniform film thickness throughout.

[Evaluation]
1) Film thickness: A cross section of the ultraviolet absorbing film was observed with a scanning electron microscope (manufactured by Hitachi, Ltd .: S-800), and a maximum film thickness [μm] was obtained from the obtained observed image.

  2) Crack (after curing): The dried UV-absorbing film was observed with the naked eye and a metal microscope, and judged by whether or not the layer surface had cracks. No cracks were observed, that is, those that could not be observed with the naked eye or the microscope were evaluated as “◯”, those that could not be observed with the naked eye but that could be observed with the microscope were “Δ”, and those that could be observed with the naked eye were “×”.

  3) Spectral characteristics were measured using a spectrophotometer (manufactured by Hitachi, Ltd .: U-4100), and calculated according to JIS-R3106, the initial visible light transmittance (Tv), and the initial and accelerated weather resistance test Judgment was made by ultraviolet transmittance (Tuv).

  4) Crack (after moisture resistance test): The specimen was put into a constant temperature and humidity chamber at 80 ° C. and 95 RH%, and after 1000 hours, the crack was determined by the same method as in 2) above.

5) Accelerated weather resistance test (light resistance evaluation): a specimen was placed on a sunshine carbon weather meter (Suga test machine: WEL-SUN-HCH), irradiation illuminance 78.5 W / m ² (300-400 nm), black panel temperature The specimen was exposed to conditions of 83 ° C. and humidity of 50 to 60 RH%, and after 1000 hours, the ultraviolet transmittance (Tuv) of the specimen was measured. Table 1 shows the amount of change ΔTuv from the initial Tuv after the accelerated weathering test. ΔTuv is preferably 1.0% or less.

(Example 2)
30.7 g of ethanol, 33.8 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 4.5 g of PEG 4000 (trade name, manufactured by Kanto Chemical Co., Ltd., molecular weight: 4000) as polyethylene glycol (PEG), and Hakkol P (as optical brightener) A product name, 0.4 g of Showa Chemical Industry Co., Ltd., 30.5 g of pure water, 0.1 g of concentrated hydrochloric acid (Kanto Chemical Co., Ltd., 35% by mass) was charged and stirred for 1 hour to form an ultraviolet absorbing film. 2 was obtained. Thereafter, one main surface of the high heat ray absorbing green glass (Tv: 75.2%, Tuv: 9.5%, length 10 cm, width 10 cm, thickness 3.5 mm, manufactured by Asahi Glass Co., Ltd., commonly known as UVFL) whose surface is cleaned. The ultraviolet absorbing film forming composition 2 obtained above was applied to the entire upper surface by a spin coating method and dried in the atmosphere at 180 ° C. for 30 minutes to obtain an ultraviolet absorbing glass article 2. The characteristics of the obtained ultraviolet absorbing glass article 2 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
An ultraviolet absorbing glass article 3 was produced using the ultraviolet absorbing film forming composition 2 in the same manner as in Example 2 except that the film thickness was changed as shown in Table 1. The characteristics of the obtained ultraviolet absorbing glass article 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Examples 4 to 6)
Ultraviolet absorbing glass articles 4 to 6 were produced using the ultraviolet absorbing film forming composition 1 in the same manner as in Example 1 except that the film thickness was changed as shown in Table 1. The characteristics of the obtained ultraviolet absorbing glass articles 4 to 6 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Examples 7 and 8)
Ultraviolet absorbing glass articles 7 and 8 were produced using the ultraviolet absorbing film forming composition 2 in the same manner as in Example 2 except that the film thickness was changed as shown in Table 1. The characteristics of the obtained ultraviolet absorbing glass articles 7 and 8 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
In all the above examples, the ultraviolet absorbing film in the obtained ultraviolet absorbing glass article had a substantially uniform film thickness throughout.

  As can be seen from Table 1, Examples 1 to 3, which are the UV-absorbing glass articles of the present invention, are excellent in crack resistance, particularly crack resistance in long-term use under high temperature and high humidity, and initial ultraviolet absorption ability. There is little deterioration of UV absorption ability by long exposure. The UV-absorbing glass articles of Examples 4 to 8, which are comparative examples, have a film thickness or initial Tuv outside the range of the present invention, and have crack resistance, particularly crack resistance and long-time exposure in long-term use under high temperature and high humidity. It is not possible to maintain the UV absorption ability due to.

  The UV-absorbing glass article of the present invention is excellent in crack resistance, particularly crack resistance in long-term use under high temperature and high humidity, and initial UV-absorbing ability, as well as less UV-absorbing ability due to long-time exposure. It can also be applied to parts that require a high degree of mechanical durability such as wear resistance and crack resistance as well as ultraviolet absorption, such as automotive windshields and sliding windows.

Claims (5)

A glass substrate and an ultraviolet absorbing glass article having an ultraviolet absorbing film formed on the surface of at least a part of the glass substrate using the ultraviolet absorbing film forming composition,
The composition for forming an ultraviolet absorbing film is a silicon oxide matrix raw material component composed of hydrolyzable silicon compounds containing a tetrafunctional hydrolyzable silicon compound in terms of SiO ₂ with respect to the total solid content in the composition. 50 to 93% by mass, 5 to 30% by mass of a hydrophilic organic polymer, and 2 to 20% by mass of an optical brightener, and the content of the tetrafunctional hydrolyzable silicon compound with respect to the total solid content The proportion is at least 50% by mass in terms of SiO ₂ ,
The ultraviolet absorbing film has a thickness of 5.0 μm or less,
And the ultraviolet absorption glass article whose initial ultraviolet transmittance defined by JIS-R3106 in the ultraviolet absorption film formation field of the glass article is 0.2% or less.   The ultraviolet-absorbing glass article according to claim 1, wherein the tetrafunctional hydrolyzable silicon compound is selected from tetramethoxysilane and / or tetraethoxysilane.   The ultraviolet absorbing glass article according to claim 1 or 2, wherein the hydrophilic organic polymer contains a polyoxyalkylene group.   The ultraviolet light absorbing glass article according to any one of claims 1 to 3, wherein the optical brightener is soluble in a polar solvent.   The ultraviolet-absorbing glass article according to any one of claims 1 to 4, wherein the composition for forming an ultraviolet-absorbing film further contains an ultraviolet absorber.