WO2016204003A1

WO2016204003A1 - Glass article and method for producing same

Info

Publication number: WO2016204003A1
Application number: PCT/JP2016/066677
Authority: WO
Inventors: 雄一 ▲桑▼原; 平社　英之; 剛介吉田; 朋広山田; 秀文小▲高▼; 信孝青峰; 崇平見矢木; 鈴木　賢一; 修二種田; 阿部　啓介
Original assignee: 旭硝子株式会社
Priority date: 2015-06-18
Filing date: 2016-06-03
Publication date: 2016-12-22

Abstract

Provided is a glass article with an antireflection film having improved durability that obtains excellent antifouling performance by a simple structure. The glass article 1 is provided with a glass substrate 2, a laminated film 3 disposed on the glass substrate 2, and an antifouling film 4 disposed on the outermost layer of the laminated film 3, and the glass article 1 has an antireflection function. The antifouling film 4 contains particle aggregates and a binder.

Description

Glass article and method for producing the same

The present invention relates to a glass article and a manufacturing method thereof, and more particularly to a glass article having antireflection performance and a manufacturing method thereof.

Various glass articles in which a functional film such as an antireflection film is provided on a glass substrate are known. For example, in a form in which a glass article is used for construction, it may be used such that the surface provided with a functional film is on the outdoor side. Since the glass article with an antireflection film has high permeability, it is expected to be applied to outdoor buildings such as a facade of a building, a store, and a courtyard. As the glass with an antireflection film, for example, a structure in which a laminated film having a TiO ₂ layer, an Al-doped SiO ₂ layer, a TiO ₂ layer, and an Al-doped SiO ₂ layer in this order on a glass substrate is known, The reflectance of the glass substrate is suppressed by the laminated film (see Patent Document 1).

As a glass article having antireflection properties and antifogging properties, for example, the uppermost layer of a single-layer or multilayer antireflection film is formed of an inorganic material film having at least one of pores and fine irregularities, and an inorganic material film. Articles composed of an antifogging film made of a hydrophilic substance fixed to pores and fine irregularities (see Patent Document 2), and an antireflection film in which a high refractive index layer and a low refractive index layer are laminated An article (see Patent Document 3) in which a low refractive index layer is formed of an antifogging film made of a polymer layer obtained by curing a composition containing a hydrophilic polymer is known.

International Publication No. 2005/030663 JP-A-9-127302 JP 2012-203150 A

However, it is difficult to say that conventional glass articles with an antireflection film have good antifouling properties of the laminated film. For this reason, when a conventional glass article is applied to an outdoor building or the like, dirt such as sand adheres to the antireflection film on the surface of the glass article, so that the antireflection performance is lowered or the translucency of the glass article is reduced. There is a problem of deterioration.

In the antireflection film described in Patent Document 3, a polymer layer obtained by curing a composition containing a hydrophilic polymer is provided as the uppermost layer. Since the surface of the polymer layer (the outermost surface of the antireflection film) is flat, hydrophilicity is likely to be lost due to organic contamination, and this tends to reduce the antifogging performance. Therefore, the antifogging film made of the polymer layer has a problem in durability.

An object of the present invention is to provide a glass article with an antireflection film that has excellent antifouling performance with a simple structure and has improved durability, and a production method that can easily produce such a glass article. And

According to a first aspect of the present invention, there is provided a glass substrate, a laminated film that is disposed on the glass substrate and includes a plurality of layers having different refractive indexes, an agglomerate of particles that is disposed on the outermost layer of the laminated film, A glass article having an antireflection function, comprising an antifouling film containing a binder.

The second aspect of the present invention includes a step of forming a laminated film including a plurality of layers having different refractive indexes on a glass substrate, and an aggregate of particles and a binder precursor on the outermost layer of the laminated film. Applying the antifouling film-forming composition to obtain a coating film of the antifouling film-forming composition, and applying the treatment for curing the binder precursor to the coating film to form the binder from the binder precursor. By this, it is the manufacturing method of the glass article which comprises the process of forming the antifouling film containing the aggregate of the said particle | grains and the said binder.

It is sectional drawing which shows the structure of the glass article of one Embodiment of this invention. It is sectional drawing which expands and shows the antifouling film | membrane of the glass article shown in FIG. It is sectional drawing which shows one structural example of the glass with an antireflection film in this invention. It is sectional drawing which shows the other structural example of the glass with an antireflection film in this invention. It is a flowchart which shows schematically the manufacturing method of the glass with an antireflection film by one Example of this invention.

Hereinafter, embodiments of the present invention will be described. In the following description, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The term “process” is included in this term as long as the initial purpose of the process is achieved, even when the process is not clearly distinguishable from other processes.

[Glass articles]
The glass article of the present invention includes a glass substrate, a laminated film that is disposed on the glass substrate and includes a plurality of layers having different refractive indexes, an agglomerate of particles and a binder that are disposed on the outermost layer of the laminated film. A glass article having an antireflection function, comprising an antifouling film containing. Since the glass article of the present invention has antireflection performance and antifouling performance, it is applied to lenses such as glasses and cameras, window glass, car windshields, helmet shields, underwater glasses, bathroom mirrors, and the like. However, it is not limited to these.

The glass article of the present invention comprises a glass substrate and a difference in visible light reflectance before and after the test which was provided on the glass substrate and immersed in an aqueous NaOH solution having a concentration of 0.1 kmol / m ³ heated to 90 ° C. for 2 hours. A laminated film having a protective layer having a thickness of 0.4 or less, and two types of JIS test powder 1 (silica sand having a median diameter of 27 to 31 μm) provided on the laminated film and left to stand for 10 seconds. Then, tilting 135 °, touching the ground twice at a speed of 10 cm / second from a height of 3 cm, dropping the powder and measuring the haze value a plurality of times, and calculating the haze value before the test from the average value It is preferable to provide an antifouling film having a subtracted value of 1.0 or less.

The glass article of the present invention has antifouling properties against various stains. As dirt, inorganic dirt such as dust in the atmosphere, remaining alkali content from concrete walls (water dry spots), water stains, burns on the glass itself, atmospheric soot and automobile exhaust gas, Examples include organic stains such as cigarette smoke and oil. The glass article of the present invention has a better antifouling effect against dust and oil stains. The antifouling property of the antifouling article can be evaluated by, for example, a change in haze value measured by a “dirt adhesion test” in Examples described later. The change in haze value of the antifouling article is preferably 5% or less, more preferably 2% or less, and particularly preferably 1% or less, when measured by a “dirt adhesion test” in Examples described later. If the change in haze value exceeds 5%, there is a possibility that practical antifouling properties cannot be expressed. The haze value can be measured using a commercially available haze measuring device.

FIG. 1 shows an example of the glass article of the present invention. Hereinafter, taking the glass article 1 shown in FIG. 1 as an example, each configuration of the glass article of the present invention will be described in detail. A glass article 1 shown in FIG. 1 is disposed on a glass substrate 2, a laminated film 3 provided on the glass substrate 2 for imparting antireflection properties, and an outermost layer (34) of the laminated film 3. The antifouling film 4 is provided. As shown in FIG. 2, the antifouling film 4 contains aggregates 6 of particles 5 and a binder 7, and has an uneven surface based on the aggregates 6 of particles 5.

(Glass substrate)
The glass substrate 2 has a function of maintaining the structure among the components of the glass article 1. The glass substrate 2 is a substrate having a haze value of 1% or less, and the thickness can be appropriately selected depending on the application. The glass substrate 2 is preferably colorless, but can be appropriately colored depending on the application.

The composition of the glass is not particularly limited. The glass substrate 2 may be, for example, alkali-free glass, soda lime glass, aluminosilicate glass, or the like. The glass may be physically strengthened or chemically strengthened. If it is chemically strengthened glass, the plate thickness of the glass can be 1.5 mm or less. For example, in the case of soda lime glass, the composition of the glass substrate 2 is expressed in terms of mass percentage on the basis of oxide, SiO ₂ is 60 to 75%, Al ₂ O ₃ is 2 to 12%, MgO is 2 to 11%, CaO 0-10%, SrO 0-3%, BaO 0-3%, Na ₂ O 10-18%, K ₂ O 0-8%, ZrO ₂ 0-4% (The total of the above components is 100% or less, and usually 95% or more). In the case of an aluminosilicate glass, SiO ₂ is 61 to 70%, Al ₂ O ₃ is 1 to 18%, MgO is 0 to 15%, CaO is 0 to 5%, and SrO is expressed in terms of mole percentage based on oxide. 0-1%, BaO 0-1%, Na ₂ O 8-18%, K ₂ O 0-6%, ZrO ₂ 0-4%, B ₂ O ₃ 0-8% May be.

(Laminated film)
The laminated film 3 in the glass article 1 includes a first layer 31, a second layer 32, a third layer 33, and a fourth layer 34 in order from the glass substrate 2 side. By appropriately designing the number of layers constituting the laminated film 3, the material of each layer, the order of arrangement, and the like, the glass article 1 can exhibit antireflection properties.

The first layer 31 and the third layer 33 can have a refractive index smaller than that of the second layer 32 and the fourth layer 34. In this case, the first layer 31 and the third layer 33 are referred to as “low refractive index layers”, and the second layer 32 and the fourth layer 34 are referred to as “high refractive index layers”. The refractive index of the first layer 31 and the third layer 33 is preferably 1.4 to 1.8, and more preferably 1.45 to 1.7. Examples of the material constituting the low refractive index layer include silicon oxide and aluminum oxide. Silicon oxide may be doped with other elements such as aluminum. The thickness of the first layer 31 is preferably 30 to 60 nm or 174 to 224 nm, and more preferably 35 to 55 nm or 189 to 209 nm. The thickness of the third layer 33 is preferably 20 to 80 nm, and more preferably 30 to 70 nm.

The refractive index of the second layer 32 and the fourth layer 34 is preferably 2.0 or more, and more preferably 2.1 or more. Examples of the material constituting the high refractive index layer include titanium oxide, niobium oxide, zirconium oxide, cerium oxide, and tantalum oxide. The thickness of the second layer 32 is preferably 1 to 52 nm, and more preferably 3 to 45 nm. The thickness of the fourth layer 34 is preferably 1 to 39 nm, and more preferably 6 to 34 nm. The fourth layer 34 may be made of the same material as that of the second layer 32 and may have the same refractive index.

The laminated film 3 may have a fifth layer, a sixth layer,... An nth layer (n is an integer of 5 or more) in addition to the first to fourth layers 31 to 34. . In this case, if the high refractive index layer and the low refractive index layer are alternately laminated and the outermost layer is the high refractive index layer, the first layer 31 does not necessarily need to be a low refractive index layer, and the high refractive index layer It may be a rate layer.

The outermost layer in the laminated film 3 is preferably composed of silica doped with zirconia. A silica layer doped with zirconia (hereinafter also referred to as “ZrO ₂ -doped SiO ₂ layer”) exhibits good resistance to alkali. When the outermost layer is a ZrO ₂ -doped SiO ₂ layer, the outermost layer of the laminated film 3 functions as a protective film against alkali. For this reason, even if the laminated film 3 comes into contact with moisture containing an alkali component, it is possible to significantly suppress the deterioration of the laminated film 3. Thereby, it is possible to provide a glass with an antireflection film that has significantly higher resistance to alkali than in the past.

According to the present inventors, it has been found that in a laminated film in which a silica layer is disposed immediately below a ZrO ₂ -doped SiO ₂ layer, resistance to alkali is likely to be reduced. Therefore, immediately below the ZrO ₂ doped SiO ₂ layer, the silica layer is not arranged, that is, immediately below the ZrO ₂ doped SiO ₂ layer, it is preferable that a layer containing no silica is disposed.

In the present specification, the term “outermost layer” means a layer arranged on the outermost side in the laminated film 3. Therefore, the “outermost layer” is not necessarily the outermost layer in the glass article 1 with an antireflection film. In the glass article 1 shown in FIG. 1, the antifouling film 4 is the outermost layer.

Next, with reference to FIG. 3, a configuration example of the laminated film having excellent alkali resistance according to the present invention will be described. A glass 100 with an antireflection film shown in FIG. 3 includes a glass substrate 120 and a laminated film 130. The glass substrate 120 has a first surface 122 and a second surface 124, and the laminated film 130 is disposed on the first surface 122 side of the glass substrate 120.

In the example shown in FIG. 3, the laminated film 130 includes three layers, that is, a first layer 140, a second layer 145, and an outermost layer 160. The first layer 140 has a higher refractive index than the second layer 145. For example, the first layer 140 has a refractive index of 2.0 or more, and the second layer 145 has a refractive index in the range of 1.4 to 1.8. The second layer is composed of a layer other than silica. By using the two

layers

140 and 145 having different refractive indexes for the laminated film 130, the glass 100 with the antireflection film can exhibit low reflection characteristics.

The outermost layer 160 is made of silica doped with zirconia, that is, a ZrO ₂ -doped SiO ₂ layer. Since the glass 100 with an antireflection film having such a configuration has a ZrO ₂ -doped SiO ₂ layer in the outermost layer 160, it can exhibit significantly improved alkali resistance characteristics as compared with the conventional glass with an antireflection film. Can do. Moreover, in the glass 100 with an antireflection film, it is preferable that a silica layer is not disposed immediately below the outermost layer 160, that is, the ZrO ₂ -doped SiO ₂ layer. In that case, it can suppress significantly that the tolerance with respect to the alkali of the glass 100 with an antireflection film falls with time.

Next, each constituent member will be further described by taking the glass 200 with an antireflection film shown in FIG. 4 as an example. Therefore, the reference numerals shown in FIG. 4 are used to represent each member. However, it will be apparent to those skilled in the art that the following description can be similarly applied to the glass article 1 shown in FIG. 1, the glass 100 with an antireflection film shown in FIG.

(Laminated film 230)
The laminated film 230 includes a first layer 240, a second layer 245, a third layer 250, a fourth layer 255,... In this order from the glass substrate 220 side. The laminated film 230 preferably has an outermost layer 260 at the top, that is, a ZrO ₂ -doped SiO ₂ layer.

The first layer 240 has a higher refractive index than the second layer 245. For this reason, the first layer 240 is referred to as a “high refractive index layer” 240, the second layer 245 is referred to as a “low refractive index layer” 245, and both are referred to as a “different refractive index layer set”.

In this case, in the example of FIG. 3, the number of different refractive index layer sets in the laminated film 130 is 1 (total of three layers), and in the example of FIG. 4, the number of different refractive index layer sets in the laminated film 230. Becomes 2 (5 layers in total). The number of different refractive index layer sets may be 3 or more (a total of 7 or more layers).

The portion immediately below the outermost layer 260 is not necessarily a low refractive index layer (145, 255), and the portion immediately below the outermost layer 260 may be a high refractive index layer (for example, the third layer 250). For example, when the third layer 250 (high refractive index layer) is directly below the outermost layer 260, the number of different refractive index layer sets can be expressed as 1.5. According to such a notation, the number of different refractive index layer sets in the laminated film 230 may be 2.5, 3.5, 4.5...

(First layer 240)
The first layer 240 has a higher refractive index than the second layer 245 disposed immediately above. For example, the first layer 240 may have a refractive index of 2.0 or more. The refractive index of the first layer 240 may be 2.1 or more, for example. The material constituting such a “high refractive index layer” 240 is not limited to this, and examples thereof include titania, niobium oxide, zirconia, ceria, and tantalum oxide. The thickness of the first layer 240 is, for example, in the range of 5 to 20 nm, and preferably in the range of 7 to 17 nm.

(Second layer 245)
The second layer 245 has a smaller refractive index than the first layer 240 disposed immediately below. When the number of different refractive index layer sets is 1.5 or more, the second layer 245 has a smaller refractive index than the third layer 250 disposed immediately above. The second layer 245 may have a refractive index in the range of 1.4 to 1.8, for example. The refractive index of the second layer 245 may be, for example, in the range of 1.45 to 1.7.

The material constituting such a “low refractive index layer” 245 is not limited to this, and examples thereof include silica and alumina. Silica may be doped with other elements such as aluminum. However, when the number of different refractive index layer sets is 1.0, the second layer 245 is preferably a layer other than silica. The thickness of the second layer 245 is, for example, in the range of 15 to 45 nm, and preferably in the range of 20 to 40 nm.

(Third layer 250)
In the laminated film 230, when the number of different refractive index layer sets is 1.5 or more, the third layer 250 is present. The third layer 250 has a higher refractive index than the second layer 245 disposed immediately below. When the number of different refractive index layer sets is 2.0 or more, the third layer 250 has a refractive index larger than that of the fourth layer 255 disposed immediately above.

The third layer 250 may have a refractive index of 2.0 or more, for example. The refractive index of the third layer 250 may be 2.1 or more, for example. The thickness of the third layer 250 is, for example, in the range of 45 to 125 nm, and preferably in the range of 50 to 115 nm. The third layer 250 may be made of the same material as the first layer 240 and may have the same refractive index.

(Fourth layer 255)
In the laminated film 230, when the number of different refractive index layer sets is 2.0 or more, the fourth layer 255 is present. The fourth layer 255 has a smaller refractive index than the third layer 250 disposed immediately below. When the number of different refractive index layer sets is 2.5 or more, the fourth layer 255 has a refractive index smaller than that of the fifth layer disposed immediately above.

The fourth layer 255 may have a refractive index in the range of 1.4 to 1.8, for example. The refractive index of the fourth layer 255 may be, for example, in the range of 1.45 to 1.7. The material constituting the “low refractive index layer” 255 is not limited to this, and examples thereof include silica and alumina. Silica may be doped with other elements such as aluminum. The thickness of the fourth layer 255 is, for example, in the range of 0 to 110 nm, and preferably in the range of 0 to 100 nm. The fourth layer 255 may be made of the same material as the second layer 245 and may have the same refractive index. However, when the number of different refractive index layer sets is 2.0, the fourth layer 255 is preferably a layer other than silica.

(5th and subsequent layers)
If present, the fifth layer, the sixth layer,..., And the nth layer (n is an integer of 5 or more) may form a mutually different refractive index layer set with an adjacent layer. For example, the fifth layer has a higher refractive index than the fourth layer and the sixth layer. The sixth layer has a smaller refractive index than the fifth layer and the seventh layer. The same applies hereinafter. For the specifications of these layers, the description in the above-mentioned column of (first layer 240) and (second layer 245) can be referred to.

(Outermost layer 260)
The outermost layer 260 is preferably composed of a ZrO ₂ -doped SiO ₂ layer. The thickness of the outermost layer 260 is not particularly limited, but is in the range of 5 to 110 nm, for example, and may be in the range of 10 to 100 nm, for example.

The amount of zirconia doped in the silica film doped with zirconia is not particularly limited, but for example, it is preferably in the range of 5 to 50 mol% in terms of mol% based on oxide. When the doping amount of zirconia is 5 mol% or more, the alkali resistance property in the laminated film 230 is improved. The lower limit of the zirconia doping amount is preferably, for example, 6 mol%, more preferably 7 mol%, further preferably 8 mol%, particularly preferably 9 mol%. When the doping amount of zirconia is 50 mol% or less, resistance to acid is improved. The doping amount of zirconia is more preferably in the range of 10 to 33 mol%.

When the doping amount of zirconia is 5 mol%, the refractive index of the outermost layer 260 is about 1.50. When the doping amount of zirconia is 10 mol%, the refractive index of the outermost layer 260 is about 1.54. When the doping amount of zirconia is 33 mol%, the refractive index of the outermost layer 260 is about 1.69. When the doping amount of zirconia is 50 mol%, the refractive index of the outermost layer 260 is about 1.79.

Each layer constituting the laminated film 230 may be installed by any method. Each layer may be formed by, for example, an evaporation method, a sputtering method, a CVD (chemical vapor deposition) method, or the like.

(Anti-fouling film)
In the glass article 1 shown in FIG. 1, the antifouling film 4 is disposed on the outermost layer 34 of the laminated film 3 and contains an aggregate 6 of particles 5 and a binder 7. The antifouling film 4 may contain not only the aggregate 6 but also particles (non-aggregated particles) 5 that exist alone. Based on the shape of the aggregate 6 of the particles 5 in the antifouling film 4, the amount of the particles 5 in the antifouling film 4 (volume ratio of the particles 5 to the binder 7), particularly the amount of the aggregates 6 of the particles 5, etc. By making the surface of the dirty film 4 an uneven surface, the antifouling performance can be enhanced.

It is preferable that the particles 5 are hydrophilic particles and the binder 7 is a hydrophilic binder because the antifouling film 4 can function as an antifogging film. In that case, since the moisture adhering to the glass article 1 spreads on the uneven surface of the antifouling film (antifogging film) 4, it is possible to suppress the occurrence of fogging due to the formation of water droplets due to condensation of moisture. Furthermore, the uneven surface suppresses a decrease in hydrophilicity due to organic contamination or the like. Therefore, the antifogging durability of the antifouling film 4 is improved, and the antifogging performance can be maintained for a long time.

The uneven surface of the antifouling film 4 includes a plurality of protrusions (protrusion regions) including aggregates 6 and binders 7 of particles 5 and other regions (for example, non-aggregated particles 5 and binders 7). It is preferable to have a convex portion or a region having only the hydrophilic binder 7). In that case, since the plurality of protrusions are aggregates of the aggregates 6 and the binders 7 of the particles 5 that are non-uniformly present on the surface of the outermost layer 34 of the laminated film 3, unevenness formed by the particles 5 alone. Compared to the above, more appropriate unevenness is formed. Therefore, the antifouling performance and antifogging performance of the glass article 1 can be further improved.

The antifouling film 4 in the glass article 1 is sprinkled with two types of JIS test powder 1 (silica sand having a median diameter of 27 to 31 μm), left to stand for 10 seconds, tilted 135 °, and from a height of 3 cm to 10 cm / It is preferable that the value of subtracting the haze value before the test from the average value is within 1.0, by repeating a plurality of times of measuring the haze value by dropping the powder by touching the ground twice with the momentum of seconds.

The antifouling film 4 has a plurality of protrusions including aggregates 6 of particles 5 and a binder 7 on the surface, and 90% or more based on the protrusions having the maximum height from the substrate surface in the protrusions. The ratio of the total covered area by the particles 5 to the area of the substrate on which the average distance between the vertices of adjacent protrusions T is 100 to 1000 nm and the antifouling film 4 is disposed. Is preferably 12 to 100%.

Since the above-described protrusion is an aggregate of the aggregate 6 and the binder 7 that exists non-uniformly on the surface of the substrate, more appropriate unevenness is formed compared to the unevenness formed by the particles alone, and the There is a tendency for soiling to improve more. Since the dirt adhering to the glass article 1 first comes into contact with the convex portions present on the surface of the antifouling film 4, the dirt comes into contact with the protrusions in the glass article 1. Therefore, in the antifouling film 4, the area in contact with dirt can be further reduced, and the antifouling film 4 having better antifouling properties can be obtained. On the other hand, when the distance between vertices described later is 100 nm or more, adsorption due to capillary action can be suppressed even when the dirt is oil dirt. As a result, oil stains are difficult to adhere, and even if they adhere, they can be easily removed by washing with water.

The shape of the protrusion is not particularly limited, and examples thereof include a substantially quadrangular pyramid, a substantially triangular pyramid, and a substantially cone. When a region from the top of the protrusion to the height of 50% is approximated to a partial spherical surface, the radius of curvature of the partial spherical surface is not particularly limited, but is preferably 5 nm or more, and more preferably 5 to 15 nm. The height of the protrusion is not particularly limited, but is preferably 10 nm or more, and more preferably 30 to 200 nm. The height of the protrusion is the height from the base surface to the apex of the protrusion, and can be measured using a scanning electron microscope.

The size of the bottom surface of the protrusion is not particularly limited, but is preferably 10 to 700 nm, and more preferably 30 to 200 nm. The average value of the angle between the bottom surface (surface parallel to the substrate) and the side surface of the protrusion is not particularly limited, but is preferably 10 to 90 °, more preferably 20 to 70 °. If the angle between the bottom surface and the side surface of the protrusion is 10 ° or more, a steeper protrusion is obtained. Here, the size of the bottom surface of the protrusion is defined as the diameter of a circle in which the bottom shape of the protrusion is inscribed. The bottom size of the protrusion can be measured using a scanning electron microscope.

Among the protrusions present on the surface of the antifouling film 4, the distance between the apexes of the adjacent protrusions T in the protrusion T having a height of 90% or more with reference to the protrusion having the maximum height from the base surface. Is preferably 100 to 1000 nm, more preferably 100 to 800 nm, and even more preferably 100 to 500 nm. That the distance between the vertices is 100 to 1000 nm means that the unevenness formed by the protrusions T on the surface of the antifouling film 4 is large. Moreover, since the protrusion T includes two or more particles 5 and the binder 7, a large convex structure is formed as compared with the surface irregularity of the antifouling film formed by the convex part including the single particle and the binder. Means. Accordingly, the antifouling film 4 having better antifouling properties can be obtained. Further, the antifouling film 4 is hardly soiled with oil, and even if it adheres, it can be easily removed by washing with water.

The distance between vertices can be measured with a scanning electron microscope. Specifically, the distance between the vertices is the maximum height among the protrusions existing in a predetermined region in a direction parallel to the surface of the glass substrate 2 having the antifouling film 4 from the cross-sectional photograph of the glass article 1. Select the protrusions having 90% or more of the protrusions, select the protrusions T having a height of 90% or more, measure the distance between the vertices of the adjacent protrusions T (vertex interval), and calculate the average value. Can be obtained.

The ratio of the total covered area by the particles 5 to the area of the glass substrate 2 on which the antifouling film 4 is disposed (hereinafter also referred to as “convex portion coverage”) is preferably 12 to 100%. When the convex portion coverage is 12% or more, the presence ratio of the aggregates 6 of the particles 5 that can come into contact with dirt in the antifouling film 4 and the protrusions including the binder 7 is increased, so that sufficient antifouling properties can be obtained. . The convex portion coverage is more preferably 15 to 100%, further preferably 20 to 100%, and particularly preferably 50 to 100%. The convex portion coverage can be measured with a scanning electron microscope. Specifically, it can be measured by a measuring method of “convex portion coverage” which will be described later in Examples.

The arithmetic average roughness (hereinafter also referred to as “Ra”) of the antifouling film 4 is not particularly limited, but is preferably 5 to 30 nm, more preferably 6 to 25 nm, and even more preferably 7 to 20 nm. When Ra is 5 nm or more, contact between the portion having a smaller film thickness than the apex of the convex portion including single particles and a binder and dirt is suppressed, and more excellent antifouling property is obtained. When Ra is 30 nm or less, the wear resistance is excellent. Ra can be measured with a scanning probe microscope.

The thickness of the antifouling film 4 is not particularly limited, but is preferably 20 to 350 nm, more preferably 30 to 300 nm, and particularly preferably 50 to 300 nm. If the film thickness of the antifouling film 4 is 20 nm or more, the antifouling property tends to be sufficiently exhibited. When the film thickness of the antifouling film 4 is 350 nm or less, the mechanical strength is excellent and the economy is excellent. The film thickness of the antifouling film 4 can be determined by observing with a scanning electron microscope.

The ratio of the particles 5 to the binder 7 in the antifouling film 4 is preferably set so that the volume ratio of the particles 5 to the binder 7 is 7/93 to 95/5. If the volume ratio between the particles 5 and the binder 7 is 7/93 or more, appropriate unevenness and protrusions can be formed on the surface of the outermost layer 34 of the laminated film 3, so that good antifouling properties can be obtained. When the volume ratio of the particles 5 to the binder 7 is 95/5 or less, the adhesion of the antifouling film 4 to the outermost layer 34 of the laminated film 3 can be obtained satisfactorily. The upper limit of the volume ratio between the particles 5 and the binder 7 is more preferably 80/20, and even more preferably 70/30. The lower limit of the volume ratio is more preferably 20/80 and even more preferably 30/70.

When using the antifouling film 4 as an antifogging film, the contact angle of the antifouling film 4 with water is preferably 10 ° or less, and more preferably 5 ° or less. When the contact angle with water is 10 ° or less, moisture easily spreads on the surface of the antifogging film, and excellent antifogging properties are obtained. The contact angle with water can be measured by a static method described in JIS R 3257: 1999.

The nitrogen adsorption amount of the antifouling film 4 reflects the ability of the antifouling film 4 to absorb organic contaminants that hinder the spread of moisture. Organic substances in the air tend to be adsorbed on the surface to increase the contact angle with water, suppress moisture from spreading and reduce antifogging properties. Therefore, when the amount of nitrogen adsorbed on the antifouling film 4 is large, the antifouling film 4 absorbs organic matter in the air, so that the tendency of moisture to spread can be secured, and the deterioration of the antifogging property can be suppressed. it can.

The nitrogen adsorption amount is measured by the following method. That is, a laminated film and an antifouling film are formed on a smooth glass plate, cut into 5 mm × 30 mm strips, and the obtained 20 strips are put into a BET specific surface area measuring apparatus, and nitrogen gas is used. The BET specific surface area is measured. The nitrogen adsorption amount is preferably 1.5 to 5 times, preferably 2 to 4 times that in the case where the antifouling film 4 is not formed, that is, the case where only the laminated film 3 is formed and measured in the same manner. It is more preferable. Specifically, the nitrogen adsorption amount is preferably ^{3.0 ~ 7.5m 2 / g, 4.5} ~ 6.5m 2 / g is more preferable.

(particle)
The particles 5 in the antifouling film 4 are not particularly limited as long as the aggregate 6 and the binder 7 form an aggregate and can form irregularities and further protrusions on the surface of the antifouling film 4. The particles 5 may be inorganic particles or organic particles, but inorganic particles are preferable, and hydrophilic inorganic particles are more preferable. Examples of the hydrophilic inorganic particles include metal oxide particles such as silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), and zirconium oxide (zirconia). The particles 5 are preferably silicon oxide particles. If the particles 5 are silicon oxide particles, light scattering is suppressed, and the color of the glass substrate 2 is not impaired, which is preferable.

The particles 5 may be a single type or a combination of two or more types. When the particle 5 is a combination of two or more, the content of silicon oxide in the particle 5 is preferably 50% by mass or more, and more preferably 75% by mass or more. By setting the content of silicon oxide to 50% by mass or more, unevenness having a more appropriate shape is more easily formed, and the antifouling property tends to be further improved.

(Aggregate)
The aggregate 6 of the particles 5 may be either a primary aggregate in which the aggregation state of the particles is reversible or a secondary aggregate in which the aggregation state of the particles is irreversible. In adjusting, it is preferably a secondary aggregate. The shape of the aggregate 6 of the particles 5 is not particularly limited, but a chain shape or a pearl necklace shape is preferable. As the aggregate 6 of the particles 5, pearl necklace-like silica is particularly preferable. If the aggregate 6 is pearl necklace-like silica, when the antifouling film 4 is formed, protrusions capable of obtaining more appropriate irregularities are formed, and the antifouling property tends to be further improved. The pearl necklace-like silica is an elongated silica particle aggregate that may have either a linear shape or a branched shape in which a plurality of spherical silica particles having an average primary particle diameter of 5 to 300 nm are connected and secondary-aggregated. It is.

The average primary particle diameter of the particles 5 constituting the aggregate 6 is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm, further preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. When the average primary particle diameter of the particles 5 is 5 nm or more, the particles 5 are more easily aggregated to easily form protrusions, and the antifouling property tends to be further improved. Moreover, if the average primary particle diameter of the particle | grains 5 is 300 nm or less, since it is sufficiently shorter than the wavelength of visible light, a haze value can be reduced more.

Each of the chain particle aggregate and the pearl necklace particle aggregate has an elongated shape in which a plurality of particles 5 are connected (nicked). The chain particle aggregate is, for example, an average primary particle diameter d of 10 to 100 nm, an average length (L) of 50 to 500 nm, and a ratio of an average length to an average primary particle diameter of 3 to 20 (L / d). It is an elongated particle aggregate having the following structure. The pearl necklace-like particle aggregate is different from the chain particle aggregate in the existence ratio of the spherical portion. The pearl necklace-like particle aggregate is a pearl necklace in which a circular figure caused by a spherical portion has a roundness of 70% or more in a two-dimensional image obtained by an electron microscope, and the inscribed circle of each circular figure has a total area. It has a shape that occupies 70% or more of the total projected area of the particle-shaped aggregate and the inscribed circles of the circular figures do not overlap each other. The roundness is represented by the ratio of the radius of the inscribed circle to the radius of the circumscribed circle of the target figure outline, and is 100% for a perfect circle. In the chain particle aggregate, the existence ratio of the spherical portion is smaller than that of the pearl necklace particle aggregate. The secondary particle diameter of the pearl necklace-like particle aggregate is preferably 40 to 200 nm, more preferably 50 to 100 nm, and still more preferably 60 to 90 nm.

As the aggregate 6 of the particles 5, chain silica or pearl necklace silica is particularly preferable. If the aggregate 6 is chain-like silica or pearl necklace-like silica, appropriate irregularities and protrusions can be formed on the surface of the antifouling film 4, and the antifouling property tends to be further improved. The pearl necklace-like silica is an elongated silica particle in which a plurality of spherical silica particles having an average primary particle diameter of 5 to 300 nm are connected and secondary-aggregated so as to have an average length of 50 to 500 nm. preferable. The connection state of the spherical silica particles may be either linear or branched.

The average primary particle diameter of the particles is a value observed with a scanning electron microscope. The aggregate particle size is a value measured by a dynamic light scattering method.

Examples of commercially available spherical silica include IPA-ST, IPA-STL, and IPA-STZL (all manufactured by Nissan Chemical Industries, Ltd.).
Examples of commercially available pearl necklace-shaped silica include ST-PS-S, ST-PS-SO, ST-PS-M, and ST-PS-MO (all manufactured by Nissan Chemical Industries, Ltd.).
Examples of commercial products of chain silica include ST-OUP and ST-U (both manufactured by Nissan Chemical Industries, Ltd.).

(Binder)
The binder 7 is not particularly limited as long as it can adhere the particles 5 and the substrate, but an inorganic binder is preferable from the viewpoint of heat resistance, and a hydrophilic inorganic binder is more preferable. Examples of the hydrophilic inorganic binder include metal oxides such as silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), zirconium oxide (zirconia), tantalum oxide, and tin oxide. The binder 7 preferably contains silicon oxide as a main component, and more preferably silicon oxide. When the binder 7 is silicon oxide, the antifouling property is further improved.

The silicon oxide as the binder 7 is preferably a hydrolyzate of a silane compound having a hydrolyzable group, or a dehydrated or dehydrated condensate of silicic acid, and an alkoxysilane compound hydrolyzate or silicic acid alkali metal salt. More preferred is a dehydrated or dehydrated condensate of demineralized silicic acid obtained by removing at least a part of the alkali metal from These hydrolysates, dehydrates or dehydrated condensates may have unreacted silanol groups (Si—OH). For the binder 7, a cured product of a binder precursor described later is used.

(Further ingredients)
The antifouling film 4 can contain further components as long as the effects of the present invention are not impaired. Further components include surfactants, antifoaming agents, leveling agents, ultraviolet absorbers, viscosity modifiers, antioxidants, fungicides, pigments and the like. The content of further components is preferably 5% by mass or less in the antifouling film 4 and more preferably 1% by mass or less.

[Glass article manufacturing method]
Although the manufacturing method of the glass article of this invention is not specifically limited, The manufacturing method of embodiment shown below is used suitably. The manufacturing method of the embodiment includes the following steps (I) to (III). Other steps may be performed before, between and after the steps (I) to (III) as long as each step is not affected.
Step (I): A step of forming a laminated film including a plurality of layers having different refractive indexes on a glass substrate.
Process (II): The process of apply | coating the antifouling film forming composition containing the aggregate of particle | grains and a binder precursor (sol) on the outermost layer of a laminated film, and obtaining the coating film of an antifouling film forming composition .
Step (III): A step of forming an antifouling film containing agglomerates of particles and a binder by applying a binder precursor to the coating film and forming the binder from the binder precursor.

The method for producing a glass article of the embodiment includes a step of providing a plurality of layers on a glass substrate, a step of providing an outermost layer using a cylindrical magnetron sputtering method, and a step of providing an antifouling film using a sol-gel method. It is preferable to provide. In this case, the step of providing a plurality of layers on the glass substrate and the step of providing the outermost layer using a cylindrical magnetron sputtering method are included in the above-described step (I).

Furthermore, the manufacturing method of a glass article is
(1) forming a first layer on the first surface side of the glass substrate;
(2) forming a second layer directly on the first layer;
(3) a step of forming a third layer directly on the second layer, wherein the third layer includes a layer not containing silica;
(4) A step of forming an outermost layer composed of silica doped with zirconia directly on the third layer, wherein the outermost layer composed of silica doped with zirconia is formed by cylindrical magnetron sputtering. Steps formed by the law;
(5) A step of forming an antifouling film directly on the outermost layer, wherein the antifouling film is formed by a sol-gel method in which an antifouling film forming composition (sol) is applied and cured. When,
It is preferable to have.

(Process (I))
The step of forming the laminated film 3 is a step of forming the first layer 31, the second layer 32, the third layer 33, and the fourth layer 34 in this order on the glass substrate 2. The method for forming the first to fourth layers 31 to 34 is not particularly limited. The first to fourth layers 31 to 34 are formed by, for example, vapor deposition, sputtering, CVD (chemical vapor deposition), or the like. Further, a fifth layer or higher layers are formed as necessary.

(Process (II))
The antifouling film-forming composition coating step is performed by applying an antifouling film-forming composition containing an aggregate of particles and a binder precursor onto the uppermost layer 34 of the laminated film 3. This is a step of obtaining a coating film. The application method of the antifouling film forming composition is not particularly limited, and examples thereof include spin coating, dip coating, spray coating, flow coating, curtain flow coating, die coating, and squeegee coating, and spin coating is preferred. The coating thickness of the antifouling film forming composition is appropriately set according to the film thickness of the antifouling film 4.

(Manufacturing method of glass with antireflection film according to one embodiment of the present invention)
Next, an example of a method for producing an antireflection film-coated glass according to an embodiment of the present invention having the above-described features will be briefly described.

In addition, the manufacturing method of the glass with an antireflection film shown below is only an example, and the glass with an antireflection film according to the present invention may be manufactured by another method. In the following description, as an example, in the glass 200 with antireflection film shown in FIG. 4, a configuration in which the fourth layer 255 in the laminated film 230 is omitted (that is, an antireflection film having a laminated film having a four-layer structure). The manufacturing method will be described by taking glass with a film as an example. In FIG. 5, an example of the flow of the manufacturing method of such glass with an antireflection film is shown roughly.

As shown in FIG. 5, this manufacturing method (hereinafter referred to as “first manufacturing method”)
Forming a first layer on the first surface side of the glass substrate (step S110);
Forming a second layer directly on the first layer (step S120);
Forming a third layer directly on the second layer, wherein the third layer comprises a layer not containing silica (step S130);
Forming a layer composed of silica doped with zirconia directly on the third layer, wherein the layer composed of silica doped with zirconia is formed by a cylindrical magnetron sputtering method; Step (step S140);
After step S140, heat-treating the glass substrate (step S150);
Applying an antifouling film-forming composition on the layer composed of silica doped with zirconia (step S160);
Step of curing antifouling film forming composition to form antifouling film (step S170)
Have However, step S150 may be omitted.

Hereafter, each step will be described. In the following description, for the sake of clarity, the reference numerals shown in FIG. 4 are used when describing each member.

(Step S110)
First, a glass substrate 220 having first and

second surfaces

222 and 224 is prepared. The composition of the glass substrate 220 is not particularly limited. The glass substrate 220 may be, for example, alkali-free glass, soda lime glass, aluminosilicate glass, or the like.

Next, the first layer 240 is formed on the first surface 222 side of the glass substrate 220. As described above, the first layer 240 is made of a material having a refractive index higher than that of the second layer 245 formed in the subsequent step S120. The first layer 240 may be, for example, titania, niobium oxide, zirconia, ceria, tantalum oxide, or the like.

The method for forming the first layer 240 is not particularly limited. The first layer 240 may be formed on the first surface 222 of the glass substrate 220 by, for example, a vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method, or the like.

(Step S120)
Next, the second layer 245 is formed immediately above the first layer 240. As described above, the second layer 245 is made of a material having a refractive index lower than that of the first layer 240 and having a refractive index lower than that of the third layer 255 formed in the subsequent step S130. Is done. The second layer 245 may be, for example, silica or alumina.

The formation method of the second layer 245 is not particularly limited. The second layer 245 may be formed by, for example, a vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method, or the like.

(Step S130)
Next, the third layer 250 is formed immediately above the second layer 245. As described above, the third layer 250 is made of a material having a higher refractive index than that of the second layer 245. The third layer 250 may be, for example, titania, niobium oxide, zirconia, ceria, tantalum oxide, or the like. Note that the third layer 250 is formed of a layer not containing silica.

The method for forming the third layer 250 is not particularly limited. The third layer 250 may be formed by, for example, a vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method, or the like.

(Step S140)
Next, a ZrO ₂ -doped SiO ₂ layer (so-called outermost layer) 260 is formed immediately above the third layer 250. The doping amount of zirconia in the outermost layer 260 is not particularly limited, but may be in the range of 5 to 50 mol%, for example.

The outermost layer 260 can be formed by, for example, a sputtering method. In particular, among the sputtering methods, the cylindrical magnetron sputtering method is preferable. In this cylindrical magnetron sputtering method, a hollow cylindrical target is used instead of a normal flat target. Sputtering film formation is carried out while rotating the hollow cylindrical target in the direction of the stretching axis (see, for example, the specification of Japanese Patent No. 4636964).

As described in detail later, when the outermost layer 260 is formed by a cylindrical magnetron sputtering method, adhesion of debris (foreign matter) to the laminated film is significantly suppressed. Therefore, it is possible to obtain a glass with an antireflection film with few defects.

(Step S150)
Next, if necessary, the glass substrate 220 on which the stacked film 230 (the first layer 240, the second layer 245, the third layer 250, and the outermost layer 260) is formed on the first surface 222 is heat-treated. The The heat treatment is performed for strengthening or bending the glass substrate 220. However, this step may be omitted.

The heat treatment is performed, for example, in the air at a temperature range of 550 ° C. to 700 ° C. The heat treatment may be performed, for example, by rapidly cooling the glass substrate 220 heated to 650 ° C. by air blowing.

(Step S160)
The step of applying the antifouling film forming composition includes particles capable of forming protrusions and a binder precursor on the laminated film 230 formed on the substrate, and the particles capable of forming the protrusions and the binder precursor. And an antifouling film-forming composition having a mass ratio in terms of metal oxide of 7/93 to 95/5, to form an antifouling film-forming composition layer.

Preferably, step S160 includes a pearl necklace-like silica having an average primary particle diameter of 5 to 300 nm and a silicon oxide precursor, and the mass of the pearl necklace-like silica and the silicon oxide precursor in terms of silicon oxide. A step of applying an antifouling film-forming composition having a ratio (pearl necklace-like silica / silicon oxide precursor) of 7/93 to 95/5 to form an antifouling film-forming composition layer; .

(Anti-fouling film forming composition)
The antifouling film forming composition preferably contains an aggregate of particles and a binder precursor. The antifouling film forming composition is prepared by mixing an aggregate of particles and an aqueous solution of a binder precursor. In addition to these, the antifouling film-forming composition may contain water, a solvent, and the like, and may further contain other components.

(Particles and aggregates)
The aggregate of particles that can form protrusions is preferably pearl necklace-like silica having an average primary particle diameter of 5 to 300 nm. When an antifouling film-forming composition containing only spherical silica particles is applied to the surface of the substrate, the particles are easy to laminate relatively uniformly, so that the resulting coating forms irregularities sufficient to exhibit antifouling properties. Not.

(Binder precursor)
A binder precursor is a component which forms a binder, for example by heat processing. Examples of the binder precursor include inorganic binder precursors, and metal oxide precursors such as a silicon oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a zirconium oxide precursor, a tantalum oxide precursor, and a tin oxide precursor. Is preferred. Examples of the silicon oxide precursor include a silane compound having a hydrolyzable group and silicic acid. Examples of the binder precursor other than the silicon oxide precursor include a metal compound having a hydrolyzable group. The metal oxide precursor is a component that forms a metal oxide by a hydrolysis reaction. As the binder precursor, a silicon oxide precursor is preferable. When the antifouling film-forming composition contains a silicon oxide precursor, the adhesion between the antifouling film 4 to be formed and the substrate can be further improved. The binder precursor may be one kind alone or a combination of two or more kinds.

(Silicon oxide precursor)
Examples of the silicon oxide precursor include silicic acid and a silane compound having a hydrolyzable group. As the silicon oxide precursor, desalted silicic acid obtained by removing at least a part of an alkali metal from an alkali metal salt of silicic acid described later, or an alkoxysilane compound or a partially hydrolyzed condensate thereof is preferable. The antifouling film-forming composition is formed by containing demineralized silicic acid obtained by removing at least a part of an alkali metal from an alkali metal salt of silicic acid and / or an alkoxysilane compound or a partial hydrolysis condensate thereof. The adhesion between the antifouling film and the laminated film can be further improved.

(Silicic acid)
Examples of silicic acid include orthosilicic acid, metasilicic acid, and metadisilicic acid, with metasilicic acid being preferred. The silicic acid is preferably demineralized silicic acid obtained by removing at least part of the alkali metal from the alkali metal salt of silicic acid (hereinafter also simply referred to as “demineralized silicic acid”). Desalted silicic acid is preferably obtained by a method of reducing alkali metal ions from an aqueous solution of an alkali metal salt of silicic acid using a cation exchange resin. The amount of the alkali metal ion of the desalted silicic acid is not particularly limited, but the alkali metal ion is preferably 0.001 to 1 part by mass, and 0.001 to 0.2 part by mass with respect to 100 parts by mass of silicic acid. More preferred is 0.001 to 0.15 parts by mass. The alkali metal ion concentration of silicic acid can be measured by ICP emission spectrometry.

The cation exchange resin is not particularly limited, a strongly acidic cation exchange resin (RSO 3 _H type), weakly acidic cation exchange resin (RCOOH type) and the like, a strongly acidic cation exchange resin is a reaction rate This is preferable. The amount of alkali metal ions to be reduced can be adjusted by controlling the amount of cation exchange resin used, the contact time, the contact method, and the like.

Examples of the alkali metal salt of silicate include sodium silicate, lithium silicate, potassium silicate and the like, sodium silicate and / or lithium silicate are preferable, and sodium silicate is particularly preferable.

(Silane compound having hydrolyzable group)
A silane compound having a hydrolyzable group is a compound having 1 to 4 hydrolyzable groups bonded to a silicon atom in one molecule. Examples of the hydrolyzable group include an alkoxy group, an isocyanato group, an acyloxy group, an aminoxy group, a halogen group, and the like, and an alkoxy group is preferable. Moreover, as a silane compound which has a hydrolysable group, an alkoxysilane compound is preferable. The alkoxysilane compound may be a condensate in which at least some of the molecules are hydrolytically condensed (hereinafter also referred to as “partially hydrolyzed condensate of alkoxysilane compound”).

The alkoxysilane compound is a compound having 1 to 4 alkoxy groups bonded to a silicon atom in one molecule. Examples of the alkoxysilane compound include compounds represented by the following general formula (1).
(R ¹ O) _p SiR ² _(4-p) (1)
In the formula, each R ¹ independently represents an alkyl group having 1 to 4 carbon atoms, and each R ² independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms. P represents a number from 1 to 4. When a plurality of R ¹ or R ² are present, they may be the same as or different from each other.

R ¹ is an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group, and a methyl group and an ethyl group are preferable. The alkyl group having 1 to 10 carbon atoms in R ² is linear or branched, and is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, decyl group. Groups and the like. R ² is preferably an alkyl group having 1 to 6 carbon atoms. The substituent in R ² is not particularly limited, but is an epoxy group, glycidoxy group, methacryloyloxy group, acryloyloxy group, isocyanato group, hydroxy group, amino group, phenylamino group, alkylamino group, aminoalkylamino group, ureido group And a mercapto group. The “alkyl group having 1 to 10 carbon atoms” in R ² means that the alkyl group portion excluding the substituent has 1 to 10 carbon atoms.

Examples of the alkoxysilane compound include tetraalkoxysilane compounds having an alkoxy group bonded to four silicon atoms in one molecule such as tetramethoxysilane and tetraethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidide Xylpropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltri Methoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino 1 to 3 alkoxy bonded to a silicon atom in one molecule such as propylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Examples thereof include alkoxysilane compounds having a group. As the alkoxysilane compound, a tetraalkoxysilane compound is preferable.

(Water and acid catalyst)
The antifouling film forming composition may contain water and an acid catalyst under the condition that a hydrolysis condensate of the binder precursor is obtained.

The antifouling film-forming composition may contain water. Hydrolysis condensation reaction advances because antifouling film formation composition contains water. The amount of water is preferably 10 to 500 parts by weight and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the binder precursor. Here, the amount of the binder precursor is an amount in terms of metal oxide.

The antifouling film forming composition may contain an acid catalyst. When the antifouling film forming composition contains an acid catalyst, the reaction rate of the hydrolysis condensation of the binder precursor can be adjusted. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid and the like. The amount of the acid catalyst is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.5 parts by mass with respect to 100 parts by mass of the binder precursor. Here, the amount of the binder precursor is an amount in terms of metal oxide.

(solvent)
The antifouling film forming composition may contain a solvent. There exists a tendency for workability | operativity to improve because antifouling film forming composition contains a solvent. The solvent is not particularly limited as long as it can disperse particles and binder precursors that can form protrusions and has low reactivity with these components. Examples of the solvent include alcohols (methanol, ethanol, 2-propanol, etc.), esters (acetic esters such as butyl acetate), ethers (diethylene glycol dimethyl ether, etc.), ketones (methyl ethyl ketone, etc.), and esters and alcohols are preferred. Alcohol is more preferred. The solvent may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but is preferably 1000 to 100,000 parts by mass, more preferably 2000 to 50000 parts by mass with respect to 100 parts by mass in total of the particles and the binder precursor. When the content of the solvent is 1000 parts by mass or more with respect to 100 parts by mass in total of the particles and the binder precursor, rapid progress of hydrolysis and condensation reaction can be prevented. If content of a solvent is 100,000 mass parts or less, a hydrolysis and a condensation reaction will advance more. Here, the amount of the particles and the binder precursor is a metal oxide equivalent amount.

(Further ingredients)
The antifouling film-forming composition can contain further components as long as the effects of the present invention are not impaired. Examples of such components include surfactants, antifoaming agents, leveling agents, ultraviolet absorbers, viscosity modifiers, antioxidants, fungicides, and pigments. The content of further components in the antifouling film forming composition is not particularly limited, but is preferably 0.02 to 1 part by weight, preferably 0.02 to 0 parts per 100 parts by weight in total of the particles and the binder precursor. 0.5 part by weight is more preferable, and 0.02 to 0.3 part by weight is still more preferable. Here, the amount of the particles and the binder precursor is a metal oxide equivalent amount.

(Method for applying antifouling film forming composition)
The application of the antifouling film-forming composition can be performed by a wet coating method. The wet coating method is not particularly limited, and examples thereof include spin coating, dip coating, spray coating, flow coating, and die coating, and spin coating is preferable. The antifouling film forming composition is preferably applied to at least a part of the surface of the substrate and applied to the entire surface of at least one main surface of the substrate.

The thickness of the antifouling film-forming composition layer is not particularly limited as long as it is an amount that provides a desired thickness of the antifouling film 4. The application amount of the antifouling film-forming composition applied on the substrate is not particularly limited as long as it is an amount that will be the thickness of the antifouling film 4 described above, and the solid content is 1.6 to 1600 g / m ^2. And more preferably 8.0 to 800 g / m ² . In the present invention, the content of the component in terms of solid content refers to the mass of the residue excluding volatile components such as water.

(Process (III))
The antifouling film 4 is formed by subjecting the coating film of the antifouling film forming composition to a treatment for curing the binder precursor, and forming the binder from the binder precursor, whereby the aggregates 6 of the particles 5 and the binder 7 are formed. Is a step of forming the antifouling film 4 containing Examples of the curing treatment of the binder precursor include heat treatment, but are not limited thereto.

(Step 170)
The antifouling film 260 is obtained by curing the antifouling film forming composition layer by heat treatment.

By heat-treating the antifouling film forming composition layer, the binder precursor alone or reacts with the particles to become a binder, and the antifouling film 4 is formed. When the antifouling film-forming composition contains pearl necklace-like silica and a silicon oxide precursor, the silicon oxide precursor reacts to obtain a binder. When the silicon oxide precursor is silicic acid and an alkoxysilane compound, the silicic acid and the alkoxysilane compound are hydrolyzed and condensed to obtain silicon oxide that is a hydrolyzate of the silicic acid and the alkoxysilane compound. In some cases, at least a part of the silicic acid and the alkoxysilane compound is hydrolyzed and condensed with silanol groups present in the pearl necklace-like silica particles.

The heat treatment of the antifouling film forming composition layer can be performed by any heating means such as an electric furnace, a gas furnace, an infrared heating furnace set at a predetermined temperature. The heat treatment temperature is preferably 20 to 700 ° C, more preferably 80 to 500 ° C, and particularly preferably 100 to 400 ° C. When the heat treatment temperature is 20 ° C. or higher, the adhesion between the laminated film and the antifouling film is further improved. When the heat treatment temperature is 700 ° C. or lower, deterioration of the base material due to heat is suppressed, and the productivity is excellent. The heat treatment time varies depending on the heat treatment temperature, but is preferably 1 to 180 minutes, more preferably 5 to 120 minutes, and particularly preferably 10 to 60 minutes. When the heat treatment time is 1 minute or longer, the adhesion between the substrate and the antifouling film 4 is further improved. When the heat treatment time is 180 minutes or less, deterioration of the base material due to heat is suppressed, and the productivity is excellent.

Through the above steps, a glass with an antireflection film constituted by the glass substrate 220 and the laminated film 230 can be manufactured. Furthermore, the glass article 1 having antireflection performance and antifouling performance, in which the antifouling film 260 is formed on the laminated film 230 (3), can be manufactured.

In addition, the manufacturing method of the glass with an antireflection film according to an embodiment of the present invention described above is merely an example, and it is obvious to those skilled in the art that the glass with an antireflection film can be manufactured by other methods. For example, in the above description, the case where only the outermost layer 260 is formed by the cylindrical magnetron sputtering method has been described as an example. However, at least one of the first to third layers is formed by the cylindrical magnetron sputtering method. Also good.

Further, in the above description, the manufacturing method has been described by taking as an example a configuration in which the fourth layer 255 in the laminated film 230 is omitted in the glass 200 with an antireflection film shown in FIG. However, it will be apparent to those skilled in the art that the first manufacturing method can be similarly applied to a glass with an antireflection film having a laminated film having other configurations.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[Example of glass article having antifouling performance and antifogging performance]
First, examples of glass articles having antifouling performance and antifogging performance will be described. In the following description, Examples 1 and 2 are examples of glass articles having antifouling performance and antifogging performance of the present invention, and Examples 3 to 4 are comparative examples.

(Formation of laminated film)
A laminated film was formed on one surface of the glass substrate by the following method to produce a low reflection laminated structure sample. First, a glass substrate made of soda lime glass having a shape of 25 mm long × 50 mm wide × 2 mm thick was prepared. Next, a total of four laminated films composed of the first to fourth layers were formed on one surface of the glass substrate by sputtering. The laminated film has the following layer structure from the side close to the glass substrate.
First layer: SiO ₂ layer, thickness 198 nm
Second layer: TiO ₂ layer, thickness 8 nm
Third layer: SiO ₂ layer, thickness 66 nm
Fourth layer: TiO ₂ layer, thickness 11 nm

The first layer was formed by sputtering using an Si target as a target and under an Ar + O ₂ atmosphere (oxygen: 60% by volume). The sputtering pressure was 0.17 Pa. The second layer uses a TiO _x target (x <2) (product name: TXO target, manufactured by AGC Ceramics) as a target, and is formed by sputtering under an Ar + O ₂ atmosphere (oxygen: 8% by volume). did. The sputtering pressure was 0.37 Pa. The third layer was formed by sputtering using an Si target as a target and under an Ar + O ₂ atmosphere (oxygen: 60% by volume). The sputtering pressure was 0.17 Pa. The fourth layer was formed by sputtering using the above-described TiO _x target (x <2) as a target under an Ar + O ₂ atmosphere (oxygen: 8% by volume). The sputtering pressure was 0.37 Pa.

(Example 1)
(Preparation of binder precursor (1))
While stirring 237.5 g of distilled water, sodium silicate 4 (manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ : 24.0 mass%, Na ₂ O: 7.0 mass%, SiO ₂ / Na ₂ O 62.5 g of a molar ratio of 3.5 / 1) and 180 g of a cation exchange resin (Diaion SK1BH, manufactured by Mitsubishi Chemical Corporation) were added in this order, and the mixture was stirred for 10 minutes or more and then positively filtered by suction filtration. The ion exchange resin was separated, and a binder precursor (1), which is a silicon oxide precursor, was obtained as a desalted sodium silicate solution having a solid content concentration in terms of silica of 5% by mass.

(Preparation of antifouling film forming composition)
While stirring 6.58 g of 2-propanol, a dispersion of pearl necklace-like silica in which spherical silica having a primary particle diameter of 10 to 18 nm is bonded to a length of 80 to 120 nm (Snowtex PS, manufactured by Nissan Chemical Co., Ltd.) -SO, average primary particle size: 15 nm, average secondary particle size: 88 nm) and 2.18 g of the binder precursor (1) were added in this order, and the solid content concentration in terms of silica was 2. An antifouling film-forming composition having a solid content mass ratio in terms of silica of .95% by mass and pearl necklace-like silica and sodium desalted silicate solution was prepared.

(Manufacture of glass articles)
A low-reflection laminate structure sample was set on a spin coater, and 2.0 g of the antifouling film forming composition was dropped on the surface of the low-reflection laminate structure sample and spin-coated. Next, the coating film of the antifouling film-forming composition was heat-treated at 150 ° C. for 30 minutes to form an antifouling film on the low-reflective laminated structure sample to produce a glass article. In the formed antifouling film, the volume ratio of the pearl necklace-like silica as the hydrophilic particles to the silica as the hydrophilic binder was 57/43.

(Example 2)
A dispersion of chain silica in which spherical silica particles having a primary particle size of 10 to 18 nm are bonded to a length of 80 to 120 nm (manufactured by Nissan Chemical Co., Ltd., Snowtex ST-OUP, average primary particle size: 15 nm, average secondary particles) A glass article was produced by forming an antifouling film on a low reflection laminate structure sample in the same manner as in Example 1 except that the diameter was 88 nm), and subjected to the following evaluation.

(Example 3)
Low reflection laminated structure in the same manner as in Example 1 except that a dispersion of spherical silica particles having a primary particle size of 10 to 18 nm (manufactured by Nissan Chemical Co., Ltd., Snowtex IPA-ST, average primary particle size: 15 nm) is used. An antifouling film was formed on the sample to produce a glass article, which was subjected to the following evaluation.

(Example 4)
A laminated film consisting of five layers was formed in the same manner as in Examples 1 to 3. However, the following layer structure was used from the side close to the glass substrate.
First layer: SiO ₂ layer, thickness 52 nm
Second layer: TiO ₂ layer, thickness 15 nm
Third layer: SiO ₂ layer, thickness 29 nm
Fourth layer: TiO ₂ layer, thickness 106 nm
Fifth layer: SiO ₂ layer, thickness 85 nm

(Evaluation of glass articles)
Evaluation of the glass articles of Examples 1 to 3 and the laminated film sample of Example 4 was performed as follows. The evaluation results are shown in Table 1.

(Average primary particle size of particles)
The surface of the antifouling film of the glass article is observed from above with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800), and randomly obtained from the obtained image. 100 particles were extracted, and the average diameter of each particle was determined as the average primary particle diameter of the particles.

(Surface roughness (Ra))
Ra was measured using a scanning probe microscope (SII Nanotechnology, Model: SPA400).
(Microscope setting conditions)
The cantilever was measured with SI-DF40 (with rear surface AL), 256 XY data, and scanning area of 10 μm × 10 μm.

(Vertex distance)
The cross section of the glass article is observed with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800), and the obtained image is randomly selected in a direction parallel to the surface of the laminated film having the antifouling film. In the extracted range of 1.5 μm, the protrusion having the highest height from the surface of the laminated film is used as a reference, and the protrusion having a height of 90% or more of the height is between apexes of adjacent protrusions. All the distances were measured, and the average value of the distance between the vertices was calculated.

(Coverage)
The surface of the antifouling film is observed from above with respect to the main surface of the glass article with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800), and image conversion software (image J ) To calculate the area ratio of the portion where the silica particles are adhered within the randomly extracted range of 1 μm × 1 μm.

(Nitrogen adsorption amount)
The glass article was processed into a 5 mm × 30 mm strip, and 20 sheets were put into a specific surface area measuring device and measured, and the nitrogen adsorption amount was calculated.

(Contact angle with water)
In order to evaluate the influence of organic contaminants on the contact angle, the sample was left in a sealed glass container with oleic acid in a container without a lid for 12 hours, and then the contact angle with water was evaluated. The contact angle was evaluated based on JIS R 3257.

(Anti-fogging property)
A sealable container having a vapor outlet formed at the top was prepared. A warm bath was placed inside the container and heated to 40 ° C. to generate steam. This evaluation apparatus was installed in an environment of 25 ° C. and 55% RH, and a glass article was placed at the vapor outlet to evaluate the time when it began to cloud visually.

(Reflectance)
After performing antireflection treatment (roughening treatment) on the surface of the glass substrate on which the laminated film is not disposed, the wavelength is measured using a spectrophotometer (model U-4100, manufactured by Hitachi, Ltd.) based on JIS R 3106. The spectral reflectance in the range of 400 to 700 nm was measured, and the maximum reflectance in this wavelength region is shown in Table 1.

As shown in Table 1, it can be seen that the glass articles of Examples 1 and 2 are excellent in antifouling performance and antifogging performance from the evaluation results of contact angle with water, nitrogen adsorption amount, and antifogging property. In Example 3 using silica particles (non-aggregated particles) as hydrophilic particles, although the contact angle with water and the amount of nitrogen adsorption are slightly improved compared to Example 4 in which an antifouling film is not formed, sufficient protection is achieved. No haze performance was obtained.

[Examples of glass with laminated film having alkali resistance]
Next, the Example of the glass with a laminated film provided with alkali resistance is described. In the following description, Examples 5 to 8 are examples of the glass with a laminated film having alkali resistance of the present invention, and Example 9 is a comparative example.

(Example 5)
A laminated film was formed on one surface of the glass substrate by the following method to produce a glass sample with an antireflection film (hereinafter referred to as “sample according to Example 5”).

First, a glass substrate (soda lime glass) of 25 mm length × 50 mm width × 2 mm thickness was prepared. Next, a total of four laminated films composed of the first to fourth layers were formed on one surface of the glass substrate by sputtering. The laminated film has the following layer structure from the side close to the glass substrate.
First layer: TiO ₂ layer, thickness 11 nm
Second layer: SiO ₂ layer, thickness 31 nm
Third layer: TiO ₂ layer, thickness 99 nm
Fourth layer: 90 mol% SiO ₂ -10 mol% ZrO ₂ layer, thickness 83 nm

The first layer was formed by sputtering under an Ar + O ₂ atmosphere (oxygen: 8% by volume) using a TiOx target (x <2) (product name: TXO target, manufactured by AGC Ceramics) as a target. The sputtering pressure was 0.37 Pa.

The second layer was formed by sputtering using an Si target as a target and under an Ar + O ₂ atmosphere (oxygen: 60% by volume). The sputtering pressure was 0.17 Pa.

The third layer was formed by sputtering using the above-described TiOx target (x <2) as a target under an Ar + O ₂ atmosphere (oxygen: 8% by volume). The sputtering pressure was 0.37 Pa.

The fourth layer was formed by sputtering under an Ar + O ₂ atmosphere (oxygen: 60% by volume) using a Si target doped with 10 atomic% Zr as a target. The sputtering pressure was 0.12 Pa.

In addition, an antireflection treatment (roughening treatment) was performed on the surface of the glass substrate on which the laminated film is not disposed.

(Example 6)
A glass sample with an antireflection film (hereinafter referred to as “sample according to Example 6”) was produced in the same manner as in Example 5. However, in Example 6, the laminated film has the following layer configuration.
First layer: TiO ₂ layer, thickness 13 nm
Second layer: SiO ₂ layer, thickness 28 nm
Third layer: TiO ₂ layer, thickness 97 nm
Fourth layer: 80 mol% SiO ₂ -20 mol% ZrO ₂ layer, thickness 68 nm
Note that the fourth layer was formed by sputtering under an Ar + O ₂ atmosphere (oxygen: 60% by volume) using a Si target doped with 20 atomic% Zr as a target. The sputtering pressure was 0.12 Pa.

(Example 7)
A glass sample with an antireflection film (hereinafter referred to as “sample according to Example 7”) was produced in the same manner as in Example 5. However, in Example 7, the laminated film had the following layer configuration.
First layer: TiO ₂ layer, thickness 16 nm
Second layer: SiO ₂ layer, thickness 25 nm
Third layer: TiO ₂ layer, thickness 65 nm
Fourth layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer, thickness 76 nm
Note that the fourth layer was formed by a sputtering method under an Ar + O ₂ atmosphere (oxygen: 60% by volume) using a Si target doped with 33 atomic% of Zr as a target. The sputtering pressure was 0.12 Pa.

(Example 8)
A glass sample with an antireflection film (hereinafter referred to as “sample according to Example 8”) was produced in the same manner as in Example 5. However, in Example 8, the same laminated film was formed on both sides of the glass substrate. Therefore, the antireflection treatment (roughening treatment) is not performed on the glass substrate. Each laminated film had the following layer configuration.
First layer: TiO ₂ layer, thickness 12 nm
Second layer: SiO ₂ layer, thickness 30 nm
Third layer: TiO ₂ layer, thickness 99 nm
Fourth layer: 90 mol% SiO ₂ -10 mol% ZrO ₂ layer, thickness 81 nm

(Example 9)
A glass sample with an antireflection film (hereinafter referred to as “sample according to Example 9”) was produced in the same manner as in Example 5. However, in Example 9, the laminated film had the following layer configuration.
First layer: TiO ₂ layer, thickness 13 nm
Second layer: SiO ₂ layer, thickness 28 nm
Third layer: TiO ₂ layer, thickness 97 nm
Fourth layer: SiO ₂ layer, thickness 81 nm
Note that the fourth layer was formed by sputtering using an Si target as a target and under an Ar + O ₂ atmosphere (oxygen: 60% by volume). The sputtering pressure was 0.17 Pa.

(Evaluation of laminated film)
The alkali resistance characteristics were evaluated using the samples according to Examples 5 to 9 manufactured by the method described above. The evaluation of alkali resistance was performed by the following alkali resistance test.

(Alkali resistance test)
Each sample is irradiated with light from the side where the laminated film is disposed (one side in the sample according to Example 8), and the reflectance (initial reflectance) is measured by a spectrophotometer. Next, each sample is immersed in an aqueous NaOH solution having a concentration of 0.1 kmol / m ³ heated to 90 ° C. for 2 hours. The sample is removed from the aqueous solution, washed with pure water, and then dried. Using the sample after drying, the same measurement as before the immersion treatment is performed, and the reflectance (reflectance after treatment) is measured. In each sample, the initial reflectance and the reflectance after treatment are compared to evaluate the alkali resistance.

Here, the uppermost layer preferably has a difference in visible light reflectance before and after the test immersed in an aqueous NaOH solution having a concentration of 0.1 kmol / m ³ heated to 90 ° C. for 2 hours within 0, Is more preferably within 3 and particularly preferably within 0.1.

(Visible light reflectance)
It can be said that the lower the visible light reflectance of the glass with an antireflection film, the better the low reflection characteristics.

When the laminated film is formed only on one surface of the glass substrate and the other surface is roughened, the visible light reflectance of the glass with an antireflection film measured based on ISO 9050 (2003) is 1%. In the case of exceeding, the low reflection characteristics are insufficient. The visible light reflectance is preferably 1% or less.

In the state where laminated films are formed on both surfaces of the glass substrate, when the visible light reflectance of the glass with antireflection film measured based on ISO 9050 (2003) exceeds 2%, the low reflection characteristics are insufficient. is there. The visible light reflectance is preferably 2% or less, and more preferably 1% or less.

(Reflective color)
In general, glass with an antireflection film whose reflection color is red or orange tends to be avoided, and glass with an antireflection film whose reflection color is blue or green is often preferred. However, even if the reflected color is blue or green, if the saturation is too strong, it tends to be avoided.

When the reflection color in the standard illuminant D65, 10-degree field of view is expressed by the color coordinates (a ^* , b ^* ) of the L ^* a ^* b ^* color system specified in ISO11664-2, The reflection color is inside the pentagon with 5 points (0,0), (20, -20), (-15, -20), (-15,10), and (0,10) as vertices It is preferable. In such a case, the reflection color of the glass with an antireflection film is not red or orange, and the saturation is not too strong.

Table 2 below shows the specifications of the laminated films according to Examples 5 to 9.

Table 3 below collectively shows the visible light reflectance, color coordinates a ^* , b ^* , and alkali resistance test results of the samples according to Examples 5 to 9 before and after the immersion treatment. The visible light reflectance is a value measured based on ISO9050 (2003). Further, the color coordinates a ^* and b ^* are reflected colors in the standard illuminant D65, 10-degree field of view, and are based on the L ^* a ^* b ^* color system according to ISO11664-2 (2007).

In the sample according to Example 5, the reflectance characteristics were almost the same before and after the immersion treatment, and no significant difference was observed between the two. That is, it was found that the sample according to Example 5 exhibited a sufficiently low reflectance over a wavelength range of about 400 nm to about 650 nm both before and after the immersion treatment. As shown in Table 3, the visible light reflectance before and after the immersion treatment of the sample according to Example 5 was 0.26% and 0.26%, respectively. That is, the visible light reflectance of the sample according to Example 5 was 1% or less before and after the immersion treatment. Thus, it was confirmed that the sample according to Example 5 has good alkali resistance.

Further, as shown in Table 3, the reflection colors (a ^* , b ^* ) before and after the immersion treatment of the sample according to Example 5 were (−0.47, −4.14), (−0.45, − 3.61). That is, the reflection color of the sample according to Example 5 before and after the immersion treatment was inside the pentagon described above.

Also in the sample according to Example 6, the reflectance characteristics were almost the same before and after the immersion treatment, and no significant difference was observed between the two. That is, it was found that the sample according to Example 6 exhibited a sufficiently low reflectance over a wavelength range of about 400 nm to about 650 nm both before and after the immersion treatment. As shown in Table 3, the visible light reflectance before and after the immersion treatment of the sample according to Example 6 was 0.87% and 0.90%, respectively. That is, the visible light reflectance of the sample according to Example 6 was 1% or less before and after the immersion treatment. Thus, it was confirmed that the sample according to Example 6 has good alkali resistance.

As shown in Table 3, the reflection colors (a ^* , b ^* ) before and after the immersion treatment of the sample according to Example 6 were (−3.35, 0.75), (−2.84, −1.03), respectively. )Met. That is, the reflection color of the sample according to Example 6 was inside the above pentagon before and after the immersion treatment.

Also in the sample according to Example 7, the reflectance characteristics were almost the same before and after the immersion treatment, and no significant difference was observed between the two. That is, it was found that the sample according to Example 7 had a sufficiently low reflectance over a wavelength range of about 450 nm to about 650 nm both before and after the immersion treatment. As shown in Table 3, the visible light reflectance before and after the immersion treatment of the sample according to Example 7 was 0.71% and 0.70%, respectively. That is, the visible light reflectance of the sample according to Example 7 was 1% or less before and after the immersion treatment. Thus, it was confirmed that the sample according to Example 7 has good alkali resistance.

Further, as shown in Table 3, the reflection colors (a ^* , b ^* ) before and after the immersion treatment of the sample according to Example 7 were (9.98, −15.44), (11.02, −17. 86). That is, the reflection color of the sample according to Example 7 before and after the immersion treatment was inside the above pentagon.

Here, the visible light reflectances of Examples 5 to 7 are compared. The outermost layers of Examples 5 to 7 are 90 mol% SiO ₂ -10 mol% ZrO ₂ layer, 80 mol% SiO ₂ -20 mol% ZrO ₂ layer and 67 mol% SiO ₂ -33 mol% ZrO ₂ layer, respectively. However, it can be seen that the 90 nm% SiO ₂ -10 mol% ZrO ₂ layer having the lowest refractive index is the outermost layer, and the visible light reflectance of Example 5 is the lowest and the low reflection characteristics are good.

Also in the sample according to Example 8, the reflectance characteristics were almost the same before and after the immersion treatment, and no significant difference was observed between the two. That is, it was found that the sample according to Example 8 had a sufficiently low reflectance over a wavelength range of about 450 nm to about 650 nm both before and after the immersion treatment. As shown in Table 3, the visible light reflectance before and after the immersion treatment of the sample according to Example 8 was 0.77% and 0.74%, respectively. Samples according to the Example 8, as with Example 5, a low refractive index as ZrO ₂ doped SiO ₂ layer 90 mole% _SiO 2 -10 mol% ZrO ₂ layer is the outermost layer. Therefore, although the laminated film is formed on both surfaces of the glass substrate, the visible light reflectance is 2% or less and 1% or less, and it can be seen that the low reflection characteristic is good. Thus, it was confirmed that the sample according to Example 8 has good alkali resistance.

As shown in Table 3, the reflection colors (a ^* , b ^* ) before and after the immersion treatment of the sample according to Example 8 were (−1.76, −6.28) and (−1.18, 2.34), respectively. )Met. That is, the reflection color of the sample according to Example 8 was inside the above pentagon before and after the dipping treatment.

In the sample according to Example 9, a significant difference was observed in the reflectance characteristics before and after the immersion treatment. That is, it was found that the sample according to Example 9 showed good low reflection characteristics before the immersion treatment, but increased the reflectance over the wavelength range of about 400 nm to about 750 nm after the immersion treatment. As shown in Table 3, the visible light reflectance before and after the immersion treatment of the sample according to Example 9 was 0.27% and 10.35%, respectively. Thus, it was confirmed that the sample according to Example 9 does not exhibit good alkali resistance.

As described above, it was confirmed that the alkali resistance characteristics were significantly improved in the samples according to Examples 5 to 8 adopting the configuration of the glass with a preferable antireflection film according to the present invention.

(Productivity evaluation)
Next, the glass with an antireflection film according to one example of the present invention was continuously produced, and the productivity was evaluated.

The glass with an antireflection film has a four-layer laminated film similar to Example 5 on the first surface of a glass substrate (made of soda lime glass) having a vertical and horizontal dimension of 100 inches × 144 inches. It was. Here, the constituent conditions of each layer are as follows.
First layer: TiO ₂ layer, thickness 12 nm
Second layer: SiO ₂ layer, thickness 35 nm
Third layer: TiO ₂ layer, thickness 105 nm
Fourth layer (outermost layer): 90 mol% SiO ₂ -10 mol% ZrO ₂ layer, thickness 84 nm

Among these, the first layer was formed by a sputtering method using a normal flat TiOx target (x <2). The second to fourth layers were formed by a cylindrical magnetron sputtering method using a cylindrical target.

The glass with an antireflection film was continuously produced by causing a glass substrate having the above dimensions to be conveyed by a roller in a single coater. The atmosphere in the coater was Ar + O ₂ atmosphere.

A total of 290 glasses with an antireflection film were produced in about 1.5 days of the latter half of the continuous discharge for about 4 days including the thickness adjustment of each layer. The total number of each antireflection film-coated glass produced was visually observed for adhesion of surface debris and the presence or absence of defects in the laminated film. As a result, there was no product that was defective in production, and the defective product rate was 0 (zero).

Thus, it was confirmed that the glass with an antireflection film produced by the above-described method has few defects and a high yield can be obtained.

(Heat resistance evaluation)
Next, the heat resistance of the glass with an antireflection film according to one example of the present invention was evaluated.

As the sample for evaluation, the glass with an antireflection film having the vertical and horizontal dimensions of 100 inches × 144 inches manufactured in the above section (Productivity evaluation) was used. The glass with an antireflection film was heated to 650 ° C. in the air, and then cooled to room temperature by air blowing. The haze of the glass with an antireflection film before and after heating was measured with a haze measuring apparatus.

As a result of haze measurement, the haze of the glass with an antireflection film before heat treatment was 0.09%. On the other hand, the haze of the glass with an antireflection film after heat treatment was 0.35%, and it was found that the increase in haze was significantly suppressed even when heat treatment was performed. Thus, it was confirmed that the glass with an antireflection film manufactured by the above-described manufacturing method has good heat resistance.

[Example of glass article having antifouling performance]
Next, the Example of the glass article provided with the antifouling performance of this invention is described. In the following description, Examples 10 to 12 and Example 25 are examples of glass articles having antifouling performance, Examples 13 to 14 are reference examples, Examples 15 to 24, and Examples 26 is a comparative example.

(Formation of antifouling film)
(Preparation of Binder Precursor (1) (Desalted Sodium Silicate Solution))
While stirring 237.5 g of distilled water, sodium silicate No. 4 (manufactured by Nippon Chemical Industry Co., Ltd., (SiO ₂ : 24.0% by mass, Na ₂ O: 7.0% by mass. SiO ₂ / Na ₂ 62.5 g of O molar ratio: 3.5 / 1) and 180 g of cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd., Diaion SK1BH) were added in order, and the mixture was stirred for 10 minutes or more and then cation exchange resin by suction filtration. And a binder precursor (1) was obtained as a desalted sodium silicate solution having a solid content concentration in terms of silicon oxide of 5% by mass.

(Preparation of antifouling film forming composition)
While stirring 6.58 g of 2-propanol, 1.19 g of a pearl necklace-like silica dispersion (manufactured by Nissan Chemical Co., Snowtex PS-SO, average primary particle size 15 nm, average secondary particle size 88 nm), 2.18 g of the binder precursor (1) was added in order, the solid content in terms of silicon oxide was 2.95% by mass, in terms of silicon oxide between the particles (pearl necklace-like silica) and the binder precursor (desalted sodium silicate solution) An antifouling film-forming composition (A1) having a solid content mass ratio of 60/40 was prepared.

(Example 10)
A sample according to Example 5 kept at room temperature was set on a spin coater, 2.0 g of the antifouling film forming composition (A1) was dropped on the surface, spin-coated, and then baked at 300 ° C. for 30 minutes to obtain a glass article. Manufactured.

(Example 11 to Example 14)
Antifouling film-forming compositions A2 to A5 were prepared in the same manner as in Example 10 except that the mass ratio of particles to binder (particle / binder) was changed to the amount shown in Table 4. Subsequently, a glass article was produced in the same manner as in Example 10 using the antifouling film-forming compositions A2 to A5.

(Example 15 to Example 19)
The pearl necklace-like silica dispersion is changed to a spherical silica dispersion having an average primary particle size of 11 nm (manufactured by Nissan Chemical Co., Snowtex OS), and the mass ratio of the particles to the binder is changed to the amount shown in Table 4. Except for the above, antifouling film-forming compositions A6 to A10 were prepared in the same manner as in Example 10. Next, a glass article was produced in the same manner as in Example 10 using the antifouling film-forming compositions A6 to A10.

(Example 20 to Example 24)
The pearl necklace-like silica dispersion was changed to a spherical silica dispersion having a mean primary particle size of 30 nm (manufactured by Nissan Chemical Co., Ltd., Snowtex O-40), and the mass ratio of the particles to the binder was adjusted to the amounts shown in Table 4. Antifouling film-forming compositions A11 to A15 were prepared in the same manner as in Example 10 except for changing. Next, a glass article was produced in the same manner as in Example 10 using the antifouling film-forming compositions A11 to A15.

(Example 25)
(Preparation of binder precursor (2) (solution of partially hydrolyzed condensate of alkoxysilane compound))
While stirring 16.45 g of 2-propanol, 1.18 g of methyl silicate polymer (manufactured by Tama Chemical Industry Co., Ltd., M silicate 51, 51% solid content in terms of silica, methanol solvent), 2.26 g of distilled water. A 10% by mass aqueous nitric acid solution was added in order, and the mixture was stirred at 25 ° C. for 60 minutes to obtain a binder precursor (2) as a partially hydrolyzed condensate solution of an alkoxysilane compound having a silica-converted solid content concentration of 3% by mass. Got.

(Preparation of antifouling film forming composition)
An antifouling film-forming composition A16 was prepared in the same manner as in Example 10 except that the binder precursor (1) was changed to the binder precursor (2).

(Manufacture of glass articles)
A glass article was produced in the same manner as in Example 10 using the antifouling film-forming composition A16.

(Example 26)
The sample according to Example 5 was evaluated as it was.

(Evaluation of glass articles having antifouling performance)
Evaluation of the glass article in each example was performed as follows.

(Average primary particle size of particles)
From the image obtained by observing the surface of the antifouling film from above with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800) with respect to the surface of the glass article having the antifouling film, randomly 100 particles were extracted, and the average diameter of each particle was defined as the average primary particle diameter of the particles.

(Surface roughness (Ra))
It measured using the scanning probe microscope (SII nanotechnology company make, type SPA400).
(Setting conditions)
The cantilever was measured with SI-DF40 (with rear surface AL), 256 XY data, and scanning area of 10 μm × 10 μm.

(Vertex distance)
Randomly extracted in a direction parallel to the surface of the glass plate having the antifouling film from an image obtained by observing a cross section of the glass article with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800) In the range of 1.5 μm, with respect to the protrusion having the highest height from the surface of the glass plate, the distance between the vertices of adjacent protrusions is determined for the protrusion having a height of 90% or more of the height. All were measured and the average value was calculated.

(Convex coverage)
From the image obtained by observing the surface of the antifouling film from above with respect to the main surface of the substrate with a scanning electron microscope (manufactured by Hitachi, Ltd., model: S-4800), image conversion software (image J) The area ratio of the part to which particles adhered in the range of 1 μm × 1 μm extracted for the purpose was calculated.

(Stain adhesion test)
The glass article was cut into 5 cm × 5 cm, and the initial haze value was measured. Thereafter, 0.5 g of two types of JIS test powder 1 (silica sand having a median diameter of 27 to 31 μm) was sprinkled on the glass article evenly using a tea strainer. After standing for 10 seconds, the glass article was tilted 135 °, the edge of the substrate was brought into contact with the ground twice at a rate of 10 cm / second from a height of 3 cm, the powder was dropped, and the haze value was measured again. This was repeated 10 times, and the value obtained by subtracting the initial haze value from the average value of the 8th, 9th and 10th haze values was defined as the change in haze value (ΔHaze) after the dry sanding test.

Here, the antifouling film is sprinkled with the above-mentioned test powder, left still for 10 seconds, tilted 135 °, and brought into contact with the ground twice at a rate of 10 cm / second from a height of 3 cm, dropping the powder. It is preferable that the value obtained by subtracting the haze value before the test from the average value is within 1.0, more preferably within 0.9, more preferably within 0.8. It is particularly preferred.

(Measurement conditions of haze value)
The haze of the glass member was measured with a haze measuring device (Bic Gardner, model name: haze guard plus).

Table 4 below shows the specifications of the glass articles according to Examples 10 to 26.

Table 5 below shows the measurement evaluation results of the samples according to Examples 10 to 26.

As shown in Table 5, it can be seen that the glass articles of Examples 10 to 12 and Example 25 are excellent in antifouling property. On the other hand, Example 26 having no antifouling film was not sufficiently antifouling. The glass article of Example 13 in which the proportion of the area where particles are present on the surface of the antifouling film is less than 12%, and the glass article of Example 14 in which the percentage of the area is less than 7% is more resistant than Examples 10 to 12 and Example 25. Dirty was inferior. Further, the glass articles of Examples 15 to 24 using spherical silica and having a distance between apexes of the antifouling film of less than 100 nm were not sufficiently antifouling.

The glass article of the present invention can be used, for example, for glass with antireflection and antifouling films for buildings. The usage form is not limited to the form in which the antireflection and antifouling film is disposed only on one side of the glass substrate, and the form in which the antireflection and antifouling film is disposed on both sides of the glass substrate. For example, two glass substrates having antireflection and antifouling films disposed on only one side may be prepared and used as laminated glass. Alternatively, two glass substrates having antireflection and antifouling films disposed on both sides may be prepared to form a multilayer glass. Or you may arrange | position the film | membrane which has another effect in the other surface of the glass substrate in which the antireflection and antifouling film | membrane was arrange | positioned only on one side.

Since the glass article of the present invention has antifouling performance, window glass (for example, window glass for transportation equipment such as automobiles, railways, ships, airplanes, etc.), walls (for example, partitions, road walls, etc.), refrigerated Showcases, mirrors (for example, vanity mirrors, bathroom mirrors, etc.), optical equipment, tiles, toilets, bathtubs, bathroom walls, vanity tables, curtain walls, aluminum sashes, faucets, building boards, Can be used for lenses. Furthermore, when the glass article of the present invention has antireflection performance, antifouling performance, and antifogging performance, lenses such as glasses and cameras, window glass, car windshields, helmet shields, underwater glasses, and bathroom use This is useful for mirrors.

Claims

A glass substrate;
A laminated film disposed on the glass substrate and including a plurality of layers having different refractive indexes;
A glass article having an antireflection function, comprising an antifouling film disposed on the outermost layer of the laminated film and containing an aggregate of particles and a binder.
The glass article according to claim 1, wherein the outermost layer of the laminated film is composed of silica doped with zirconia.
The glass article according to claim 1 or 2, wherein an average primary particle diameter of the particles is 5 nm or more and 300 nm or less.
The glass article according to any one of claims 1 to 3, wherein the aggregate includes at least one selected from a chain-like particle aggregate in which a plurality of the particles are connected and a pearl necklace-like particle aggregate. .
The antifouling film has a plurality of protrusions including the aggregates of the particles and the binder, and the protrusion having the maximum height from the surface of the outermost layer of the laminated film among the plurality of protrusions. 5, in the protrusion T having a height of 90% or more, the average value of the distance between the vertices of the adjacent protrusions T is 100 nm or more and 1000 nm or less. The glass article according to item.
The glass article according to any one of claims 1 to 5, wherein a ratio of a total covered area by the particles to an area of an outermost layer of the laminated film is 12% or more and 100% or less.
The glass article according to any one of claims 1 to 6, wherein the particles are hydrophilic particles, and the binder is a hydrophilic binder.
The particles include at least one selected from silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide,
The glass article according to any one of claims 1 to 7, wherein the binder includes at least one selected from silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, and tin oxide.
The glass article according to any one of claims 1 to 8, wherein a nitrogen adsorption amount is 3.0 m 2 / g or more and 7.5 m 2 / g or less.
The antifouling film is sprinkled with two types of JIS test powder 1 (silica sand with a median diameter of 27 to 31 μm), left to stand for 10 seconds, tilted 135 °, and from a height of 3 cm to a speed of 10 cm / second. The value obtained by dropping the powder twice in contact with the ground and measuring the haze value a plurality of times and subtracting the haze value before the test from the average value is within 1.0. The glass article according to any one of 9.
When the reflected color in the standard illuminant D65, 10 degree field of view is expressed by the color coordinates (a * , b * ) of the L * a * b * color system, the reflected color is (0, 0), (20 , −20), (−15, −20), (−15, 10), and (0, 10) are located inside a pentagon having 5 points as vertices. The glass article according to item.
Forming a laminated film including a plurality of layers having different refractive indexes on a glass substrate;
Applying an antifouling film-forming composition containing an aggregate of particles and a binder precursor on the outermost layer of the laminated film to obtain a coating film of the antifouling film-forming composition;
Forming the antifouling film containing the aggregates of the particles and the binder by performing a treatment for curing the binder precursor on the coating film and forming a binder from the binder precursor. A method for producing a glass article.
The step of forming the laminated film includes
Providing the plurality of layers on the glass substrate;
Using a cylindrical magnetron sputtering method, the difference in visible light reflectance before and after the test immersed in an aqueous NaOH solution having a concentration of 0.1 kmol / m 3 heated to 90 ° C. for 2 hours on the plurality of layers was 0.4. The method for producing a glass article according to claim 12, further comprising: providing a protective layer that is within a range.
The average primary particle diameter of the particles is 5 nm or more and 300 nm or less,
The method for producing a glass article according to claim 12 or 13, wherein the aggregate includes at least one selected from a chain particle aggregate and a pearl necklace-like particle aggregate in which a plurality of the particles are connected.
The antifouling film forming composition contains the binder precursor so that the volume ratio of the particles to the binder in the antifouling film is 7/93 or more and 95/5 or less. The method for producing a glass article according to any one of 14.