JP2016033109A - Glass with film and film-forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass with a film which is excellent in antibacterial and antiviral activity owing to containing silver and in which an occurrence of yellowing owing to silver is suppressed.SOLUTION: There is provided a glass with a film comprising: a glass substrate; and a film formed on the substrate. The film using silicon oxide as the matrix includes silver ions and at least one ion of alkali metal selected from the group consisting of sodium, potassium, and lithium. The glass with the film has a difference in yellowness index ΔYI of 1.8 or less, in which the yellowness index between before and after a humidity test performing under predetermined conditions is measured according to JIS-K7373 (2006) and calculated. In an antibacterial test that is performed by applying JIS Z 2801 (2010) by using Escherichia coli, Staphylococcus aureus or influenza virus alternate phage, an antibacterial activity value at the point in time of 1 hour after the start of the test is 2.0 or more.SELECTED DRAWING: None

Description

  The present invention relates to a glass with a film and a composition for forming a film, and particularly relates to a glass with a film having antibacterial and antiviral properties and a composition for forming a film for forming a coating having antibacterial and antiviral properties.

  Since glass is excellent in transparency, it is used for various windows such as for buildings, vehicles, and showcases. Until now, attempts have been made to apply an antibacterial film containing silver to glass, but when a film containing silver is applied and the glass is baked, silver ions in the film diffuse into the glass and colloid, causing plasma resonance. May develop yellow color due to absorption. Further, even if it is colorless immediately after firing, it has a problem of developing a yellow color depending on the subsequent environment.

  For example, Patent Document 1 describes a transparent article on which a silver-containing antibacterial film containing silicon oxide as a main component is formed. The technique described in Patent Document 1 is considered to have no problem with transparency, but if the silver concentration is increased in order to increase the antibacterial performance, there is a concern that yellowing tends to occur and long-term durability is lacking.

JP 2008-213206 A

  The present invention has been made from the above viewpoint, and contains silver, which has antibacterial and antiviral properties by containing silver and suppresses yellowing due to the silver, and contains silver. An object of the present invention is to provide a film-forming composition capable of forming a film that has antibacterial and antiviral properties and is capable of forming a film in which yellowing due to silver is suppressed even when formed on glass.

（式（Ａ）中、Ｒ^Ｆ１は、ペルフルオロアルキル基を示す。ａ、ｂ、ｃ、ｄ、ｅは、それぞれ独立して、０または１以上の整数を示し、ａ＋ｂ＋ｃ＋ｄ＋ｅは、少なくとも１以上であり、ａ、ｂ、ｃ、ｄ、ｅでくくられた各繰り返し単位の存在順序は、式中において限定されない。）
Ｑ^１：−Ｃ（＝Ｏ）ＮＨ−、−Ｃ（＝Ｏ）Ｎ（ＣＨ_３）−、−Ｃ（＝Ｏ）Ｎ（Ｃ_６Ｈ_５）−から選ばれるアミド結合、ウレタン結合、エーテル結合、エステル結合、−ＣＦ_２−基およびフェニレン基から選ばれる１種または２種を含有してもよい、−ＣＨ_２−単位の繰返しからなる炭素原子数２〜１２の２価の有機基を示す（ただし、−ＣＨ_２−基の水素原子の１個は−ＯＨ基で置換されていてもよい。）。
Ｘ^１：炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のオキシアルコキシ基、炭素原子数２〜１０のアシロキシ基、炭素原子数２〜１０のアルケニルオキシ基、ハロゲン原子またはイソシアネート基を示す。ｍ個のＸ^１は互いに同一であっても異なってもよい。
Ｒ^１：水素原子または、水素原子の一部または全部が置換されていてもよい炭素原子数１〜８の一価炭化水素基を示す。３−ｍ個のＲ^１は互いに同一であっても異なってもよい。
［１５］前記被膜形成用組成物を用いて形成される被膜は、前記被膜の表面において大腸菌、黄色ブドウ球菌またはインフルエンザウイルス代替ファージを用いてＪＩＳ Ｚ ２８０１（２０１０）を準用し、暗所、２５℃の条件で行われる抗菌試験における前記抗菌試験開始から１時間後の抗菌活性値が２．０以上である、［９］〜［１４］のいずれかに記載の被膜形成用組成物。 This invention provides the glass with a film of the following structures, and the composition for film formation.
[1] A glass with a coating having a glass substrate and a coating formed on the surface of the glass substrate, wherein the coating contains silicon oxide as a matrix, contains silver ions, and contains sodium, potassium, and lithium JIS-K7373 (2006), which contains at least one alkali metal ion selected from JIS-K7373 (2006) before and after a moisture resistance test held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 1000 hours. As for the yellowness YI measured and calculated according to the above, ΔYI obtained by subtracting the value before the moisture resistance test from the value after the moisture resistance test is 1.8 or less, and Escherichia coli, Staphylococcus aureus or JIS Z 2801 (2010) is applied mutatis mutandis using influenza virus surrogate phage, and it is performed in the dark at 25 ° C. Glass with a coating having an antibacterial activity value of 2.0 or more after 1 hour from the start of the antibacterial test in the antibacterial test
[2] The coating with glass, surface elution ion amount to be determined by the following measuring method, the silver ion is ^{0.3ng / cm 2 ~1000ng / cm 2} , for a lithium ion, sodium ion and potassium ion, a coated glass according to a 0.3ng ^/ cm ² ~200ng ^/ cm 2 in total [1].
(Measurement method of surface elution ion quantity)
The glass substrate portion of the coated glass is masked with a tape made of polytetrafluoroethylene, immersed in 10 mL of 0.1% by mass nitric acid, sonicated for 5 minutes at 28 kHz, and the amount of ions eluted is determined by ICP-MS. Measured by, and normalized by the film area.
[3] The coating may further contain copper ions, coating according to the surface ions eluted weight determined by the measuring method is 0.3ng ^/ cm ² ~1000ng ^/ cm 2 for copper ions [2] With glass.
[4] The glass with a coating according to any one of [1] to [3], wherein the Martens hardness measured on the surface of the coating is 1600 N / mm ² or more.
[5] The glass with a film according to any one of [1] to [4], wherein the film contains particles having a cation adsorption ability.
[6] The coated glass according to [5], wherein the constituent material of the particles having cation adsorption ability is at least one selected from the group consisting of zeolite, smectite, and a calcium phosphate compound.
[7] The film-coated glass according to any one of [1] to [6], wherein the film has a fluorine-containing antifouling layer on the outermost layer.
[8] From the start of the antibacterial test in the antibacterial test performed at 25 ° C. in the dark, using JIS Z 2801 (2010) on the surface of the coating, using Escherichia coli, Staphylococcus aureus, or influenza virus alternative phage. The coated glass according to any one of [1] to [7], wherein the antibacterial activity value after time is 2.0 or more for any of the bacteria.
[9] A silicon oxide raw material component that forms a matrix of silicon oxide, and at least one alkali metal ion selected from sodium, potassium, and lithium is 0.01% by mass to 1% by mass with respect to the total solid content, and The composition for film formation which contains 0.01 mass%-30 mass% of silver ions with respect to the total solid.
[10] The film forming composition according to [9], further containing copper ions, wherein the content of the copper ions is 0.01% by mass to 30% by mass with respect to the total solid content.
[11] The film forming composition as described in [9] or [10], further comprising particles having a cation adsorption ability.
[12] The film forming composition according to [11], wherein the constituent material of the particles having cation adsorption ability is one or more selected from zeolite, smectite, and calcium phosphate compound.
[13] The film forming composition according to any one of [9] to [12], further comprising a fluorine-containing antifouling agent.
[14] The film forming composition according to [13], wherein the fluorine-containing antifouling agent includes a compound represented by the following formula (1A) and / or a compound represented by the following formula (1B).
A ¹ -Q ¹ -SiX ¹ _m R ¹ _3-m (1A)
A ¹ -Q ^1- {CH ₂ CH (SiX ¹ _m R ¹ _3-m )} _n -H (1B)
Symbols in Formula (1A) and Formula (1B) are as follows.
A ¹ is a group represented by the following formula (A).

(In Formula (A), R ^F1 represents a perfluoroalkyl group. A, b, c, d, and e each independently represent 0 or an integer of 1 or more, and a + b + c + d + e is at least 1 or more. , A, b, c, d, e, the order of existence of each repeating unit is not limited in the formula.)
Q ¹ : amide bond, urethane bond, ether bond selected from —C (═O) NH—, —C (═O) N (CH ₃ ) —, —C (═O) N (C ₆ H ₅ ) — , an ester bond, -CF 2 _- shows a consisting of repeating units divalent organic group having 2 to 12 carbon atoms _- may contain one or two elements selected from group and phenylene group, -CH 2 (However, one of the hydrogen atoms in the —CH ₂ — group may be substituted with an —OH group.)
X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m X ^{1 s} may be the same as or different from each other.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms in which part or all of the hydrogen atoms may be substituted. 3-m R < ¹ > may mutually be same or different.
[15] The film formed using the film-forming composition is JIS Z 2801 (2010) using Escherichia coli, Staphylococcus aureus, or influenza virus surrogate phages on the surface of the film. The composition for film formation according to any one of [9] to [14], wherein an antibacterial activity value after 1 hour from the start of the antibacterial test in an antibacterial test performed at a temperature of 2.0 ° C is 2.0 or more.

ADVANTAGE OF THE INVENTION According to this invention, it can provide the glass with a film which has antibacterial and antiviral property by containing silver, and the generation | occurrence | production was suppressed about yellowing by this silver.
The coated glass of the present invention has durability in antibacterial and antiviral properties, and is excellent in mechanical durability such as wear resistance.
The composition for forming a film of the present invention is a composition that has antibacterial and antiviral properties by containing silver, and can form a film in which the occurrence of yellowing due to silver is suppressed even when formed on glass. It is.

Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
[Glass with film]
The coated glass of the present invention is a coated glass having a glass substrate and a coating formed on the surface of the glass substrate, the coated film having the following constitution (i), and the coated glass Has moisture resistance (ii) and antibacterial and antiviral properties (iii) according to the following yellowness YI.

(I) Using silicon oxide as a matrix and containing silver ions, it contains ions of at least one alkali metal selected from sodium, potassium and lithium.
(Ii) The glass with a coating film is measured for the yellowness YI measured and calculated according to JIS-K7373 (2006) before and after a moisture resistance test held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 1000 hours. ΔYI obtained by subtracting the value before the moisture resistance test from the value after the moisture resistance test is 1.8 or less.
(Iii) One hour from the start of the antibacterial test in the antibacterial test performed at 25 ° C. in the dark, using JIS Z 2801 (2010) on the surface of the coating using Escherichia coli, Staphylococcus aureus, or influenza virus surrogate phage The later antibacterial activity value is 2.0 or more.

  In this specification, the film having “antibacterial and antiviral properties” means a case where the condition (iii) is satisfied. That is, in any one of Escherichia coli, Staphylococcus aureus, and influenza virus substitute phage, a coating having an antibacterial activity value of 2.0 or more after 1 hour from the start of the antibacterial test is a coating having antibacterial / antiviral properties. . The coating film having antibacterial / antiviral properties is also referred to as an antibacterial / antiviral film.

  In glass products in which an antibacterial / antiviral film containing conventional silver ions is formed on a glass substrate, silver ions in the antibacterial / antiviral film diffuse from the interface between the antibacterial / antiviral film and glass to the glass side. As a result, there has been a problem that the glass is colored yellow. In the present invention, the presence of at least one alkali metal ion selected from sodium, potassium, and lithium together with silver ions in the antibacterial / antiviral film allows the diffusion of silver ions from the film to the glass. It was made possible to suppress, and the condition (ii) was satisfied. Thereby, in the glass with a film of the present invention, both the antibacterial and antiviral sustainability of silver ions are improved and the yellowing of the glass is suppressed.

  The alkali metal ions are likely to move because of their relatively small ionic radii, and are preferentially diffused into the glass in preference to silver ions, thereby suppressing the diffusion of silver ions into the glass. As a result, it is speculated that the antibacterial / antiviral membrane has a higher ability to retain silver ions and the above effect can be obtained.

Hereafter, each component of the glass with a film of this invention is demonstrated.
(Glass substrate)
The material and shape of the glass substrate used for the coated glass of the present invention are appropriately selected according to the use as the coated glass. Examples of the material of the glass substrate include ordinary soda lime glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass. As the glass substrate, a glass substrate made of glass or tempered glass that absorbs ultraviolet rays or infrared rays may be used.

  Examples of the shape of the glass substrate include a plate shape and a rod shape. The surface of the glass substrate may be flat, uneven, or the entire surface or a part thereof may have a curvature. For example, when the glass substrate is plate-shaped, the thickness can be appropriately selected depending on the use of the coated glass obtained. In general, it is preferably 0.5 to 10 mm. The glass substrate may be a laminated glass in which a plurality of glass plates are bonded with an intermediate film interposed therebetween.

(Antimicrobial / antiviral membrane)
The coated glass of the coated glass of the present invention has on the surface of at least a part of the glass substrate, contains silicon oxide as a matrix, contains silver ions, and at least one alkali metal selected from sodium, potassium, and lithium Antibacterial and antiviral membranes containing

  The region where the antibacterial / antiviral film is disposed on the glass substrate is a region where antibacterial / antiviral properties are required, and can be appropriately selected depending on the application. When the glass substrate is a glass plate, it may be disposed in the entire region of one or both main surfaces of the glass plate, for example, may be disposed in the entire region of one main surface.

  Here, in this specification, “a film having silicon oxide as a matrix” (hereinafter also referred to as “silicon oxide-based matrix film” or simply “film”) refers to —Si—O—Si from a silicon oxide raw material component. A film mainly containing polysiloxane having a three-dimensional network structure obtained by generating a siloxane bond represented by − and increasing the molecular weight linearly or three-dimensionally. Hereinafter, polysiloxane having a three-dimensional network structure is referred to as a “silicon oxide matrix”.

  The antibacterial / antiviral membrane according to the present invention is a silicon oxide matrix membrane containing silver ions (a) and ions (b) of alkali metals (consisting of at least one selected from sodium, potassium and lithium). It is. In other words, the antibacterial / antiviral membrane includes a silver ion (a), an ion (b) of an alkali metal (made of at least one selected from sodium, potassium, and lithium), and a silicon oxide matrix (c). It is a film | membrane containing.

  The silver ion (a) is a component that imparts antibacterial and antiviral properties to the silicon oxide matrix film. The content of silver ions (a) may be an amount that can be contained in the silicon oxide matrix film to obtain the desired antibacterial and antiviral properties. Specifically, the content of silver ions (a) is preferably 0.01% by mass to 30% by mass and more preferably 0.05% by mass to 10% by mass with respect to the total mass of the silicon oxide matrix film. . By making content of silver ion (a) into the said range, while antibacterial property and antiviral property are fully expressed, generation | occurrence | production of yellowing can also be suppressed. In addition, the range of the content of the silver ions is a range in which the occurrence of yellowing becomes a problem in the conventional silicon oxide matrix film containing silver ions.

In the silicon oxide matrix film, silver ions (a) are contained in the form of a salt containing silver. Examples of the salt include silver nitrate (Ag ⁺ .NO ₃ ⁻ ), silver acetate (Ag ⁺ .CH ₃ COO ⁻ ), silver perchlorate (Ag ⁺ .ClO ₄ ⁻ ), and the like.

  The silicon oxide matrix film preferably contains copper ions (d) for the purpose of further improving antibacterial and antiviral properties. Generally, silver ions and copper ions are considered to have different types of bacteria and viruses that exhibit antibacterial and antiviral properties. Therefore, it is preferable to contain copper ions in addition to silver ions because antibacterial and antiviral properties are expressed against various bacteria and viruses.

  The content of the copper ion (d) may be an amount that can be contained in the silicon oxide matrix film to obtain the desired antibacterial and antiviral properties. Specifically, the content of the copper ion (d) is preferably 0.01% by mass to 30% by mass, more preferably 3% by mass to 30% by mass with respect to the total mass of the silicon oxide matrix film. 5 mass%-15 mass% are especially preferable. By making the content of the copper ion (d) in the above range, the antibacterial and antiviral properties are sufficiently expressed against various bacteria and viruses in combination with the silver ion (a), and in a short time. Antibacterial and antiviral properties can be expressed.

  In the coated glass of the present invention, antibacterial and antiviral properties are evaluated by the index of (iii) above using Escherichia coli, Staphylococcus aureus, or influenza virus substitute phage.

  When an antibacterial test was performed on the surface of the coating using an Escherichia coli, Staphylococcus aureus, or influenza virus substitute phage in the dark at 25 ° C., JIS Z 2801 after 1 hour from the start of the test. It can be said that it has sufficient antibacterial and antiviral properties when the antibacterial activity value specified in (1) can be 2.0 or more in any of the above antibacterial tests. The antibacterial activity value is more preferably 3.0 or more.

Here, the copper ions (d) are contained in the form of a salt containing copper in the same manner as the silver ions (a) in the silicon oxide matrix film. Examples of the salt include copper sulfate (Cu ²⁺ .SO ₄ ²⁻ ), copper chloride (Cu ²⁺ .2Cl ⁻ ), copper nitrate (Cu ²⁺ .2NO ₃ ⁻ ), and the like. The valence in the copper ion (d) may be monovalent or divalent, and these may be used in combination.

  The silicon oxide matrix membrane preferably contains particles having a cation adsorption ability. The silver ions (a) and / or copper ions (d) are preferably supported on particles having cation adsorption ability and contained in the silicon oxide matrix film. By doing so, movement of silver ions (a) and / or copper ions (d) due to heat can be suppressed, and the silver ions (a) and / or copper ions (d) are converted into a silicon oxide matrix film. It can be held stably for a longer time. Further, it can be stably held in the film through a high-temperature treatment step such as a strengthening step, for example, a high-temperature treatment at 400 to 700 ° C. That is, when silver ions (a) and / or copper ions (d) are supported on particles having cation adsorption ability, antibacterial and antiviral long-term sustainability can be improved by the high temperature treatment.

The particles having the cation adsorbing ability (hereinafter also referred to as “cation adsorbing particles”) can be used without affecting the antibacterial and antiviral properties of silver ions (a) and / or copper ions (d). There is no particular limitation as long as it is a particle capable of adsorbing and supporting an amount of silver ions (a) and / or copper ions (d). Specific examples include zeolite particles, smectite particles, bentonite particles, calcium phosphate compound particles, and the like. The calcium phosphate compound particles, hydroxyapatite _{(Ca 10 (PO 4) 6} (OH) 2), tricalcium phosphate _{(Ca 3 (PO 4) 2} , calcium zinc phosphate _{(CaαZnβAl y (PO 4) 6} , CaαZnβ (PO ₄ ) ₂ ) and the like.

  From the viewpoint of adsorptivity of silver ions (a) and / or copper ions (d), zeolite particles, smectite particles, and calcium phosphate compound particles are preferable. When both the silver ion (a) and the copper ion (d) are contained in the silicon oxide matrix film, only the silver ion (a) may be supported on the cation-adsorptive particles and used. Only d) may be used supported on cation-adsorbing particles, or both may be used supported on cation-adsorbing particles. When both are supported on cation-adsorbing particles, both may be supported on the same cation-adsorptive particles, and only cation-adsorptive particles supporting only silver ions (a) and copper ions (d). A combination of the supported cation-adsorbing particles may be used.

  The total amount of silver ions (a) and / or copper ions (d) that can be carried by the cation-adsorbing particles can be approximately 150 mg to 1500 mg in total with respect to 100 g of the cation-adsorbing particles. When silver ions (a) and copper ions (d) contained as necessary are supported on cation-adsorbing particles, the amount can be the same as when not used on the cation-adsorbing particles.

  The particle size of the cation-adsorbing particles used is such that the average particle size measured by the dynamic light scattering method is 0.005 to 0.5 μm from the viewpoint of ensuring the transparency of the silicon oxide matrix film. Preferably, 0.005 to 0.3 μm is more preferable. The measurement of the average particle diameter by the dynamic light scattering method can be performed using, for example, a dynamic light scattering nanotrack 150 particle size distribution meter (manufactured by Nikkiso Co., Ltd.).

  The method for supporting silver ions (a) and / or copper ions (d) on the cation-adsorptive particles is a conventional method. Alternatively, a commercial product in which silver ions (a) or copper ions (d), or silver ions (a) and copper ions (d) are adsorbed on cation-adsorbing particles may be used.

  The silicon oxide-based matrix membrane contains the silver ion (a) as an essential component as a component that exhibits antibacterial and antiviral properties, and optionally contains copper ion (d), as well as sodium, potassium, and lithium. And at least one alkali metal ion (b) selected from (hereinafter also referred to as “alkali metal ion (b)”). The total content of alkali metal ions (b) is preferably 0.01 to 1% by mass.

  Even when 0.01% by mass or more of alkali metal ions (b) is contained, the silicon oxide matrix film generally contains a sufficient amount of silver ions (a) exhibiting antibacterial and antiviral properties. It is possible to suppress the occurrence of yellowing in the obtained glass with a coating. In addition, by setting the content of the alkali metal ion (b) to 1% by mass or less, mechanical strength such as wear resistance of the obtained silicon oxide matrix film can be substantially ensured at an intended level, Moreover, antibacterial durability can be substantially ensured at a desired level during a long-term durability test such as a moisture resistance test. As for content of an alkali metal ion (b), 0.05 mass%-1 mass% are more preferable. Among the alkali metal ions, sodium ions are particularly preferable from the viewpoint of a small ion radius and easy diffusion into glass.

  The silicon oxide matrix (c) in the silicon oxide matrix film is not particularly limited as long as it is a polysiloxane having a three-dimensional network structure. The content of the silicon oxide matrix (c) in the silicon oxide-based matrix film can be approximately 70 to 99.98% by mass with respect to the total amount of the silicon oxide-based matrix film. The content is preferably 90 to 99.98% by mass.

The glass with a coating of the present invention contains at least one kind of alkali metal ion (b) selected from silver ion (a) and sodium, potassium and lithium contained in the coating, for example, by the following measuring method. It can be defined as the amount of eluted ions.
(Measurement method of surface elution ion quantity)
The amount of ions eluted by masking the glass substrate portion of the coated glass with polytetrafluoroethylene (PTFE) tape, immersing in 10 mL of 0.1% by weight nitric acid aqueous solution for 5 minutes, and sonicating at 28 kHz. Is measured by ICP-MS and normalized by the film area.

The silver ion (a) the amount of a coated glass is contained in the coating amount of the surface ions eluted amount is 0.3ng ^/ cm ² ~1000ng ^/ cm 2 are ^{preferred, 15ng / cm 2 ~800ng / cm} 2 Is more preferred.

Similarly, the amount of at least one alkali metal ion (b) selected from sodium, potassium, and lithium contained in the coating glass is 0.3 ng / cm ^{2 to} 200 ng in total. / cm ² and qs are ^preferred, and more preferred amount of a ^{0.3ng / cm 2 ~100ng / cm 2} .

In the glass with a film of the present invention, when the film further contains copper ions, the amount of copper ions (d) contained in the film with the glass with a film is 0.3 ng / cm ^{2 to} 1000 ng as described above. / cm ² and qs are ^preferred, and more preferred amount of a ^{15ng / cm 2 ~800ng / cm 2} .

  In the glass with a coating of the present invention, the thickness of the coating is preferably 20 to 100 nm, and more preferably 30 to 60 nm. If the thickness of the coating is less than 20 nm, the antibacterial / antiviral function may be insufficiently sustained and the effect may not be sufficiently exhibited. Moreover, when the film thickness exceeds 100 nm, cracks may occur.

  In the glass with a coating of the present invention, the coating preferably has a fluorine-containing antifouling layer as the outermost layer. A film having a fluorine-containing antifouling layer as the outermost layer can be obtained, for example, by forming a film by adding a fluorine-containing antifouling agent to the film-forming composition of the present invention described later. Moreover, when a film has a fluorine-containing antifouling layer as an outermost layer, this fluorine-containing antifouling layer is not limited to what is formed by making the said film forming composition contain a fluorine-containing antifouling agent. For example, after forming a silicon oxide matrix layer without containing a fluorine-containing antifouling agent in the film forming composition, a liquid composition containing a fluorine-containing antifouling agent is applied onto the layer. A fluorine antifouling layer may be formed.

  In the coated glass of the present invention, ΔYI is 1.8 or less before and after the moisture resistance test of (ii) above. When ΔYI is 1.8 or less, it can be said that the coated glass of the present invention is excellent in yellowing resistance. ΔYI before and after the moisture resistance test (ii) is more preferably 1.0 or less.

  The coated glass of the present invention has the antibacterial / antiviral properties of (iii). In particular, when the antibacterial test is performed using Escherichia coli, Staphylococcus aureus, or influenza virus substitute phages in the dark, at 25 ° C. in the dark, on the surface of the above-mentioned coating, particularly from the start of the test. It is preferable that the antibacterial activity value defined by JIS Z 2801 after 1 hour can be 2.0 or more in any of the antibacterial tests described above.

  Furthermore, the coated glass of the present invention is also excellent in antibacterial durability, specifically, the antibacterial activity value defined in JIS Z 2801 after leaving it in an environment of 85 ° C. and 85% RH for 1000 hours. It is preferable that it can be 2.0 or more.

  The coated glass of the present invention has a solar transmittance (Te) measured according to JIS-R3106 (1998) of preferably 80% or more, and more preferably 85% or more. In the glass with a film of the present invention, the haze value is preferably 1% or less, and more preferably 0.5% or less.

The glass with a coating of the present invention has a Martens hardness of 1600 N / mm ² or more measured on the surface of the coating with a loading speed of 0.05 mN / 10 s, a creep of 5 s, and an unloading speed of 0.05 mN / 10 s. It is preferable. The Martens hardness of the coating is more preferably 2000 N / mm ² or more. The upper limit of the Martens hardness of the coated glass in the coated glass of the present invention is not particularly limited, but is typically 10,000 N / mm ² or less.

  Here, among the components constituting the coating film, the silicon oxide matrix (c) is a component forming the film itself, and usually forms the silicon oxide matrix (c) and forms the silicon oxide matrix film. Are performed simultaneously. That is, other film-containing components cannot be added to the silicon oxide matrix (c) after the formation of the silicon oxide matrix (c). Accordingly, a silicon oxide matrix comprising a silicon oxide raw material component for forming a silicon oxide matrix (c) and the above components that the silicon oxide matrix film contains in addition to the silicon oxide matrix (c). By preparing a film-forming composition (hereinafter also referred to as “film-forming composition”) and forming a film, the silicon oxide matrix film according to the glass with a film of the present invention can be obtained. As the film forming composition for obtaining a film related to the glass with a film of the present invention, for example, the film forming composition of the present invention described below can be used.

[Coating composition]
The film-forming composition of the present invention comprises a silicon oxide raw material component that forms a silicon oxide matrix and at least one alkali metal ion selected from sodium, potassium, and lithium with respect to the total solid content of 0.01 mass. % To 1% by mass and 0.01% to 30% by mass of silver ions based on the total solid content. The film forming composition of the present invention further contains copper ions, and the content of the copper ions is preferably 0.01% by mass to 30% by mass with respect to the total solid content.

  The silicon oxide matrix in the film-forming composition of the present invention corresponds to the silicon oxide matrix (c) described above. At least one alkali metal ion selected from silicon oxide raw material component, silver ion (a), sodium, potassium, and lithium for forming the silicon oxide matrix (c) contained in the film forming composition of the present invention The range of the content of (b) and the optionally contained copper ion (d) with respect to the total solid content, including the preferable content range, can be the same as the content in the silicon oxide matrix film of the glass with coating. .

  The film-forming composition of the present invention preferably further contains particles having a cation adsorption ability. Moreover, it is preferable that silver ions (a) and / or copper ions (d) are supported on particles having a cation adsorbing ability and blended in the film-forming composition. Examples of the particles having a cation adsorption ability include the same particles as those contained in the silicon oxide matrix film of the glass with a film.

  As the silicon oxide raw material component of the silicon oxide matrix (c) contained in the film forming composition, for example, a solution containing a silicon oxide raw material component is used. The solution containing the silicon oxide raw material component is preferably a solution containing water and a product obtained by removing a part of the alkali metal from the alkali metal salt of silicic acid. In the present invention, the coating prepared by the following method The forming composition (X) is particularly preferably used.

  The film-forming composition (X) comprises a curable silicic acid compound (hereinafter also referred to as “silicic acid compound (c ′)”) produced by desalting an aqueous solution of an alkali silicate compound, and an alkali metal. An alkali metal is at least one selected from sodium, potassium, and lithium, a silver ion, and an organic solvent, and the content of the alkali metal ion with respect to the total solid content is 0.01. It is a liquid composition of mass% to 1 mass%. Here, the solid content in this specification means a silicon oxide-based matrix film constituent component among the components contained in the film forming composition, and volatilizes by heating in the film forming process of water, organic solvent, etc. All components other than sex components are shown.

  As the alkali silicate compound, at least one selected from sodium silicate, potassium silicate, and lithium silicate is used. The aqueous solution of the alkali silicate compound can easily reduce the content of alkali metal ions to the desired concentration by the desalting treatment.

  That is, by this desalting treatment, the aqueous solution of the alkali silicate compound contains the silicate compound (c ′) as a raw material of the silicon oxide matrix (c) as a main component, and alkali metal ions (however, , At least one selected from sodium, potassium, and lithium.) As a content after adding a predetermined amount of silver and other optional components to 0.01% by mass to 1% based on the total solid content It can be set as the film formation composition (X) containing the quantity used as the mass%.

Such desalting treatment of an alkali silicate compound can be explained as follows, for example, in sodium silicate.
Sodium silicate is a compound generally represented by a molecular formula of Na ₂ O.nSiO ₂ .mH ₂ O. The coefficient n in the molecular formula indicates the molar ratio of SiO ₂ to Na ₂ O (SiO ₂ / Na ₂ O). The range of n in commercially available sodium silicate is about 0.5 to 4.0.

Here, in order to produce an antibacterial / antiviral membrane, Patent Document 1 discloses a method of forming a film by mixing silver and / or copper without performing a desalting treatment on the aqueous solution of sodium silicate. It was the method that was done. According to this method, silicate gel is generated from sodium silicate, and SiO ₂ fine particles are generated by solidification. The generated SiO ₂ fine particles have silanol groups on the surface, thereby bonding particles and bonding with a substrate glass to form a film, but this is a problem in terms of durability.

On the other hand, when preparing the film forming composition (X) according to the present invention, first, sodium silicate is desalted using the aqueous solution of sodium silicate. In an aqueous solution of the sodium silicate, sodium molecules silicate rather than dissolved in the state of the _{Na 2 O · nSiO 2 · mH} 2 O, present in ionic form, desalination of aqueous sodium silicate solution Specifically, the treatment is performed using a strongly acidic cation exchange resin.

  By the desalting treatment, the sodium ions in the sodium silicate aqueous solution are ion-exchanged with the strong acid cation exchange resin, and the ratio of sodium ions to the total solid content in the aqueous solution is sufficiently reduced, so that the aqueous solution A silicic acid compound (c ′) is obtained. In the desalting treatment, the ratio of sodium ions to the total solid content in the aqueous solution after the treatment is 0.01% by mass to 1% by mass after adding silver ions (a) and copper ions (d). It is preferable to carry out to such an extent that it becomes more than 0.01 mass% and 1.6 mass% or less. The solid content in the aqueous solution after the desalting treatment is composed of a silicon compound (c ′) and sodium ions, and the proportion of the silicate compound (c ′) in the total solid content is from 100% by mass to the sodium. The amount obtained by subtracting the amount of ions.

  Although the structure of the silicate compound (c ′) is not clear in detail, the silicate compound (c ′) is linear or 3 to the extent that water-solubility can be maintained by a —Si—O—Si— siloxane bond. It is a compound having a high molecular weight in dimension and partially having a Si-OH group.

  The aqueous solution obtained by desalting the sodium silicate aqueous solution in this manner is hereinafter referred to as a “desalted sodium silicate solution”. Similarly, an aqueous solution obtained by desalting an aqueous alkali silicate compound solution is hereinafter referred to as a “desalted alkali silicate solution”. Using a desalted sodium silicate solution is the same as forming a polysiloxane film having a three-dimensional network structure by a sol-gel method using a conventionally known solution containing a hydrolyzable silicon compound and water. A polysiloxane film having a simple structure can be formed.

The alkali silicate compound used for the desalting treatment is not particularly limited, but a compound having a low alkali metal content is preferable from the viewpoint of work efficiency. For example, in sodium silicate, sodium silicate having a large value of n in the molecular formula is preferred. Specifically, sodium silicate having a value of n of 3 or more is preferable. Similarly, when potassium silicate and lithium silicate are used, it is preferable to use a compound having a high molar ratio of SiO _{2 in} the molecule.

  The concentration of the alkali silicate compound in the aqueous alkali silicate compound solution used for the desalting treatment is preferably about 1 to 6% by mass. The desalting treatment is performed, for example, by adding a predetermined amount of the particulate strong acidic cation exchange resin to the alkali silicate compound aqueous solution and stirring the mixture at a predetermined temperature for a predetermined time. The above-mentioned input amount and stirring time are the concentration of the alkali silicate compound in the alkali silicate aqueous solution to be treated, the concentration of alkali metal ions in the desired desalted alkali silicate solution, and the treatment of the strongly acidic cation exchange resin used. It is appropriately selected according to the ability and the like.

  The film-forming composition (X) is prepared by adding silver ions (a) and an organic solvent to the demineralized silicate liquid, and the alkali in the demineralized silicate liquid relative to the total solid content of the composition (X). It can manufacture easily by adding so that content of a metal ion may be 0.01 mass%-1 mass%. Furthermore, it is preferable to add copper ion (d) as an optional component so as to satisfy the above conditions. In addition, as for content of the said alkali metal ion in the composition (X) for film formation, 0.05 mass%-1 mass% are more preferable.

Here, the antibacterial / antiviral film according to the present invention produced using the film forming composition (X) as described above is Si (OR) ₄ (R: an alkyl group, in general, which is a conventional alkoxysilane. Specifically, SiO _p (OH) _q (OR) _r (p and q are integers of 0 or more, r is an integer of 1 or more, and p + q + r = 4)) (wherein an oxygen atom that is not a hydroxyl group is chemically bonded to another silicon atom in the structure) is formed by adding silver to a composition containing a product. Compared to the coating film, color development by silver can be remarkably suppressed.

  The silver ions (a) and the copper ions (d) optionally blended can be blended into the film-forming composition (X) in the same form as described for the silicon oxide matrix film. The content of silver ions (a) and copper ions (d) in the film-forming composition (X) is as described above.

The ratio of the silicon oxide matrix (c) in the silicon oxide matrix film is the remainder obtained by removing the content (mass%) of each component from 100 mass%, and can be approximately 70 to 99.98 mass%. The content of the silicic acid compound (c ′) in the film-forming composition (X) can be approximately 70 to 99.98% by mass in the total solid content as described above in terms of SiO ₂ .
Moreover, 0.1-3 mass% is preferable and, as for content of the total solid with respect to the whole quantity of composition (X) for film formation, 0.5-2 mass% is more preferable.

  5-50 mass% is preferable with respect to the whole quantity of the composition (X) for film formation, and, as for content of water in the composition (X) for film formation, 10-20 mass% is more preferable.

  Specific examples of the organic solvent used in the film-forming composition (X) include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetyl acetone; tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, Ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diisopropyl ether; esters such as ethyl acetate, butyl acetate, isobutyl acetate, methoxyethyl acetate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, 1-methoxy-2-propanol, 2-ethoxyethyl Nord, alcohols such as diacetone alcohol; n-hexane, n- heptane, Isokutan, benzene, toluene, xylene, gasoline, diesel fuel, hydrocarbons such as kerosene; acetonitrile, nitromethane and the like.

  These may be used alone or in combination of two or more. Further, the amount of the organic solvent to be used is appropriately adjusted depending on the kind and blending ratio of each of the above blending components.

  In order to obtain a state in which each component contained in the film-forming composition (X) is stably dissolved or dispersed, the organic solvent contains at least 20% by mass, preferably 50% by mass or more alcohol. Examples of the alcohol used in such an organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, and 2-ethoxy. Ethanol, 4-methyl-2-pentanol, 2-butoxyethanol and the like are preferable.

  Among these, an alcohol having a boiling point of 80 to 160 ° C. is preferable from the viewpoint that the solubility of the silicate compound (c ′) is good and the coating property to the coated surface is good. 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.

  30-90 mass% is preferable with respect to the whole quantity of the composition for film formation (X), and, as for the quantity of the organic solvent contained in the composition for film formation (X), 50-85 mass% is more preferable. The total amount of water and organic solvent in the film-forming composition (X) is an amount that allows the total solid content to be in the above range from the viewpoint of improving workability.

  The film-forming composition may optionally contain functional components such as an ultraviolet absorber, an infrared absorber, and a fluorine-containing antifouling agent. The film-forming composition can further contain various optional compounding agents as necessary within a range not impairing the effects of the present invention. As an optional compounding agent, an additive such as a surface conditioner, an antifoaming agent or a viscosity conditioner may be included for the purpose of improving the coatability on the surface to be formed, usually the substrate surface, and to the substrate surface. For the purpose of improving adhesion, an additive such as an adhesion-imparting agent may be included. The compounding quantity of these additives is 0.01-0.0 for every additive component with respect to the raw material component of the silicon oxide matrix (c), specifically, 100 parts by mass of the silicate compound (c ′). An amount of 2 parts by mass is preferred. The composition for forming a film may contain a dye, a pigment, a filler, and the like as long as the object of the present invention is not impaired.

  When the film-forming composition optionally contains a fluorine-containing antifouling agent, the resulting silicon oxide-based matrix film has a fluorine-containing antifouling layer as the outermost layer. When the film-forming composition contains a fluorine-containing antifouling agent, the film-forming composition is applied on a glass substrate, and if necessary, the solvent is removed, and then the film is cured and cured in a film-forming process. The fluorine-containing antifouling layer imparting excellent antifouling property can be formed as the outermost layer of the silicon oxide matrix film finally obtained by transferring the agent to the upper surface of the film.

  Moreover, the fluorine-containing antifouling layer that the silicon oxide-based matrix film has as the outermost layer is not limited to those formed by adding a fluorine-containing antifouling agent to the above-mentioned film forming composition. For example, after forming a silicon oxide matrix layer without containing a fluorine-containing antifouling agent in the film forming composition, a liquid composition containing a fluorine-containing antifouling agent is applied onto the layer. A fluorine antifouling layer may be formed.

Below, the case where a fluorine-containing antifouling agent is contained in the film forming composition to form a silicon oxide matrix film will be described.
As the fluorine-containing antifouling agent, a fluorine-containing antifouling agent capable of undergoing a condensation reaction with the silanol group of the silicic acid compound (c ′) in the film forming composition is preferable. If such a fluorine-containing antifouling agent is used, the fluorine-containing antifouling agent is easily fixed to the silicon oxide matrix film.

  Examples of such fluorine-containing antifouling agents include fluorine-containing hydrolyzable silane compounds. Examples of the fluorine-containing hydrolyzable silane compound include a hydrolyzable silane compound having a fluorine-containing polyether group, a hydrolyzable silane compound having a fluorine-containing alkyl group or a fluorine-containing alkylene group, and a polydimethylsiloxane bonded with a fluorine-containing organic group. Examples thereof include silane compounds having a chain structure.

As the hydrolyzable silane compound having a fluorine-containing polyether group, a hydrolyzable silane compound having a perfluoropolyether group is preferable. Specific examples of the hydrolyzable silane compound having a perfluoropolyether group include a compound represented by the following formula (1A) and a compound represented by the following formula (1B).
A ¹ -Q ¹ -SiX ¹ _m R ¹ _3-m (1A)
A ¹ -Q ^1- {CH ₂ CH (SiX ¹ _m R ¹ _3-m )} _n -H (1B)
Symbols in Formula (1A) and Formula (1B) are as follows.
A ¹ is a group represented by the following formula (A).

In formula (A), R ^F1 represents a perfluoroalkyl group. a, b, c, d and e each independently represents 0 or an integer of 1 or more, a + b + c + d + e is at least 1 or more, and each repeating unit enclosed by a, b, c, d and e The order of presence of is not limited in the formula.

In the formula (A), the perfluoropolyether chain excluding R ^F1 is, for example, a perfluoropolyether chain represented by — (OCF ₂ CF ₂ ) _a — (OCF ₂ CF ₂ CF ₂ CF ₂ ) _e — each repeating unit, _{i.e., - (OCF 2 CF 2)} - units and _{- (OCF 2 CF 2 CF 2} CF 2) - unit, needs to have a number and e-number, respectively in total. If there are a and e units in total, respectively, one or more perfluoropolyether chains in which only-(OCF ₂ CF ₂ ) -units are repeatedly bonded and-(OCF ₂ CF ₂ CF ₂ CF ₂ )-It may consist of a combination with one or more perfluoropolyether chains in which only units are repeatedly bonded, and-(OCF ₂ CF ₂ )- OCF ₂ CF ₂ CF ₂ CF ₂ ) —0 or 1 or more of perfluoropolyether chains in which only units are repeatedly bonded, and — (OCF ₂ CF ₂ ) — and — (OCF ₂ CF ₂ CF ₂ CF ₂ ) — are bonded. _{- (OCF 2 CF 2 CF 2} CF 2 -OCF 2 CF 2) - unit is repeated bound one or more perfluoropolyether chains It may be a combination of.

Q ¹ : amide bond, urethane bond, ether bond selected from —C (═O) NH—, —C (═O) N (CH ₃ ) —, —C (═O) N (C ₆ H ₅ ) — , an ester bond, -CF 2 _- shows a consisting of repeating units divalent organic group having 2 to 12 carbon atoms _- may contain one or two elements selected from group and phenylene group, -CH 2 (However, one of the hydrogen atoms in the —CH ₂ — group may be substituted with an —OH group.) Hereinafter, -C (= O) N ... is shown as -CON .... For example, -C (= O) NH- is shown as -CONH-.

X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m X ^{1 s} may be the same as or different from each other.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, an alkyl group, an alkenyl group, or an aryl group) in which part or all of the hydrogen atoms may be substituted. 3-m R < ¹ > may mutually be same or different.
m: 1, 2 or 3 is shown.
n represents an integer of 1 to 10.

In A ¹ of the compound (1A) and the compound (1B), the upper limits of a, b, c, d and e are each independently preferably 200 and more preferably 50. Further, the upper limit of a + b + c + d + e is preferably 200, and more preferably 100. As A ^{1, _{specifically, R F1 - (OCF 2)}} c -, R F1 - (OCF 2 CF 2) a - (OCF 2) c -, R F1 - (OCF 2 CF 2) a -, R _{^{F1 - (OCF 2 CF 2 CF}} 2) d -, R F1 - {OCF (CF 3) CF 2} b -, R F1 - (OCF 2 CF 2 CF 2 CF 2 -OCF 2 CF 2) a - ( wherein The number e of — (OCF ₂ CF ₂ CF ₂ CF ₂ ) — units in the case of (A) is the same as a.), R ^F1 — (OCF ₂ CF ₂ ) _{a ′} — (OCF ₂ CF ₂ CF _{2 CF 2 -OCF 2 CF 2)} e - (OCF 2 CF 2 CF 2) d ( wherein (a) the case shown by _{- (OCF 2 CF 2) -} . the number a of the unit is a e + a ') or the like Is mentioned.

As the compound (1A), the following compounds are particularly preferable.
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OCH 3) 3
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OC 2 H 5) 3
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OCH 3) 3
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OC 2 H 5) 3
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OCH 3) 3
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OC 2 H 5) 3
(However, in all the above, a = 7-8, average value: 7.3 is shown.)
_{CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -CONHC 3 H 6 Si (OCH 3) 3
_{CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -CONHC 3 H 6 Si (OC 2 H 5 _{3
CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -CONHC 2 H 4 Si (OCH 3) 3
_{CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -CONHC 2 H 4 Si (OC 2 H 5 _{3
CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -C 2 H 4 Si (OCH 3) 3
_{CF 3 CF 2 - (OCF 2} CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -C 2 H 4 Si (OC 2 H 5 ₃
(However, in all the above, a ′ = 1 to 2, e = 7 to 14, d = 1 to 2)
Moreover Among _{these, CF 3 CF 2 - (OCF} 2 CF 2) a '- (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) e - (OCF 2 CF 2 CF 2) d -CONHC 3 H 6 Si (OCH ₃ ) ₃ is preferred.

The compounds (1A) and (1B) can be produced by a known method. For example, the compound whose terminal perfluoroalkyl group is CF ₃ can be specifically produced by the method described in WO2009-008380. Compound (1B) can be produced, for example, by the method described in JP-A-9-157388.

As the silane compound having a hydrolyzable group and a perfluoropolyether group, a perfluoropolyether residue-containing polyorganosiloxane represented by the following formula (2) may be used.
W ²¹ _s1 (R ²¹ ) _t1 Z ²¹ -Q ²¹ -A ² -Q ²² -Z ²² (R ²² ) _t2 W ²² _s2 (2)
In the formula (2), A ² is a divalent perfluoropolyether residue, Q ²¹ and Q ²² are each independently selected from —CONH—, —CON (CH ₃ ) —, and —CON (C ₆ H ₅ ) —. The amide bond, the urethane bond, the ether bond, the ester bond, the —CF ₂ — group and the phenylene group, which may contain one or two selected from 2 —carbon atoms composed of repeating —CH ₂ — units. 12 divalent organic groups (wherein one hydrogen atom of the —CH ₂ — group may be replaced by an —OH group), Z ²¹ and Z ²² each independently represents a siloxane bond; 3 to 11 valent polyorganosiloxane residues having at least one, R ²¹ and R ²² are each independently a monovalent alkyl group having 8 to 40 carbon atoms, t1 and t2 are each independently an integer of 1 to 8, W ²¹ and W ²² are A group shown in each independently represent the following formula (W), s1, s2 are each independently an integer from 1 to 9, however, s1 + t1 = ^(valence -1 of ^{Z 21), s2 + t2 =} ( valence of ^{Z 22} -1).

^{_{- (CH 2) p -SiX 2}} m R 23 3-m ... (W)
In the formula (W), X ² is an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. Represents a halogen atom or an isocyanate group. Among these, an alkoxy group having 1 to 10 carbon atoms, an isocyanate group, and a chlorine atom are preferable. The m X ² may be the same as or different from each other.
R ²³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and 3-m R ^{23 s} may be the same as or different from each other. m is 1, 2 or 3, and p is an integer of 2-10.

Specific examples of A ² include groups represented by the following general formula (A3), (A4), or (A5).
_{- (CF 2) e1 (OCF} 2 CFY) f O {(CF 2) g O)} h (CFYCF 2 O) i (CF 2) e2 - ... (A3)
(In Formula (A3), Y is each independently a fluorine atom or a CF ₃ group, e1 and e2 are integers of 1 to 3, g is an integer of 2 to 6, f and i are each an integer of 0 to 100, and f + i is 2 to 100, h is an integer of 0 to 6, and the arrangement of each repeating unit may be random.)
_{- (CF 2) e3 (OCF} 2 CF 2 CF 2) j O (CF 2) e4 - ... (A4)
(In formula (A4), j is an integer of 1 to 100, and e3 and e4 are integers of 1 to 3.)
_{- (CF 2) e5 (OCF} 2 CFY) k (OCF 2) l O (CF 2) e6 - ... (A5)
(In Formula (A5), Y is a fluorine atom or CF ₃ group, e5 and e6 are integers of 1 to 3, k and l are integers of 0 to 100, and k + 1 is 2 to 100, respectively. May be random.)

In the silane compound represented by the formula (2), A ² is more preferably a group represented by the following formula (A6).
_{-CF 2 - (OCF 2 CF 2} ) x - (OCF 2) y -OCF 2 - ... (A6)
(In the formula (A6), x = 0 to 50, y = 1 to 50, and x + y = 2 to 60 are integers.)
The compound (2) can be produced by a known method, for example, the method described in Japanese Patent No. 4666667.

Specific examples of the hydrolyzable silane compound having a fluorine-containing alkyl group or a fluorine-containing alkylene group include compounds represented by the following formula (3).
^{_{(A-R f) r -Si}} (R 3) v X 3 (4-r-v) ... (3)
(In the formula (3), ^{R f} is at least one divalent organic group fluoroalkylene group etheric oxygen atom has a even better 1 to 20 carbon atoms including, A is a fluorine atom or -Si ^(R 3) _v X ³ _(3-v) , R ³ is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and does not have a fluorine atom, X ³ represents a hydrolyzable group, r is 1 Or 2, v is 0 or 1, and r + v is 1 or 2. When there are a plurality of AR ^f and X ³ , these may be different or the same.

R ³ is preferably a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
In formula (3), it is particularly preferred that r is 1 and v is 0 or 1.
Examples of X ³ include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which at least one hydrogen of the amino group is substituted with an alkyl group. A hydroxyl group (silanol group) is formed by a hydrolysis reaction, and further, a reaction that forms a Si—O—Si bond through a condensation reaction between molecules easily proceeds, so that an alkoxy group having 1 to 4 carbon atoms and a halogen atom are formed. Preferably, a methoxy group, an ethoxy group, and a chlorine atom are more preferable, and a methoxy group and an ethoxy group are particularly preferable.

The hydrolyzable silane compound (3) is a fluorine-containing hydrolyzable silane compound having one or two bifunctional or trifunctional hydrolyzable silyl groups. A-R ^f and R ^f are each preferably a perfluoroalkyl group and a perfluoroalkylene group (both groups may contain an etheric oxygen atom).

Specific examples of the hydrolyzable silane compound (3) include the following compounds.
F (CF ₂ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
F (CF ₂ ) ₆ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{F (CF 2) 3 OCF (} CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3,
_{F (CF 2) 2 O (} CF 2) 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3.

(CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3 O) 3 SiCH 2} CH 2 (CF 2) 2 OCF 2 (CF 3) CFO (CF 2) 2 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3 .

Among these, F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ is preferable.
The compound (3) can be produced by a general method. Moreover, there exists a commercial item as a compound (3), and it is also possible to use such a commercial item for this invention.

  Specific examples of the hydrolyzable silane compound having a fluorine-containing organic group-bonded polydimethylsiloxane chain include compounds represented by the following formula (4).

(In the formula (4), R ^f1 is a monovalent organic group having 1 to 20 carbon atoms containing a fluorine atom, Q ⁴ is an alkylene group, z is an integer of 0 to 100, and R ⁴ is 1 to 1 carbon atoms. 5 is a monovalent hydrocarbon group, X ⁴ is a hydrolyzable group, and m is 2 or 3.)

R ^f1 is preferably a monovalent polyfluorohydrocarbon group. The “monovalent polyfluorohydrocarbon group” refers to a group in which two or more hydrogen atoms of a monovalent hydrocarbon group are substituted with fluorine atoms. R ^f1 has 1 to 20 carbon atoms, preferably 4 to 16 and particularly preferably 4 to 12. R ^f1 is preferably a polyfluoroalkyl group.

The number of fluorine atoms in R ^f1 is (number of fluorine atoms in the polyfluorohydrocarbon group) / (number of hydrogen atoms in the hydrocarbon group having the same number of carbon atoms corresponding to the polyfluorohydrocarbon group) × 100 (% ) Is preferably 60% or more, particularly preferably 80% or more. R ^f1 is preferably a perfluorohydrocarbon group (a group in which all of the hydrogen atoms in the hydrocarbon group are substituted with fluorine atoms), and particularly preferably a perfluoroalkyl group.

The structure of R ^f1 is a linear structure or a branched structure, but a linear structure is preferable. In the case of a branched structure, it is preferable that the branched portion is a short chain having about 1 to 3 carbon atoms, and the branched portion is near the end of R ^f1 .

Specific examples of R ^f1 are given below. In the following examples, structural isomeric groups having the same molecular formula are included. C ₄ F ₉ - _{(e.g., F (CF 2) 4 -} , (CF 3) 2 CFCF 2 -, (CF 3) 3 C-, CF 3 CF 2 CF (CF 3) - , _etc.), C _{5 F 11} - _{(e.g., F (CF 2) 5 -} , (CF 3) 2 CF (CF 2) 2 -, (CF 3) 3 CCF 2 -, CF 3 (CF 2) 2 CF (CF 3) - , etc.), _{C 6 F 13 -, C 8} F 17 -, C 10 F 21 -, C 12 F 25 -, C 14 F 29 -, C 16 F 33 -, C 18 F 37 -, C 20 F 41 - , and the like.

Q ⁴ is preferably — (CH ₂ ) _q — (q is an integer of 2 or more), and q is preferably an integer of 2 to 6 and particularly preferably 2 or 3. That is, Q ⁴ is particularly preferably —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —. z is an integer of 0 to 100, preferably 1 to 50, and particularly preferably 2 to 30.

R ⁴ is a monovalent hydrocarbon group having 1 to 5 carbon atoms. R ⁴ is preferably an alkyl group having 1 to 5 carbon atoms, and preferred examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. . 3-m R ⁴ may be the same or different.

X ⁴ is a hydrolyzable group, an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy having 2 to 10 carbon atoms. A group, a halogen atom, or an isocyanate group. Among these, —OR ⁴¹ (R ⁴¹ is a hydrocarbon group which may contain a monovalent oxygen atom having 1 to 10 carbon atoms), a chlorine atom, and an isocyanate group are preferable, and alkoxy having 1 to 10 carbon atoms is preferred. Particularly preferred are groups, chlorine atoms and isocyanate groups. Preferred examples of —OR ⁴¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an isopropenoxy group, and an n-butoxy group, and an acetoxy group. The m X ⁴ may be the same or different. m is 1, 2 or 3, and 2 or 3 is preferable.

  These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, according to the kind and combination of the fluorine-containing antifouling agent to be used, the content of the fluorine-containing antifouling agent in the film forming composition is appropriately adjusted. As for content of the fluorine-containing antifouling agent in the said film forming composition, 0.01-10 mass% is preferable with respect to the total solid in a film forming composition. When the content of the fluorine-containing antifouling agent in the composition for forming a film is in the above range, sufficient antifouling property can be imparted to the upper surface of the obtained silicon oxide matrix film, and unevenness occurs in the resulting film. The appearance such as is not impaired.

  The film-forming composition is applied to a predetermined region on the surface of the glass substrate to form a coating film, and the cured component contained in the coating film is cured to form a silicon oxide matrix film. Glass can be manufactured. The silicon oxide matrix film thus obtained is a film having antibacterial / antiviral properties as defined in (iii) above. Furthermore, the glass with a film obtained by using the film forming composition has the yellowing resistance defined in (ii) similar to the glass with a film of the present invention, and has other characteristics such as martens. With respect to hardness, solar transmittance, haze value, and the like, the same characteristics as those of the coated glass of the present invention can be obtained.

  Specifically, the glass with a coating comprises: (I) a step of coating a film-forming composition on the coating surface of the glass substrate to form a coating; and (II) an organic solvent as required from the resulting coating. Silane compounds (hereinafter referred to as “silane compounds”), such as the above-mentioned silicic acid compound (c ′), a fluorine-containing hydrolyzable silane compound as a fluorine-containing antifouling agent that is optionally added, And a step of curing the coating film by heating to a temperature for curing.

  First, in the step (I), the film forming composition is applied to the film forming surface of the glass substrate to form a film of the film forming composition. In addition, the coating film formed here is a coating film containing volatile components, such as the said organic solvent and water normally. The coating method of the film-forming composition on the glass substrate is not particularly limited as long as it is a uniform coating method. Flow coating method, dip coating method, spin coating method, spray coating method, flexographic printing method, screen Known methods such as a 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 of the coating solution is determined in consideration of the thickness of the finally obtained silicon oxide matrix film.

  Next, the step (II) to be performed is carried out by appropriately selecting conditions according to the silane compounds to be used. That is, in the step (II), if necessary, volatile components such as an organic solvent and water are removed from the coating film of the film-forming composition on the glass substrate, and the silane compounds are heated and cured to form a silicon oxide system. A matrix film is formed.

  In this case, it is preferable to remove the volatile component from the coating film in the step (II) by heating and / or drying under reduced pressure. After forming the coating film on the glass substrate, it is preferable to perform temporary drying at a temperature of about room temperature to 120 ° C. from the viewpoint of improving the leveling property of the coating film. Usually, during this temporary drying operation, volatile components are vaporized and removed in parallel with this operation, so it can be said that the operation of removing volatile components is included in the temporary drying.

  Moreover, when the film forming composition contains a fluorine-containing antifouling agent, the fluorine-containing antifouling agent in the film forming composition is considered to move to the vicinity of the surface of the coating film. The time for temporary drying, that is, the operation time for removing volatile components, is preferably about 3 seconds to 2 hours, although it depends on the film-forming composition used for forming the silicon oxide matrix film.

  At this time, it is preferable that the volatile component is sufficiently removed, but it may not be completely removed. That is, part of the volatile components can remain in the silicon oxide matrix film as long as the performance of the silicon oxide matrix film finally obtained is not affected. In addition, when heating is performed to remove the volatile components, heating for removing the volatile components, that is, generally temporary drying, and then curing of the silane compounds performed as follows. Heating may be carried out continuously.

  As described above, preferably, after removing the volatile component from the coating film, the cured component of the silane compound is cured by heating to obtain a silicon oxide matrix film. The heating temperature in this case can be fired at any temperature as long as it is in the temperature range from 80 ° C to 700 ° C, but the upper limit is preferably 230 ° C from the viewpoint of economy. In order to obtain the effect of promoting the reaction by heating, the lower limit of the heating temperature is preferably 80 ° C, and more preferably 150 ° C. Therefore, the heating temperature is preferably in the range of 80 to 230 ° C, more preferably in the range of 150 to 230 ° C. The heating time is preferably several minutes to several hours, although it depends on the composition of the film-forming composition used for forming the silicon oxide matrix film.

  The coated glass of the present invention has antibacterial and antiviral properties by containing silver, and is a coated glass in which the occurrence of yellowing due to the silver is suppressed, and has durability in antibacterial and antiviral properties. In addition, it has excellent mechanical durability such as wear resistance. The coated glass of the present invention can be applied to, for example, glass articles for windows, for example, window glass for vehicles such as automobiles and window glass for building materials attached to buildings such as houses and buildings. Furthermore, the present invention can be applied to display units of electronic devices such as various displays, mobile phones, portable music players, and personal computers.

  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 12 are examples, and examples 13 to 17 are comparative examples.

  Evaluation was performed by the following method using the glass with glass or glass plate (Example 15) obtained in each example as a test piece. In the test of antibacterial performance and antiviral performance, the test bacterial solution and the phage solution were dropped on the membrane except for Example 15. Example 15 was dropped on a glass plate. The following evaluation was performed at 25 ° C. unless otherwise specified.

[Antimicrobial performance]
The antibacterial effect was evaluated according to JIS Z 2801. Here, Escherichia coli and Staphylococcus aureus were used as test bacteria, respectively, and the amount of the test bacteria solution dropped onto each test piece was 100 μL. In JIS Z 2801, three unprocessed test pieces (for measuring the number of viable bacteria immediately after inoculation of the test bacteria), three unprocessed test pieces (for measuring the number of viable bacteria after 24 hours of culture), and three antibacterial processed test pieces. The place to be prepared was tested with one sheet each. In addition to the 24-hour (dark room) culture sample, a 1-hour (dark room) culture sample was prepared and tested in order to confirm the antibacterial immediate effect. The antibacterial activity value was determined by the following formula.
R = log (B / A) −log (C / A) = log (B / C)
R: antibacterial activity value A: viable cell count immediately after inoculation of unprocessed test piece B: viable cell count after 24 (1) hour culture of unprocessed test piece C: after 24 (1) hour culture of antibacterial processed test piece If the antibacterial activity value is 2 or more, it is determined that the antibacterial effect is obtained.

[Antiviral performance]
The antiviral effect was evaluated according to JIS Z 2801.
First, Escherichia coli Qβ was prepared as a test virus, and this was diluted to prepare a phage solution. Note that Escherichia coli phage Qβ is a general-purpose one as a substitute for influenza in antiviral evaluation.

  100 μL of the phage solution obtained above was dropped onto the test piece. Next, a transparent plastic sheet (a commercially available OHP sheet cut into 40 mm squares) was put on the test piece to which the phage solution was dropped. In this way, the phage solution was held between the test piece and the transparent plastic sheet.

  The test piece covered with the transparent plastic sheet was placed in a petri dish, the petri dish was covered, and left still in a dark room for 1 hour and 24 hours. After 1 hour or 24 hours, the test piece and the transparent plastic sheet were transferred to another container and washed with phosphate buffered saline. As a result, a diluted solution diluted 100 times based on the volume of the dropped phage solution was recovered.

The diluted solution obtained above was further diluted 10 ¹ to 10 ⁵ times with the above phosphate buffered saline to prepare a test solution. Next, a host solution containing a large excess of E. coli relative to the E. coli phage contained in this test solution was prepared. Next, 100 μL of the test solution and the host solution were mixed to obtain a mixed solution. The obtained liquid mixture was mixed with the upper layer agar medium, and it apply | coated to the lower layer agar medium previously fixed to the petri dish.

  Next, this petri dish was kept warm for 15 hours or more in a thermostat set at 37 ° C. After incubation, the number of plaques generated was counted visually from the bottom of the petri dish, and from the number of plaques and dilution factor, among the E. coli phages contained in the dropped phage solution, E. coli that did not lose its infectivity The concentration of was calculated. After the calculation, the antibacterial activity value was calculated in the same manner as the antibacterial test.

  All the instruments except the phage solution and the host solution were sterilized with an autoclave sterilizer and a UV sterilizer.

[Solar radiation transmittance (Te)]
Using a spectrophotometer (Hitachi, Ltd .: U-4100), the transmittance of the glass with a coating for light having a wavelength of 300 to 2100 nm was measured, and the solar transmittance (%) was calculated according to JIS-R3106 (1998).

[Abrasion test]
The film surface of the coated glass was worn 1000 times with a 1 kg load with felt, and the transmittance was measured with the above spectrophotometer to determine the average transmittance for light having a wavelength of 300 to 2100 nm. From the average transmittance before and after the test, the change (%) by the wear test was determined.

[Martens hardness]
A Vickers pyramid indenter was attached to a microhardness tester (Fischer Instruments, Inc .: Picodenter HM500), a load-unload test was performed on the coated glass film, and a load / penetration depth curve was measured. The measurement conditions are a load speed of 0.05 mN / 10 s, a creep of 5 s, and an unloading speed of 0.05 mN / 10 s. The measurement data was processed by WIN-HCU (manufactured by Fischer Instruments) to determine the Martens hardness (N / mm ² ).

[Haze value]
The haze value of the glass with a film was measured using a haze meter (manufactured by Big Gardner: Haze Guard Plus).

[Moisture resistance test]
A durability test was conducted on the moisture resistance of the coated glass in a high-temperature and high-humidity environment. That is, after the moisture resistance test held for 1000 hours in a high-temperature and high-humidity tank at 85 ° C. and 85% RH, the antibacterial property and yellowness YI of the glass with a film were measured.

YI is yellowness measured according to a spectrophotometer (manufactured by Hitachi, Ltd .: U-4100) and calculated according to JIS-K7373 (2006). For the evaluation, the yellowing degree ΔYI obtained by subtracting YI _(before) measured in the same manner before the moisture resistance test from YI _{(after) after the} moisture resistance test was used.

[Example 1]
(Preparation of desalted sodium silicate solution)
37.5 g of water and sodium silicate No. 4 (trade name: manufactured by Nippon Chemical Industry Co., Ltd. SiO ₂ : 23.35% by mass, Na ₂ O: 6.29% by mass. SiO ₂ / Na ₂ O molar ratio: 3. 83.) was added, and 30 g of a strongly acidic cation exchange resin (trade name “SK1BH”, manufactured by Mitsubishi Chemical Corporation) was added and stirred at room temperature for 10 minutes. The strong acid cation exchange resin was removed from the obtained desalted sodium silicate solution by filtration and used for the preparation of the following film-forming composition.

(Preparation of film-forming composition)
A film forming composition 1 was prepared by adding 0.078 g of silver nitrate and 20 g of sodium desalted silicate solution to 65 g of 2-propanol. The sodium ion concentration in the total solid content in the film-forming composition 1 was 0.48% by mass. The sodium ion concentration was measured and calculated by ICP-MS (Agilent 8800 manufactured by Agilent).

(Production of coated glass)
2 mL of the film-forming composition 1 obtained above was dropped on the surface of a glass plate (100 × 100 mm, 2.3 mm thick soda lime glass plate, FL2.3 (manufactured by Asahi Glass Co., Ltd.)), and spin coating was used. After the coating, it was baked for 10 minutes at 200 ° C. in an air atmosphere to obtain a glass with a coating 1 having a thickness of 50 nm. The film thickness was measured using a stylus type surface shape measuring instrument (Dektak 150 manufactured by ULVAC). In each of the following examples, the film thickness was measured in the same manner.

(Measurement of silver and sodium content eluted from the film)
The glass surface of the coated glass obtained above is masked with PTFE tape, the sample is put in a plastic bag with a chuck, and 10 mL of 0.1% by mass nitric acid aqueous solution is added, and sonication (28 kHz) is performed for 5 minutes. It was. After immersion, the liquid was collected and measured. Using ICP-MS (Agilent Agilent 8800), the amount of elution silver and the amount of elution sodium were measured and calculated. The results are shown in Table 1.

[Example 2]
Instead of silver nitrate aqueous solution, zeolite silver (trade name: Bacterite, product number: MP-102SVC13, manufactured by Fuji Chemical Co., Ltd.) is used, and the content of silver ions in the obtained film-forming composition is 4.76% by mass. A film-forming composition 2 was prepared in the same manner as in the film-forming composition 1 except that. The sodium ion concentration in the total solid content in the film-forming composition 2 was 0.76% by mass.

A film-coated glass 2 (film thickness: 50 nm) was obtained in the same manner as in Example 1 using the film-forming composition 2 instead of the film-forming composition 1.
[Example 3]
Glass with film 3 (film thickness: 50 nm) in the same manner as in Example 1 except that film forming composition 2 was used instead of film forming composition 1 and the firing conditions were changed to 300 ° C. in air for 10 minutes. )
[Example 4]
In Example 1, instead of the silver nitrate aqueous solution, silver phosphate-carrying silver (manufactured by Sangi Co., Ltd., trade name: Apacider, product number: AK) is used, and the content of silver ions in the obtained film-forming composition is 4.76% by mass. A film-forming composition 3 was prepared in the same manner as the film-forming composition 1 except that. The sodium ion concentration in the total solid content in the film-forming composition 3 was 0.60% by mass.
Using the film forming composition 3 instead of the film forming composition 1, a glass 4 with a film (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 5]
A film-forming composition 4 was obtained in the same manner as the film-forming composition 1 except that 0.19 g of copper sulfate was used together with silver nitrate. The sodium ion concentration in the total solid content in the film-forming composition 4 was 0.55% by mass.

  A film-coated glass 5 (film thickness: 50 nm) was obtained in the same manner as in Example 1 using the film-forming composition 4 instead of the film-forming composition 1.

[Example 6]
A film forming composition 5 was obtained in the same manner as the film forming composition 1 except that 0.0117 g of silver nitrate was used. The sodium ion concentration in the total solid content in the film-forming composition 5 was 0.4% by mass.

  Using the film-forming composition 5 instead of the film-forming composition 1, the film-coated glass 5 (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 7]
A film forming composition 6 was obtained in the same manner as the film forming composition 5 except that 0.19 g of copper sulfate was used together with silver nitrate. The sodium ion concentration in the total solid content in the film-forming composition 6 was 0.47% by mass.

  A glass 5 with a coating film (film thickness: 50 nm) was obtained in the same manner as in Example 1 except that the coating film-forming composition 6 was used instead of the coating film-forming composition 1.

[Example 8]
A film-forming composition 7 was obtained in the same manner as the film-forming composition 6 except that 0.077 g of copper (I) chloride was used together with silver nitrate. The sodium ion concentration in the total solid content in the film-forming composition 7 was 0.47% by mass.

  Using the film-forming composition 7 instead of the film-forming composition 1, the film-coated glass 7 (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 9]
In Example 5, using zeolite silver (trade name: Bacterite, product number: MP-102SVC13, manufactured by Fuji Chemical Co., Ltd.) instead of silver nitrate, the content of silver ions in the obtained film-forming composition was 0.94 mass. The film-forming composition 8 was obtained in the same manner as the film-forming composition 6 except that the content was%. The sodium ion concentration in the total solid content in the film-forming composition 8 was 0.75% by mass.

  Using the film forming composition 8 instead of the film forming composition 1, a glass with a film 9 (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 10]
In Example 1, a film-forming composition was the same as film-forming composition 1 except that 0.5 g of triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane was further added as fluorine-containing antifouling agent 1. Product 9 was obtained. The sodium ion concentration in the total solid content in the film-forming composition 9 was 0.57% by mass.

  Using the film-forming composition 9 instead of the film-forming composition 1, a glass 10 with a film (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 11]
In the same manner as in Example 1, an antibacterial / antiviral layer-attached glass (film thickness: 50 nm) was obtained using the film-forming composition 1. The liquid composition prepared as follows is applied to the surface of the antibacterial / antiviral layer of the obtained glass with antibacterial / antiviral layer, the fluorinated antifouling agent 2 is cured, and the outermost layer is fluorinated antifouling. A coated glass 11 having a layer (film thickness: 1 nm) was obtained.
CF ₃ CF ₂ — (OCF ₂ CF ₂ ) _{a ′} — (OCF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ ) _e — (OCF ₂ CF ₂ CF ₂ ) _d —CONHC ₃ H _A liquid composition was prepared by dissolving 0.1 g of ₆ Si (OCH ₃ ) ₃ (where a ′ = 1, e = 13, d = 1) in 2 mL of methanol.

[Example 12]
Glass with a coating film was prepared in the same manner as in Example 2, except that the firing conditions after coating the film-forming composition 2 on the glass plate was changed from 200 ° C. and 10 minutes to 600 ° C. and 10 minutes. 12 (film thickness: 50 nm) was obtained.

[Example 13]
In Example 1, a film-forming composition was prepared using a solution prepared by hydrolyzing tetraethoxysilane (TEOS) instead of the desalted sodium silicate solution. First, 69 g of tetraethoxysilane, 80 g of ethyl alcohol, and 50 g of 0.1N nitric acid aqueous solution were added and stirred for 3 hours. A film-forming composition 10 was obtained in the same manner as the film-forming composition 1 except that the prepared tetraethoxysilane hydrolyzed aqueous solution was used. The sodium ion concentration in the total solid content in the film-forming composition 10 was below the detection limit.

  Using the film-forming composition 10 instead of the film-forming composition 1, a film-coated glass 13 (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 14]
A film forming composition 12 was obtained in the same manner as the film forming composition 1 except that 0.00008 g of silver nitrate was used. The sodium ion concentration in the total solid content in the film-forming composition 12 was 0.41% by mass.
Using the film-forming composition 12 instead of the film-forming composition 1, a glass 14 with a film (film thickness: 50 nm) was obtained in the same manner as in Example 1.

[Example 15]
A soda-lime glass plate (100 × 100 mm, 2.3 mm thickness, FL2.3 (manufactured by Asahi Glass)) used as a glass substrate in each example was prepared.

[Example 16]
On a soda lime glass plate (100 × 100 mm, 3.1 mm thickness, FL3 (Asahi Glass Co., Ltd.)), a titanium oxide film having photocatalytic performance by CVD (conditions: raw material: titanium tetraisopropoxide, baking temperature: 500 ° C.) It formed and obtained glass 16 with a film (film thickness; 125 nm).

[Example 17]
On a soda lime glass plate (100 × 100 mm, 5.0 mm thickness, FL5 (Asahi Glass Co., Ltd.)), it has visible light response photocatalytic performance by sputtering (conditions: pressure 0.7 Pa before gas supply, oxygen gas 5%). A film made of a copper compound and titanium oxide was formed to obtain glass 17 with a coating film (film thickness: 26 nm).

  Moisture resistance tests were performed on the coated glasses 1 to 5 and 11 to 14 obtained in Examples 1 to 5 and Examples 11 to 14, and antimicrobial durability and ΔYI were evaluated. Further, the transmittance Te [%], haze value, and abrasion resistance were evaluated. The results are shown in Tables 1 to 3 together with the composition of the film-forming composition.

  Antibacterial and antiviral tests were carried out at 25 ° C. in the dark on the glass plates 6-10, 16, 17 and 15 of Example 6-10, Examples 16 and 17 and coated glass. The results are shown in Tables 1 to 3 together with the composition of the film-forming composition.

  In Table 2, “presence (integrated)” of the fluorine-containing antifouling layer refers to a case where an antibacterial / antiviral film having a fluorine-containing antifouling layer is formed by forming a film with the film forming composition. “Present (external coating)” refers to the case where a fluorine-containing antifouling layer is formed on a liquid composition for forming a fluorine-containing antifouling layer on the antibacterial / antiviral layer formed by the film-forming composition. . The film thickness * in Example 11 means that the film thickness is only the antibacterial / antiviral layer.

Claims (15)

A glass with a glass substrate and a film having a film formed on the surface of the glass substrate,
The coating comprises silicon oxide as a matrix, contains silver ions, and contains at least one alkali metal ion selected from sodium, potassium, and lithium,
The glass with coating is the humidity resistance test for yellowness YI measured and calculated according to JIS-K7373 (2006) before and after the humidity resistance test held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 1000 hours. ΔYI obtained by subtracting the value before the moisture resistance test from the later value is 1.8 or less,
JIS Z 2801 (2010) was applied mutatis mutandis using Escherichia coli, Staphylococcus aureus, or influenza virus surrogate phage on the surface of the coating, and 1 hour after the start of the antibacterial test in the antibacterial test performed in the dark at 25 ° C. Glass with a coating having an antibacterial activity value of 2.0 or more. The coated glass has a surface elution ion amount determined by the following measurement method.
For silver ion is ^{0.3ng / cm 2 ~1000ng / cm 2} ,
Lithium ion, for sodium ions and potassium ions, a coated glass according to claim 1 Total is 0.3ng ^/ cm ² ~200ng ^/ cm 2 at.
(Measurement method of surface elution ion quantity)
The glass substrate portion of the glass with coating is masked with a tape made of polytetrafluoroethylene, immersed in 10 mL of a 0.1% by mass nitric acid aqueous solution, subjected to ultrasonic treatment for 5 minutes at 28 kHz, and the amount of ions eluted is ICP- Measure with MS and normalize with membrane area. The glass with a coating according to claim ² , wherein the coating further contains copper ions, and a surface elution ion amount obtained by the measurement method is 0.3 ng / cm ^{2 to} 1000 ng / cm ² for copper ions. 4. The Martens hardness measured on the surface of the coating is 0.05 mN / 10 s, creep is 5 s, unloading speed F is 0.05 mN / 10 s, and the Martens hardness is 1600 N / mm ² or more. Glass with a coating according to claim 1.   The glass with a coating according to any one of claims 1 to 4, wherein the coating contains particles having a cation adsorption ability.   The coated glass according to claim 5, wherein the constituent material of the particles having cation adsorption ability is at least one selected from the group consisting of zeolite, smectite, and a calcium phosphate compound.   The glass with a coating according to any one of claims 1 to 6, wherein the coating has a fluorine-containing antifouling layer as an outermost layer.   JIS Z 2801 (2010) was applied mutatis mutandis using Escherichia coli, Staphylococcus aureus, or influenza virus surrogate phage on the surface of the coating, and 1 hour after the start of the antibacterial test in the antibacterial test performed in the dark at 25 ° C. Antibacterial activity value is 2.0 or more about any said microbe, The glass with a film as described in any one of Claims 1-7. A silicon oxide raw material component that forms a matrix of silicon oxide;
At least one alkali metal ion selected from sodium, potassium, and lithium is 0.01% by mass to 1% by mass with respect to the total solid content, and silver ion is 0.01% by mass to 30% with respect to the total solid content. mass%,
A composition for forming a film.   The composition for film formation according to claim 9, further comprising copper ions, wherein the content of the copper ions is 0.01% by mass to 30% by mass with respect to the total solid content.   The film forming composition according to claim 9 or 10, further comprising particles having a cation adsorption ability.   The composition for forming a film according to claim 11, wherein the constituent material of the particles having cation adsorption ability is at least one selected from zeolite, smectite, and a calcium phosphate compound.   The composition for film formation as described in any one of Claims 9-12 which further contains a fluorine-containing antifouling agent. The film forming composition according to claim 13, wherein the fluorine-containing antifouling agent comprises a compound represented by the following formula (1A) and / or a compound represented by the following formula (1B).
A ¹ -Q ¹ -SiX ¹ _m R ¹ _3-m (1A)
A ¹ -Q ^1- {CH ₂ CH (SiX ¹ _m R ¹ _3-m )} _n -H (1B)
Symbols in Formula (1A) and Formula (1B) are as follows.
A ¹ is a group represented by the following formula (A).

(In Formula (A), R ^F1 represents a perfluoroalkyl group. A, b, c, d, and e each independently represent 0 or an integer of 1 or more, and a + b + c + d + e is at least 1 or more. , A, b, c, d, e, the order of existence of each repeating unit is not limited in the formula.)
Q ¹ : amide bond, urethane bond, ether bond selected from —C (═O) NH—, —C (═O) N (CH ₃ ) —, —C (═O) N (C ₆ H ₅ ) — , an ester bond, -CF 2 _- shows a consisting of repeating units divalent organic group having 2 to 12 carbon atoms _- may contain one or two elements selected from group and phenylene group, -CH 2 (However, one of the hydrogen atoms in the —CH ₂ — group may be substituted with an —OH group.)
X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m X ^{1 s} may be the same as or different from each other.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms in which part or all of the hydrogen atoms may be substituted. 3-m R < ¹ > may mutually be same or different.   The film formed using the film-forming composition is applied to JIS Z 2801 (2010) using Escherichia coli, Staphylococcus aureus, or influenza virus substitute phage on the surface of the film, in the dark at 25 ° C. The composition for film formation as described in any one of Claims 9-14 whose antibacterial activity value 1 hour after the said antibacterial test start in the antibacterial test performed in is 2.0 or more.