Film-attached article and method for producing same

Abstract

Provided is a film-attached article 10 comprising a substrate 1 and a film 2 containing a silicon oxide on the substrate 1, wherein the film-attached article satisfies any one of the following (a) to (c). (a) Film thickness: less than or equal to 150 nm; Si–OH ratio: between 0.03 and 0.2, inclusive (b) Film thickness: greater than 150 nm and less than or equal to 400 nm; Si–OH ratio: between 0.07 and 0.3, inclusive (c) Film thickness: greater than 400 nm and less than or equal to 700 nm; an Si–OH ratio: between 0.15 and 0.5, inclusive The Si-OH ratio is the ratio of the peak intensity near 950 cm-1 attributed to a silanol group to the peak intensity near 1100 cm-1 attributed to a siloxane bond in Fourier transform infrared spectroscopy of the film.

Description

Film-attached article and method for manufacturing same

[0001] The present invention relates to a film-attached article including a substrate and a film containing silicon oxide.

[0002] A technology for forming a silicon oxide-containing film on a substrate by the sol-gel method is known. In the sol-gel method, silicon oxide having siloxane bonds (Si—O—Si) is produced through hydrolysis of a silicon compound having a hydrolyzable functional group such as an alkoxy group and dehydration condensation of the silanol groups (Si—OH) generated by the hydrolysis. The dehydration condensation is accelerated by heat treatment. An organic substance may be added to the silicon oxide-containing film.

[0003] Patent Document 1 discloses an organic-inorganic composite film produced by a sol-gel method. In Patent Document 1, in Fourier transform infrared spectroscopy (FT-IR) of the organic-inorganic composite film, a 950 cm sigma attributable to a silanol group was detected. -1 The peak intensity around 1100 cm is attributed to the siloxane bond. -1 The value normalized by the peak intensity around the Si-OH ratio is specified to be 0.25 or less (Claim 1). This normalized value is referred to as the "Si-OH ratio" in this specification. By developing siloxane bonds to the extent that the Si-OH ratio is 0.25 or less, the mechanical strength of the film increases. The film thickness of the organic-inorganic composite film in Patent Document 1 is greater than 0.25 μm and less than 5 μm (Claim 2). According to the examples in Patent Document 1, the Si-OH ratio increases with increasing film thickness, being 0.06 at a minimum film thickness of 460 nm (Example 1), 0.10 at a film thickness of 670 nm (Example 4), and 0.13 at a maximum film thickness of 2.88 μm (Example 3).

[0004] International Publication No. 2017 / 040258

[0005] In Patent Document 1, the improvement of the membrane is focused on the mechanical strength of the membrane, and other properties of the membrane are not considered. The present invention aims to improve the membrane from a viewpoint other than mechanical strength and to provide a novel membrane-attached article.

[0006] The present invention provides a film-attached article comprising a substrate and a film on the substrate, wherein the film contains silicon oxide, and satisfies any one of the following a) to c):

[0007] a) The film has a thickness of 150 nm or less and a Si—OH ratio of 0.03 to 0.2, b) The film has a thickness of more than 150 nm and 400 nm or less and a Si—OH ratio of 0.07 to 0.3, c) The film has a thickness of more than 400 nm and 700 nm or less and a Si—OH ratio of 0.15 to 0.5.

[0008] As described above, the Si—OH ratio was determined by measuring the film by Fourier transform infrared spectroscopy (FT-IR method) using a 1100 cm spectrum attributed to a siloxane bond. -1 The peak intensity around 950 cm attributed to silanol groups -1 The absorption peak attributable to siloxane bonds is, for example, in the range of 1000 to 1200 cm -1 The absorption peak attributable to the silanol group is, for example, at 860 to 970 cm -1 exists in.

[0009] From another viewpoint, the present invention provides a method for producing a film-attached article including a substrate and a film on the substrate, the method comprising performing a plasma treatment on a coating film on the substrate that contains a compound having a silanol group.

[0010] According to the present invention, a novel film-attached article is provided that includes a film containing silicon oxide.

[0011] FIG. 1 is a cross-sectional view showing an example of a film-attached article.

[0012] The present invention will be described in detail below, but the following description is not intended to limit the present invention to a specific embodiment. The present invention provides a film-attached article and a method for manufacturing the same in the following form. Hereinafter, the upper and lower limits of numerical values ​​can be arbitrarily combined to form a range. The "to" indicating a numerical range means that both ends are included. Therefore, for example, if lower limits of a or more and b or more are disclosed and upper limits of c or less and d or less are disclosed, all of the ranges a to c, a to d, b to c, and b to d can be read as such. Furthermore, numerical ranges for different targets can be arbitrarily combined. For example, if the above a, b, c, and d are all upper or lower limits for film thickness, the ranges e to f and g to h for the refractive index can be arbitrarily combined with all of the above four ranges for film thickness.

[0013] The first embodiment is a film-attached article comprising a substrate and a film on the substrate, wherein the film contains silicon oxide, and satisfies any one of a) to c) above.

[0014] The second embodiment is a film-attached article satisfying the above a). Specifically, the second embodiment comprises a substrate and a film on the substrate, the film containing silicon oxide, the film having a thickness of 150 nm or less, and a Fourier transform infrared spectroscopy of the film shows a peak of 1100 cm attributable to a siloxane bond. -1 The wave number assigned to the silanol group for the peak intensity around 950 cm -1 The ratio of the peak intensities around the peaks is 0.03 or more and 0.2 or less.

[0015] The third embodiment is a film-attached article satisfying the above b). Specifically, the third embodiment comprises a substrate and a film on the substrate, the film containing silicon oxide, the film having a thickness of more than 150 nm and not more than 400 nm, and in Fourier transform infrared spectroscopy of the film, a peak at 1100 cm attributed to a siloxane bond is detected. -1 The wave number assigned to the silanol group for the peak intensity around 950 cm -1 The ratio of the peak intensities around the peaks is 0.07 or more and 0.3 or less.

[0016] The fourth embodiment is a film-attached article satisfying the above c). Specifically, the fourth embodiment comprises a substrate and a film on the substrate, the film containing silicon oxide, the film having a thickness of more than 400 nm and not more than 700 nm, and in Fourier transform infrared spectroscopy of the film, a peak at 1100 cm attributed to a siloxane bond is detected. -1 The wave number assigned to the silanol group for the peak intensity around 950 cm -1 The ratio of the peak intensities around the peaks is 0.15 or more and 0.5 or less.

[0017] A fifth aspect is the film-attached article of any one of the first to fourth aspects, wherein the refractive index of the film at a wavelength of 550 nm is 1.80 or less.

[0018] A sixth aspect is the film-attached article of the fifth aspect, wherein the film has a refractive index of 1.70 or less at a wavelength of 550 nm.

[0019] A seventh aspect is the film-attached article of the sixth aspect, wherein the film has a refractive index of 1.48 or less at a wavelength of 550 nm.

[0020] An eighth aspect is the film-attached article of any one of the first to seventh aspects, wherein the refractive index of the film at a wavelength of 550 nm is 1.05 or more.

[0021] A ninth aspect is the film-attached article of the eighth aspect, wherein the refractive index of the film at a wavelength of 550 nm exceeds 1.48.

[0022] A tenth aspect is the film-attached article of any one of the first to ninth aspects, wherein the film has a refractive index B that is lower than the refractive index A after firing under conditions of 620°C and 600 seconds, where the refractive index A and the refractive index B are refractive indices at a wavelength of 550 nm.

[0023] An eleventh embodiment is the film-attached article of any one of the first to ninth embodiments, wherein the film has a refractive index B higher than the refractive index A after firing under conditions of 620°C and 600 seconds, where the refractive index A and the refractive index B are refractive indices at a wavelength of 550 nm.

[0024] A twelfth aspect is the film-attached article according to any one of the first to eleventh aspects, wherein the film is substantially free of carbon atoms.

[0025] A thirteenth aspect is the film-attached article according to any one of the first to eleventh aspects, wherein the film contains carbon atoms.

[0026] A fourteenth aspect is the film-attached article of any one of the first to thirteenth aspects, wherein the contact angle of water on the surface of the film is 30° or less.

[0027] A fifteenth aspect is a method for producing a film-attached article, comprising a substrate and a film on the substrate, the film containing silicon oxide, the method comprising performing a plasma treatment on a coating film on the substrate that contains a compound having a silanol group.

[0028] A sixteenth aspect is the manufacturing method of the fifteenth aspect, wherein the plasma treatment is an atmospheric pressure plasma treatment, and the atmospheric pressure plasma treatment is performed on the coating film while the substrate is being transported.

[0029] A seventeenth aspect is the manufacturing method of the fifteenth or sixteenth aspect, in which the plasma treatment is performed on the coating film containing at least one organic compound selected from the group consisting of polyhydric alcohols and hydroxyl group-containing organic substances having a boiling point of 120°C or higher.

[0030] An eighteenth aspect is the manufacturing method according to any one of the fifteenth to seventeenth aspects, further comprising applying a film-forming solution to the substrate to form the coating film.

[0031] An embodiment of the film-attached article will be described in more detail below with reference to the drawings. [Film-attached Article] Figure 1 shows a cross section of an example of the film-attached article of this embodiment. The film-attached article 10 comprises a substrate 1 and a film 2 formed on the substrate 1. The film contains silicon oxide. The substrate 1 and the film 2 will be described below.

[0032] (Substrate) In this embodiment, the substrate has the function of supporting the film, and there are no limitations on its shape or material as long as it can perform this function. The shape of the substrate is, for example, plate-like. The plate-like substrate may be a flat plate or a curved plate. The substrate may contain at least one selected from the group consisting of metal, resin, and inorganic compound. The substrate may contain a resin material or a glass material, or may be a resin plate or a glass plate. There are no particular limitations on the type of glass material or resin material, or the thickness of the substrate.

[0033] The substrate may have hydroxyl groups (OH groups) on its surface. The hydroxyl groups may exist as part of silanol groups. The substrate having hydroxyl groups on its surface may include the materials exemplified above. The hydroxyl groups may be present in a natural oxide layer on the surface of a metal substrate. A glass plate is one of the substrates having a surface rich in hydroxyl groups. The substrate having hydroxyl groups can be firmly bonded to the film by dehydration condensation with the silanol groups of the film.

[0034] (Film on Substrate) In this embodiment, the film contains silicon oxide. The film may contain silicon oxide as a main component. In this specification, "main component" means the component with the highest content by mass. The film may further contain a component other than silicon oxide, specifically a compound containing an element other than silicon. The compound containing an element other than silicon may be an oxide. Examples of elements other than silicon include Li, Na, K, Mg, Ca, Sr, Ba, Sc, Y, lanthanoid elements, Ti, Zr, V, Nb, Fe, Co, Ni, Zn, B, Al, In, Ge, Sn, and P.

[0035] The membrane may further contain carbon atoms (C) and may further contain an organic compound. The organic compound may be a polymer. An example of the polymer is a hydrophilic organic polymer. Specific examples of hydrophilic organic polymers are described in Patent Document 1. The organic compound may be something other than a polymer. An example of the organic compound is a polyhydric alcohol. Another example of the organic compound is a hydroxyl group-containing organic substance having a boiling point of 120°C or higher.

[0036] However, the film may be substantially free of carbon atoms. In this specification, "substantially free" means that the content is less than 1 atomic %. The carbon atom content can be measured by X-ray photoelectron spectroscopy (XPS) in combination with sputtering.

[0037] The silicon oxide in the film contains siloxane bonds. In addition to siloxane bonds, the film contains silanol groups. The ratio of silanol groups to siloxane bonds, i.e., the Si—OH ratio, can be measured by FT-IR. The silanol groups can contribute to improving adhesion to the substrate or other films. This contribution can be significant when the substrate or other films have functional groups, such as hydroxyl groups, that can react with silanol groups. The silanol groups can also contribute to improving the retention of substances in the film. This contribution can be significant when the substance to be retained in the film has polar groups, due to the interaction between the silanol groups and the polar groups. However, if there are excessive silanol groups, the mechanical strength of the film may be reduced.

[0038] The appropriate content of silanol groups in the film can be indicated by the Si—OH ratio. The appropriate Si—OH ratio varies depending on the thickness of the film. a) When the film thickness is 150 nm or less, the appropriate Si—OH ratio is 0.03 to 0.2, 0.05 to 0.2, even 0.07 to 0.17, and in some cases 0.10 to 0.15. b) When the film thickness is more than 150 nm but not more than 400 nm, the appropriate Si—OH ratio is 0.07 to 0.3, 0.1 to 0.3, even 0.15 to 0.3, and in some cases 0.2 to 0.25. c) When the film thickness is more than 400 nm but not more than 700 nm, the appropriate Si—OH ratio is 0.15 to 0.5, even 0.2 to 0.5, and in some cases 0.3 to 0.4. The lower limit of the film thickness in a) is not particularly limited, but is, for example, 5 nm or more, and further 10 nm or more. The film thickness in this embodiment is, for example, 5 to 700 nm.

[0039] In this embodiment, the film may have the following refractive index. Note that the refractive index is a value at a wavelength of 550 nm. A film with a low refractive index is useful for achieving desired optical effects such as anti-reflection and selective transmission. a) When the film thickness is 150 nm or less, the refractive index may be 1.80 or less, 1.70 or less, 1.60 or less, 1.55 or less, 1.50 or less, 1.49 or less, 1.48 or less, 1.47 or less, or even 1.46 or less. b) When the film thickness is greater than 150 nm and less than 400 nm, the refractive index may be 1.80 or less, 1.70 or less, 1.60 or less, 1.55 or less, 1.50 or less, 1.49 or less, or 1.48 or less. c) When the film thickness is greater than 400 nm and less than 700 nm, the refractive index may be 1.80 or less, 1.70 or less, 1.60 or less, 1.55 or less, 1.50 or less, or even 1.49 or less. The lower limit of the refractive index of the film is, for example, 1.05 or more, 1.20 or more, or even 1.35 or more. The lower limit of the refractive index of the film is 1.40 or more, 1.43 or more, and may be greater than 1.47, or in some cases greater than 1.48.

[0040] In this embodiment, the surface of the film may have a low water contact angle. The water contact angle is, for example, 30° or less, 15° or less, 10° or less, 7° or less, 5° or less, or even 4° or less, and in some cases 3° or less. Organic substances are less likely to adhere to a surface with a small water contact angle. The water contact angle may be, for example, 1° or more. Furthermore, a film-forming solution for overcoating easily wets and spreads on a surface with a small water contact angle. For these reasons, a film having a surface with a small water contact angle is suitable for ensuring adhesion with another film to be formed thereon.

[0041] In this embodiment, the film-attached article may have another film (overcoat) on the film. In this case, the film on the substrate is included as an undercoat film, and the film-attached article has a multilayer film. However, the present invention is not limited to this, and the film in the film-attached article may be a single-layer film.

[0042] In this embodiment, the film may have a refractive index B lower than the refractive index A after baking at 620°C for 600 seconds. Baking can be performed in an air atmosphere. The refractive index B of the film before baking may be lower than the refractive index A after baking by 0.01 or more, and even 0.02 or more. It is believed that baking collapses the voids in the film, increasing the density of the film and thereby increasing the refractive index. The relationship (refractive index B) < (refractive index A), particularly the relationship (refractive index A) - (refractive index B) ≥ 0.01 (or ≥ 0.02), indicates the presence of voids in the film that affect the refractive index.

[0043] However, in this embodiment, the film may have a refractive index B that is the same as or higher than the refractive index A after baking at 620°C for 600 seconds. For example, if the film before baking contains an organic substance with a high refractive index and that organic substance is removed from the film by baking, the refractive index may decrease due to baking. If this effect exceeds the effect of void removal associated with baking, the relationship (refractive index B) ≥ (refractive index A) will hold. This relationship may be expressed as (refractive index B) - (refractive index A) ≥ 0.01 (or ≥ 0.02).

[0044] [Method for manufacturing a film-attached article] In the manufacturing method of this embodiment, a plasma treatment is performed on a coating film containing a compound having silanol groups on a substrate. In conventional sol-gel methods, dehydration condensation of silanol groups occurs by heat treatment at a predetermined temperature. In contrast, in this embodiment, the plasma treatment causes dehydration condensation of silanol groups, and siloxane bonds are generated from some of the silanol groups.

[0045] The plasma treatment may be either a low-pressure plasma treatment or an atmospheric-pressure plasma treatment. However, atmospheric-pressure plasma treatment is superior in terms of mass productivity since it does not require a low-pressure device. Plasma treatment is also advantageous in that it enables film formation at low temperatures. As far as the inventors have investigated, plasma treatment, particularly atmospheric-pressure plasma treatment, is suitable for producing films with a relatively high Si—OH ratio.

[0046] Atmospheric pressure plasma treatment is also suitable for producing films with a low refractive index. This is because atmospheric pressure plasma treatment tends to remove organic matter from the film-forming solution, leaving voids in the film. Heat treatment is not suitable for removing organic matter while leaving voids. This is because heat treatment at high temperatures tends to crush voids due to internal stress in the film, while heat treatment at low temperatures leaves organic matter unremoved.

[0047] Therefore, according to this embodiment, it is possible to form a film containing silicon oxide that is substantially free of carbon atoms and has a refractive index of 1.48 or less at a wavelength of 550 nm. However, when the film is particularly thick, organic matter may remain in the film even after atmospheric pressure plasma treatment. The film according to this embodiment may contain carbon atoms.

[0048] The generation of voids due to the decomposition and disappearance of organic matter can be accentuated by adding an organic substance other than an organic solvent to the film-forming solution. Suitable organic substances other than organic solvents include polyhydric alcohols and / or organic compounds corresponding to hydroxyl-containing organic substances with a boiling point of 120°C or higher (hereinafter, these may be referred to as "polyhydric and / or high-boiling hydroxyl-containing organic compounds"). The boiling point of the hydroxyl-containing organic compound may be 150°C or higher, 200°C or higher, or even 250°C or higher. For example, glycerin is a polyhydric alcohol and also a hydroxyl-containing organic compound with a high boiling point (boiling point 290°C).

[0049] The upper limit of the boiling point of the hydroxyl group-containing organic compound may be, for example, 400° C. or less, 350° C. or less, or even 300° C. or less. When the base material contains a resin, the boiling point of the hydroxyl group-containing organic compound may be 120° C. or more and 350° C. or less, 150° C. or more and 300° C. or less, or even 150° C. or more and 250° C. or less.

[0050] It is believed that radicals generated by plasma are involved in the progress of dehydration condensation of silanol groups. Polyvalent and / or high-boiling hydroxyl-containing organic compounds may contribute to the promotion of dehydration condensation of silanol groups by capturing silanol groups through hydrogen bonding with the silanol groups and by releasing silanol groups through decomposition during atmospheric pressure plasma treatment.

[0051] Atmospheric pressure plasma treatment also has the following advantages. First, atmospheric pressure plasma treatment can decompose at least a portion, and in some cases, all, of organic substances such as surfactants that are sometimes added to film-forming solutions to improve film-forming properties. Here, improving film-forming properties specifically refers to controlling the wettability of the liquid and suppressing uneven appearance and defects. Organic substances used to improve film-forming properties are not limited to surfactants, but also include color-change inhibitors, antifoaming agents, and the like. These organic substances can be a factor in reducing the durability of the film. Furthermore, atmospheric pressure plasma treatment can decompose at least a portion, and in some cases, all, of residual organic groups contained in the film-forming solution. Residual organic groups are, for example, residual alkoxy groups contained in metal alkoxides, such as silicon alkoxides.

[0052] Second, atmospheric pressure plasma treatment makes it easier to suppress deformation of the substrate of a film-coated article. Removing organic matter by heating requires heat treatment at high temperatures, for example, around 600°C. Therefore, depending on the type of substrate, deformation, typified by warping, can become a problem. The deformation becomes more pronounced the larger the film thickness and the greater the associated film shrinkage, and the thinner the substrate and the more susceptible it is to shrinkage. Atmospheric pressure plasma treatment makes it possible to remove organic matter from the film while maintaining the film at a low temperature, for example, around 85°C or below, and therefore makes it possible to form a film while suppressing warping of the substrate. Incidentally, warping of the substrate is likely to be a problem, for example, with glass substrates.

[0053] The type of atmospheric pressure plasma is not particularly limited, but may be non-equilibrium plasma. The atmospheric pressure plasma may be plasma generated by dielectric barrier discharge. The exposure time to atmospheric pressure plasma depends on the film thickness and other conditions, but may be, for example, 90 seconds or less, or even 0.1 to 30 seconds, or in some cases, as short as 0.1 to 5 seconds. Because treatment can be performed in such a short time, atmospheric pressure plasma treatment greatly contributes to improving mass productivity.

[0054] Except for the use of atmospheric pressure plasma treatment instead of heating, the manufacturing method of this embodiment can be carried out in the same manner as a known sol-gel method. The preparation and application of the film-forming solution for forming the coating film may be carried out in accordance with known methods. A compound containing a silanol group or a compound capable of generating a silanol group upon hydrolysis is added to the film-forming solution. However, when atmospheric pressure plasma treatment is carried out, it is desirable that the film-forming solution contain the above-mentioned polyvalent and / or high-boiling hydroxyl-containing organic compound. Examples of the polyvalent and / or high-boiling hydroxyl-containing organic compound include glycerin, 1,1,1-tris(hydroxymethyl)ethane, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol, ethylene glycol, propylene glycol monomethyl ether, polyethylene glycol, polypropylene glycol, and polyoxyethylene tribenzyl phenyl ether.

[0055] The present invention will be described in more detail below with reference to examples and comparative examples. First, the film evaluation method will be described.

[0056] [Si-OH Ratio] The Si-OH ratio of the film was measured by forming a film on a silicon (Si) wafer under the same conditions as the film to be measured, and then performing Fourier transform infrared spectroscopy on the film. The device used was a PerkinElmer Frontier Gold Fourier transform infrared spectrophotometer. The measurement method was the transmission method, the reference was a Si wafer without a film formed thereon, the detector was a TGS detector, and the measurement range was 400 to 4000 cm -1 , resolution is 4cm -1 Based on the obtained spectrum, the 1100 cm corresponding to the siloxane bond was -1 The peak intensity around 950 cm attributed to silanol groups -1 The ratio of the peak intensities around the peak was calculated and used as the Si—OH ratio.

[0057] To ensure accuracy, the Si-OH ratio was measured using a silicon wafer as the substrate in the examples and comparative examples. However, it is also possible to measure the Si-OH ratio of a film formed on a glass plate in the same manner. In this case, a glass plate of the same type but without a film formed thereon is used as the reference. However, in this case, it is desirable to measure the ratio using the attenuated total reflection (ATR) method.

[0058] [Carbon Detection] While the film was being scraped by sputtering, XPS (X-ray photoelectron spectroscopy) was used to confirm the presence of carbon (carbon atoms) in the film. The conditions for XPS and sputtering were as follows: (XPS) - Apparatus: ULVAC-PHI PHI5000 Versa Probe III - X-ray anode: monochromatic microfocus Al Kα - Anode energy: 1486.6 eV (Al) - Beam size: φ100 μm - Anode power: 25 W - X-ray voltage: 15 kV - Stage angle: 45° (Sputtering) - Primary ion: Ar monomer ion - Acceleration voltage: 2 kV - Raster size: 2 mm x 2 mm - Sample rotation: Zalar rotation method - Sputtering rate: 4.8 nm / min (SiO2 film)

[0059] [Contact Angle of Water] The contact angle of water on the surface of the film was measured using a contact angle meter DMs-401 (manufactured by Kyowa Interface Science Co., Ltd.) with the amount of water dropped being 1.3 μL.

[0060] [Overcoat Formability] The film-forming solution used in Example 5 was applied to the film surface of a film-coated glass substrate by flow coating, and allowed to air dry for approximately 5 minutes. Then, a heat treatment was carried out at 290°C to form an overcoat film. The appearance (presence or absence of foreign matter) and the degree of adhesion (presence or absence of peeling) of the overcoat film were visually observed under a fluorescent lamp, and evaluated based on the following criteria: ◯: No foreign matter or film peeling ×: Foreign matter present, no film peeling XX: No foreign matter present, film peeling XXX: Both foreign matter present and film peeling

[0061] [Substance Supporting Ability Test] The supporting ability of organic compounds was evaluated based on the occurrence of bleed-out on the film surface after leaving the sample for a predetermined period of time in an environment of 23°C and 65% relative humidity. The presence or absence of bleed-out was visually observed under fluorescent light and evaluated based on the following criteria. However, this test was conducted on samples in which carbon was detected in the film. ◯: No bleed-out was observed even after leaving the sample for 20 days. ×: Bleed-out was observed after leaving the sample for 20 days. XX: Bleed-out was observed after leaving the sample for 1 day.

[0062] Example 1 A film-forming solution was obtained by mixing 3.472 g of tetraethoxysilane, 93.932 g of propylene glycol monomethyl ether, 0.025 g of concentrated hydrochloric acid (35% by mass), 2.099 g of pure water, and 0.472 g of glycerin and stirring the mixture for 4 hours at 20° C. Next, the film-forming solution was applied to a cleaned soda-lime silicate glass substrate (100 × 100 mm; thickness 1.1 mm; the size and thickness of the glass substrate are the same in the following Examples and Comparative Examples) by a flow coating method at 20° C. and a relative humidity of 30%, and then the mixture was allowed to air dry for about 5 minutes to obtain a glass substrate with a coating film.

[0063] The resulting coated glass substrate was subjected to atmospheric pressure plasma treatment using a 60 mm diameter plasma rotary spray gun with an output of 1000 W and an exposed opening only at the outermost periphery, using CDA (clean dry air) as the supply gas, to form a film containing silicon oxide on the glass substrate. The coated glass substrate was transported below the plasma rotary spray gun at a speed of 0.2 m / min. The distance between the exposed opening and the coating, i.e., the distance between the plasma irradiation device and the coating, was 3 mm.

[0064] Example 2 A film containing silicon oxide was formed in the same manner as in Example 1, except that the plasma irradiation in Example 1 was repeated four times.

[0065] Example 3 A film containing silicon oxide was formed in the same manner as in Example 1, except that the distance between the coating film and the plasma irradiation device in the plasma irradiation was set to 10 mm.

[0066] Example 4 A film containing silicon oxide was formed in the same manner as in Example 1, except that the silicon alkoxide concentration in terms of silica in the film-forming solution was set to 3 wt % so that the film thickness would be 300 nm.

[0067] Example 5 A film containing silicon oxide was formed in the same manner as in Example 1, except that the silicon alkoxide concentration in terms of silica in the film-forming solution was set to 5 wt % so that the film thickness would be 500 nm.

[0068] Comparative Example 1 A film containing silicon oxide was formed in the same manner as in Example 1, except that heating was applied instead of atmospheric pressure plasma irradiation. The heating temperature was 290°C.

[0069] Comparative Example 2 A film containing silicon oxide was formed in the same manner as in Comparative Example 1, except that the heating temperature was set to 620°C.

[0070] Comparative Example 3 A film containing silicon oxide was formed in the same manner as in Comparative Example 1, except that the silicon alkoxide concentration in terms of silica in the film-forming solution was set to 3 wt % so that the film thickness would be 300 nm.

[0071] Comparative Example 4 A film containing silicon oxide was formed in the same manner as in Comparative Example 1, except that the silicon alkoxide concentration in terms of silica in the film-forming solution was set to 5 wt % so that the film thickness would be 500 nm.

[0072] The results of the Examples and Comparative Examples, including the evaluation results of the membranes, are shown in Tables 1 and 2.

[0073]

[0074]

[0075] A Taber abrasion test was carried out on the film-attached articles obtained in Examples 1 to 3. This test was carried out in accordance with Japanese Industrial Standards (JIS) R 3212 under the conditions of a load of 500 g and 100 times. No film peeling was observed in any of the film-attached articles.

[0076] The film-coated articles obtained in Examples 1 to 4 were fired in an air atmosphere at 620°C for 600 seconds. Specifically, the film-coated articles were fired by being held in a furnace whose interior was maintained at 620°C for 600 seconds. Thereafter, the refractive index A was measured in the same manner as above, and the refractive index A was found to be higher by 0.01 or more than the refractive index B (see Table 1) before firing.

[0077] As described above, each example provided a film-attached article with improved properties. As shown in each example, the film-attached article according to this embodiment has an appropriate Si—OH ratio depending on the film thickness.

[0078] However, the film-attached article according to this embodiment can also be understood as follows: i) to iii).

[0079] i) A film-attached article comprising: a substrate; and a film on the substrate, wherein the film contains silicon oxide, preferably contains silicon oxide as a main component, and the contact angle of water on the surface of the film is 30° or less, 15° or less, 10° or less, preferably 5° or less.

[0080] In the above i), the refractive index may be 1.80 or less, 1.70 or less, 1.60 or less, 1.55 or less, 1.50 or less, 1.49 or less, 1.48 or less, 1.47 or less, 1.43 or less, or 1.40 or less. The lower limit of the refractive index is, for example, 1.05 or more, 1.20 or more, 1.35 or more, 1.40 or more, or even 1.43 or more, and may be greater than 1.47, or in some cases greater than 1.48.

[0081] ii) A film-attached article comprising a substrate and a film on the substrate, wherein the film contains silicon oxide, preferably contains silicon oxide as a main component, the film has a thickness of 250 nm or less, preferably 150 nm or less, and the film has a refractive index at a wavelength of 550 nm of 1.48 or less, 1.47 or less, preferably 1.46 or less, and more preferably 1.43 or less.

[0082] Preferred features of the above i) and ii) are as described in this specification. For example, the contact angle of water on the surface of the film may be 1° or more. The film may contain carbon atoms or may be substantially free of carbon atoms. The film thickness may be 5 nm or more. The upper limit of the film thickness in i) may be 700 nm or less, but is not limited thereto, and may be 3000 nm or less, 2000 nm or less, or even 1000 nm or less. However, in ii), the refractive index of the film may also be within the range determined by the upper and lower limits exemplified for i).

[0083] iii) A substrate and a film on the substrate, wherein the film contains silicon oxide, preferably silicon oxide as a main component, and a Fourier transform infrared spectroscopy analysis of the film shows a peak at 1100 cm attributed to a siloxane bond. -1 The wave number assigned to the silanol group for the peak intensity around 950 cm -1 A film-attached article, wherein the ratio of peak intensities near the peaks is 0.3 or more and 0.5 or less.

[0084] The preferred features of the above embodiment iii) are also as described herein. For example, the water contact angle on the film surface may be 1° to 30°, 1° to 15°, or even 1° to 10°, and the film thickness may be greater than 400 nm. The upper limit of the film thickness may be 700 nm or less, but may also be 5000 nm or less, 3000 nm or less, 2000 nm or less, or even 1000 nm or less.

Claims

1. A film-attached article comprising a substrate and a film on the substrate, wherein the film contains silicon oxide, and satisfies any one of the following a) to c). a) The film has a thickness of 150 nm or less and a Si—OH ratio of 0.03 to 0.2, b) The film has a thickness of more than 150 nm and 400 nm or less and a Si—OH ratio of 0.07 to 0.

3. c) The film has a thickness of more than 400 nm and not more than 700 nm, and an Si—OH ratio of 0.15 to 0.

5. The Si—OH ratio is determined by measuring the film by Fourier transform infrared spectroscopy, and the Si—OH ratio is determined by measuring the Si—OH ratio of 1100 cm attributable to siloxane bonds. -1 The peak intensity around 950 cm attributed to silanol groups -1 is the ratio of the peak intensities in the vicinity 2. The film-attached article according to claim 1, wherein the condition a) is satisfied.

3. The film-attached article according to claim 1, wherein the condition b) is satisfied.

4. The film-attached article according to claim 1, wherein the condition c) is satisfied.

5. The film-attached article according to claim 1, wherein the refractive index of the film at a wavelength of 550 nm is 1.80 or less.

6. The film-attached article according to claim 5, wherein the refractive index of the film at a wavelength of 550 nm is 1.70 or less.

7. The film-attached article according to claim 6, wherein the refractive index of the film at a wavelength of 550 nm is 1.48 or less.

8. The film-attached article according to claim 1, wherein the refractive index of the film at a wavelength of 550 nm is 1.05 or more.

9. The film-attached article according to claim 8, wherein the refractive index of the film at a wavelength of 550 nm exceeds 1.

48.

10. The film-attached article according to claim 1, wherein the film has a refractive index B that is lower than the refractive index A after baking at 620°C for 600 seconds, where the refractive index A and the refractive index B are refractive indices at a wavelength of 550 nm.

11. The film-attached article according to claim 1, wherein the film has a refractive index B higher than the refractive index A after baking at 620°C for 600 seconds, where the refractive index A and the refractive index B are refractive indices at a wavelength of 550 nm.

12. The film-attached article according to claim 1, wherein the film is substantially free of carbon atoms.

13. The film-attached article of claim 1, wherein the film comprises carbon atoms.

14. The film-attached article according to claim 1, wherein the contact angle of water on the surface of the film is 30° or less.

15. A method for producing a film-attached article comprising a substrate and a film on the substrate, the film containing silicon oxide, the method comprising performing a plasma treatment on a coating film on the substrate that contains a compound having a silanol group.

16. The manufacturing method according to claim 15, wherein the plasma treatment is an atmospheric pressure plasma treatment, and the atmospheric pressure plasma treatment is performed on the coating film while the substrate is being transported.

17. The manufacturing method according to claim 15, wherein the plasma treatment is carried out on the coating film containing at least one organic compound selected from the group consisting of polyhydric alcohols and hydroxyl-containing organic compounds having a boiling point of 120°C or higher.

18. The method of claim 15, further comprising applying a film-forming solution to said substrate to form said coating.

Images