CN107107543B

CN107107543B - Substrate with antifouling film

Info

Publication number: CN107107543B
Application number: CN201580058199.6A
Authority: CN
Inventors: 藤井健辅; 宫村贤郎; 桥本匡平
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2014-10-30
Filing date: 2015-10-27
Publication date: 2021-07-20
Anticipated expiration: 2035-10-27
Also published as: WO2016068112A1; JPWO2016068112A1; CN107107543A; TW201621001A; KR102378656B1; JP6642444B2; KR20170076660A; TWI675077B

Abstract

The present invention provides a substrate with a stain-proofing film, which is used by sequentially providing a stain-proofing film, an adhesive layer and a protective film on a main surface of a transparent substrate and removing the adhesive layer and the protective film, wherein the optical film thickness of the stain-proofing film in the state of providing the adhesive layer and the protective film is 10 nm-50 nm, and the optical film thickness of the stain-proofing film after removing the adhesive layer and the protective film is 3 nm-30 nm.

Description

Substrate with antifouling film

Technical Field

The present invention relates to a substrate with an antifouling film.

Background

Since a touch panel used in a smartphone, a tablet computer, a car navigation device, or the like contacts a finger of a person during use, dirt due to fingerprints, sebum, sweat, or the like is likely to adhere thereto. Further, when the dirt adheres, the dirt is hard to fall off, and a difference between a portion where the dirt adheres and a portion where the dirt does not adhere is conspicuous depending on a difference in scattering and reflection of light. Therefore, the touch panel having such dirt adhered thereto has a problem that visibility and appearance are impaired. Further, the same problems are pointed out in display glass, optical elements, sanitary equipment, and the like.

In order to solve such a problem, a method is known in which a substrate having an antifouling film formed of a fluorine-containing hydrolyzable silicon compound is used in a portion of the member or the device which is touched by a human finger. The antifouling film formed on the substrate is required to have high water repellency and oil repellency in order to suppress adhesion of dirt, and also required to have abrasion resistance against wiping of the adhered dirt.

As the stain-proofing film having water repellency and oil repellency, for example, patent document 1 discloses a cured film formed by modifying a 9:1 mixture of silane and a polymer containing a fluorooxyalkylene group with a polymer containing a fluorooxyalkylene group, and a glass substrate with a cured film. Patent document 2 discloses a glass substrate with an antifouling film, which is obtained by dry-coating a fluorine-containing dry coating agent diluted with a diluent and having a specific composition.

In order to prevent damage to the glass substrate with the anti-fouling film when the glass substrate with the anti-fouling film is transported after being manufactured as described above, the following operations are performed: a protective film is provided on the surface of an antifouling film formed on a glass substrate via an adhesive layer. The adhesive layer and the protective film are removed when the glass substrate with the antifouling film is used for an article.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-136833

Patent document 2: japanese patent laid-open publication No. 2013-244470

Disclosure of Invention

The following are some cases of conventional glass substrates with antifouling films: when the adhesive layer and the protective film are removed, a part of the antifouling film is peeled off from the glass substrate together with the adhesive layer, and the antifouling property and abrasion resistance of the glass substrate with the antifouling film, such as water repellency and oil repellency, are reduced.

The invention aims to provide a substrate with an antifouling film, which has excellent antifouling property and abrasion resistance after an adhesive layer and a protective film are removed.

The substrate with a stain-proofing film of the present invention is a substrate with a stain-proofing film used by sequentially providing a stain-proofing film, an adhesive layer and a protective film on a main surface of a transparent substrate and removing the adhesive layer and the protective film, wherein the optical film thickness of the stain-proofing film in a state of providing the adhesive layer and the protective film is 10nm to 50nm, and the optical film thickness of the stain-proofing film after removing the adhesive layer and the protective film is 3nm to 30 nm.

The substrate with a stain-proofing film of the present invention is a substrate with a stain-proofing film used by sequentially providing a stain-proofing film, an adhesive layer and a protective film on a main surface of a transparent substrate and removing the adhesive layer and the protective film, wherein an optical film thickness of the stain-proofing film after removing the adhesive layer and the protective film is 3nm to 30nm, and a change rate represented by { (optical film thickness of the stain-proofing film in a state of providing the adhesive layer and the protective film) - (optical film thickness of the stain-proofing film after removing the adhesive layer and the protective film) } × 100/(optical film thickness of the stain-proofing film in a state of providing the adhesive layer and the protective film) (%) is 10 to 60%.

The present invention can provide a substrate with an antifouling film, which has excellent antifouling properties and abrasion resistance after removal of an adhesive layer and a protective film.

Drawings

FIG. 1 is a sectional view showing one embodiment of a substrate with an antifouling film according to the present invention.

Fig. 2 is a sectional view showing the antifouling film after the adhesive layer and the protective film are removed.

Fig. 3 is a view schematically showing an apparatus that can be used in an embodiment of the method for producing a substrate with an antifouling film according to the present invention.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described. The present invention is not limited to the following embodiments. Various modifications and substitutions may be made to the embodiments described below without departing from the scope of the present invention.

[ substrate with antifouling film ]

FIG. 1 is a sectional view showing one embodiment of a substrate with an antifouling film according to the present invention. The substrate 1 with an antifouling film (also referred to as an antifouling body) of the embodiment includes a transparent substrate 2 and an antifouling film 3 formed on a main surface of the transparent substrate 2. The substrate 1 with the antifouling film further includes an adhesive layer 4 provided removably on the surface of the antifouling film 3, and a protective film 5 provided removably on the surface of the adhesive layer 4. The optical thickness of the antifouling film 3 in the state where the adhesive layer 4 and the protective film 5 are provided, in other words, the optical thickness of the antifouling film 3 before the adhesive layer 4 and the protective film 5 are removed, is 10nm to 50 nm.

The substrate 1 with the antifouling film is used by removing the adhesive layer 4 and the protective film 5. Fig. 2 is a sectional view showing the antifouling film 3a after the adhesive layer 4 and the protective film 5 are removed. In FIG. 2, the optical thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 is 3nm to 30 nm. The optical film thickness of the antifouling film 3a after the removal of the adhesive layer 4 and the protective film 5 is smaller than the optical film thickness of the antifouling film 3 before the removal of the adhesive layer 4 and the protective film 5.

In the substrate 1 with an antifouling film, the antifouling film 3, the adhesive layer 4, the protective film 5, and an antireflection film described later may be provided on at least one main surface of the transparent substrate 2, or may be provided on both main surfaces of the transparent substrate 2 as necessary.

The antifouling film 3 is formed by, for example, a hydrolytic condensation reaction of a fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2 as follows, and has antifouling properties such as water repellency and oil repellency. In the present specification, the fluorine-containing hydrolyzable silicon compound means a compound having a hydrolyzable silyl group in which a hydrolyzable group or atom is bonded to a silicon atom and further having a fluorine-containing organic group bonded to the silicon atom. In addition, a hydrolyzable group or atom bonded to a silicon atom to constitute a hydrolyzable silyl group is referred to as a hydrolyzable group.

That is, the hydrolyzable silyl group of the fluorine-containing hydrolyzable silicon compound is hydrolyzed to form a silanol group, and the silanol group is subjected to dehydration condensation between the fluorine-containing hydrolyzable silicon compounds to form a siloxane bond represented by-Si-O-Si-, thereby forming the antifouling film 3. Most of the fluorine-containing organic groups bonded to the silicon atoms constituting the siloxane bond are present in the vicinity of the surface of the antifouling film 3 due to the affinity of the fluorine-containing hydrolyzable silicon compound with the transparent substrate 2. Therefore, the water repellency and oil repellency are exhibited on the surface of the antifouling film 3 by the action of the fluorine-containing organic group. For example, in the case of using a glass substrate as the transparent substrate 2, the silanol group of the fluorine-containing hydrolyzable silicon compound generated by hydrolysis and the hydroxyl group present on the surface of the transparent substrate 2 undergo a dehydration condensation reaction, and the antifouling film 3 is formed on the transparent substrate 2 via a siloxane bond.

In order to protect the antifouling film 3, a protective film 5 is provided on the thus-formed antifouling film 3 via an adhesive layer 4. When the substrate 1 with the antifouling film is used, the adhesive layer 4 and the protective film 5 are removed. When removing the adhesive layer 4 and the protective film 5, the fluorine-containing hydrolyzable silicon compound constituting a part of the surface of the antifouling film 3 is inevitably removed from the antifouling film 3 together with the adhesive layer 4.

Therefore, the antifouling film 3 is formed so that the optical thickness of the antifouling film 3 at the time of formation, in other words, the optical thickness of the antifouling film 3 before removal of the adhesive layer 4 and the protective film 5 is 10nm to 50 nm. When the adhesive layer 4 and the protective film 5 are provided on the surface of the antifouling film 3 having such an optical thickness and the adhesive layer 4 and the protective film 5 are removed, the fluorine-containing hydrolyzable silicon compound that forms the vicinity of the surface of the antifouling film 3 and is not bonded to the transparent substrate 2 adheres to the adhesive layer 4 and is removed. As a result of removing a part of the fluorine-containing hydrolyzable silicon compound constituting the antifouling film 3, the optical film thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 becomes 3nm to 30 nm.

Conventionally, the optical film thickness of the antifouling film before the removal of the adhesive layer and the protective film is set to an optimum film thickness of the antifouling film at the time of use, in other words, after the removal of the adhesive layer and the protective film. That is, the optical film thickness of the antifouling film before the removal of the adhesive layer and the protective film is an optimum film thickness. Then, since the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film is removed from the transparent substrate together with the adhesive layer, the optical film thickness of the antifouling film after removing the adhesive layer and the protective film is sometimes smaller than the optimum film thickness, and the antifouling property and abrasion resistance of the antifouling film are sometimes deteriorated. In contrast, the antifouling film 3 constituting the antifouling film-coated substrate 1 of the present embodiment is set so that the optical thickness of the antifouling film 3a after the adhesive layer 4 and the protective film 5 are removed is optimal. That is, the optical film thickness of the antifouling film 3a after the adhesive layer 4 and the protective film 5 are removed is an optimum film thickness. In this way, even if a part of the fluorine-containing hydrolyzable silicon compound constituting the antifouling film 3 is removed together with the adhesive layer 4, the antifouling film 3a can maintain good antifouling property and wear resistance because the optical thickness of the antifouling film 3a is optimal.

Hereinafter, each element constituting the substrate 1 with the antifouling film of the embodiment will be described.

(transparent substrate)

The transparent substrate 2 constituting the substrate 1 with the antifouling film is not particularly limited as long as it is a transparent substrate made of a transparent material to which antifouling property is required to be imparted by the antifouling film 3, and is preferably made of glass, resin, or a combination thereof (composite material, laminate material, or the like), for example. The form of the transparent substrate 2 is not particularly limited, and may be, for example, a rigid plate or a flexible film.

Examples of the resin substrate used as the transparent substrate 2 include an acrylic resin substrate such as polymethyl methacrylate, an aromatic polycarbonate resin substrate such as a carbonate of bisphenol a, and an aromatic polyester resin substrate such as polyethylene terephthalate.

Examples of the polymer film used as the film-shaped transparent substrate 2 include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride films, acrylic resin films, polyether sulfone films, polyarylate films, and polycarbonate films.

Examples of the glass substrate used as the transparent substrate 2 include a glass substrate made of a general glass containing silica as a main component, for example, soda-lime-silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, quartz glass, and the like.

When glass is used as the material of the transparent substrate 2, the glass preferably has a composition that is formable and can be strengthened by chemical strengthening treatment, and preferably contains sodium. As such glass, for example, aluminosilicate glass, soda-lime-silicate glass, borosilicate glass, lead glass, alkali barium glass, aluminoborosilicate glass, and the like are preferable.

The composition of the glass used as the material of the transparent substrate 2 is not particularly limited, and glasses having various compositions can be used. The composition of the glass includes, for example, the following compositions of glasses (all aluminosilicate glasses).

(i) Contains 50 to 80% of SiO in terms of a composition expressed by mol%₂2 to 25% of Al₂O₃0 to 10% of Li₂O, 0-18% of Na₂O, 0 to 10% of K₂O, 0-15% of MgO, 0-5% of CaO and 0-5% of ZrO₂Glass of

(ii) Contains 50 to 74% of SiO in terms of a composition expressed by mol%₂1 to 10% of Al₂O₃6 to 14% of Na₂O, 3-11% of K₂O, 2-15% of MgO, 0-6% of CaO and 0-5% of ZrO₂And SiO₂And Al₂O₃The total content of (A) is 75% or less, Na₂O and K₂Glass having a total content of O of 12 to 25% and a total content of MgO and CaO of 7 to 15%

(iii) Contains 68 to 80% of SiO in terms of a composition expressed by mol%₂4 to 10% of Al₂O₃5 to 15% of Na₂O, 0 to 1% of K₂O, 4-15% of MgO and 0-1% of ZrO₂Glass of

(iv) Contains 67 to 75% of SiO in terms of a composition expressed by mol%₂0 to 4% of Al₂O₃7-15% of Na₂O, 1-9% of K₂O, 6 to 14% of MgO and 0 to 1.5% of ZrO₂And SiO₂And Al₂O₃The total content of (a) is 71-75%, and Na₂O and K₂Glass containing 12 to 20% of total O and less than 1% of CaO when CaO is contained

Further, as the composition of the glass used as the material of the transparent substrate 2, the following compositions of glasses (all soda-lime-silicate glasses) can be cited.

(v) Contains 65 to 75% of SiO in terms of a composition expressed by mol%₂0.1 to 5% of Al₂O₃1 to 15% of MgO, 1 to 15% of CaO,Na₂O and K₂O, and Na₂O and K₂Glass containing 10 to 18% of total O.

(vi) Contains 65 to 72% of SiO in terms of a composition expressed by mol%₂2 to 7% of Al₂O₃5-15% of MgO, 3-9% of CaO, 13-18% of Na₂O, 0 to 1% of K₂O, 0-0.2% TiO₂0.01 to 0.15% of Fe₂O₃And 0.02-0.4% of SO₃And (Na)₂O and K₂Sum of O content)/(Al₂O₃Content of) 3.5 to 6.0.

(vii) Contains 60 to 72% of SiO in terms of a composition expressed by mol%₂1 to 10% of Al₂O₃5 to 12% of MgO, 0.1 to 5% of CaO, 13 to 19% of Na₂O and 0 to 5% of K₂O, and (content of RO)/(RO and R)₂The total content of O) is 0.20 to 0.42 (wherein RO represents an alkaline earth metal oxide, and R represents₂O represents an alkali metal oxide).

Hereinafter, the content of each component contained in the glass is shown in mol%.

SiO₂Is a component constituting the skeleton of the glass. Further, the component for reducing the occurrence of cracks when a flaw (indentation) is applied to the glass surface is a component for reducing the breakage rate when an indentation is applied to the glass surface after chemical strengthening, and is also a component for reducing the thermal expansion coefficient. SiO 2₂The content of (b) is preferably 50% or more, more preferably 60% or more, further preferably 64% or more, and particularly preferably 66% or more. By SiO₂The content of (b) is 50% or more, and the glass can be prevented from being deteriorated in stability, acid resistance, weather resistance and chipping resistance. On the other hand, SiO₂The content of (b) is preferably 80% or less, more preferably 75% or less, and further preferably 70% or less. By SiO₂The content of (b) is 80% or less, and a decrease in meltability due to an increase in viscosity of the glass can be avoided.

Al₂O₃Is effective for improving ion exchange performance and chipping resistanceThe component (b) is a component that increases the surface compressive stress, and is also a component that does not easily increase the thermal expansion coefficient at or above the glass transition point. Al (Al)₂O₃The content of (b) is preferably 0.1% or more, more preferably 2% or more, further preferably 3% or more, and particularly preferably 5% or more. In addition, Al₂O₃The content of (b) is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. By Al₂O₃The content of (b) is 0.1% or more, and the ion exchange performance and the chipping resistance can be improved. On the other hand, by Al₂O₃The content of (b) is 20% or less, and a decrease in meltability due to an increase in viscosity of the glass can be avoided.

MgO is a component for stabilizing glass and is also a component necessary for maintaining a thermal expansion coefficient appropriately. The content of MgO is preferably 1% or more, more preferably 2% or more, 3% or more, 4% or more, 5% or more, or 8% or more (particularly preferably 8% or more). The content of MgO is preferably 15% or less, more preferably 14% or less, 13% or less, 12% or less, 11% or less, and 10% or less (particularly preferably 10% or less). When the content of MgO is 1% or more, the meltability at high temperature becomes good, and devitrification is hardly caused. On the other hand, when the MgO content is 15% or less, devitrification is not easily caused and a sufficient ion exchange rate can be obtained.

CaO is a component that improves the meltability of glass, and is also a component effective for maintaining a thermal expansion coefficient appropriately. The content of CaO is preferably 0.05% or more, more preferably 0.1% or more, further preferably 1% or more, and particularly preferably 4% or more. On the other hand, the content of CaO is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less. The meltability can be improved by the content of CaO being 0.05% or more, and the surface compression stress layer can be made deeper by the content of CaO being 10% or less.

Na₂O is a component that forms a surface compressive stress layer by ion exchange, and is also a component that improves the meltability of the glass. Na (Na)₂O is a component having a large thermal expansion coefficient even when the density of the glass is low, and therefore, adjustment is madeThe coefficient of thermal expansion is significant. Na (Na)₂The content of O is preferably 10% or more, more preferably 11% or more, further preferably 12% or more, and particularly preferably 13% or more. On the other hand, Na₂The content of O is preferably 19% or less, more preferably 18% or less, further preferably 16% or less, and particularly preferably 15% or less. Through Na₂The content of O is 10% or more, a desired surface compression stress layer can be formed by ion exchange, and Na passes through₂When the content of O is 19% or less, the deterioration of weather resistance and acid resistance can be avoided, and the occurrence of cracks due to indentation can be avoided.

K₂O may be contained as needed, and the content thereof is preferably 0.1% or more. K₂When the content of O is 0.1% or more, the glass can maintain the high-temperature melting property and the appropriate thermal expansion coefficient. K₂The content of O is more preferably 0.5% or more, still more preferably 1% or more, and particularly preferably 2% or more. In addition, K₂The content of O is preferably 8% or less. If K₂When the content of O is 8% or less, the density of the glass becomes low and the weight of the glass becomes low. K₂The content of O is more preferably 6% or less, and still more preferably 4% or less.

Fe₂O₃Is a component for improving the meltability of glass. In general, Fe in glass₂O₃Visible light is absorbed, but in the case of glass having a small thickness, the absorption of light is reduced, and therefore, this is not likely to be a problem. In addition, Fe has an effect of increasing the high-temperature thermal expansion coefficient (α max). Further, since Fe is a component that absorbs heat rays, it has effects such as promoting thermal convection of a glass melt to improve homogeneity of the glass, and preventing a bottom brick of a melting furnace from being heated to extend a furnace life. Fe₂O₃The content of (b) is preferably 0.005% or more, more preferably 0.01% or more, still more preferably 0.03% or more, and particularly preferably 0.06% or more. On the other hand, if it is excessively contained, Fe₂O₃The color tone produced is a problem, therefore, Fe₂O₃Is preferably less than 0.2%,more preferably less than 0.15%, still more preferably less than 0.12, and particularly preferably less than 0.095.

The method for producing the glass substrate is not particularly limited, and the glass substrate can be produced by: a desired glass raw material is continuously charged into a melting furnace, the glass raw material is heated and melted at preferably 1500 to 1600 ℃ and is clarified, and then the molten glass is supplied to a molding device, molded into a sheet shape, and slowly cooled.

The method of forming the glass substrate is not particularly limited, and for example, a down-draw method (e.g., an overflow down-draw method, a slobbering down-draw method, a redraw method, etc.), a float method, a roll-out method, a press method, and the like can be used.

The thickness of the transparent substrate 2 may be appropriately selected depending on the purpose. For example, when the transparent substrate 2 such as a resin substrate or a glass substrate is plate-shaped, the thickness of the transparent substrate 2 is preferably 0.1 to 5mm, and more preferably 0.2 to 2 mm. In particular, when a chemical strengthening treatment described later is performed using a glass substrate as the transparent substrate 2, and the purpose is to reduce the weight, the thickness of the glass substrate is preferably 5mm or less, and more preferably 3mm or less, in order to efficiently perform the chemical strengthening treatment and the reduction in weight. When the glass substrate is used for a touch panel for a portable electronic device such as a smartphone or a tablet computer, since weight reduction is particularly important, the thickness of the glass substrate is more preferably 1mm or less, and particularly preferably 0.7mm or less. On the other hand, when the touch panel is used for a touch panel for an in-vehicle electronic device such as a car navigation system, the thickness of the glass substrate is more preferably 0.7mm or more, particularly preferably 1.0mm or more, because rigidity is regarded more important than weight reduction.

When the transparent substrate 2 such as a polymer film is in the form of a film, the thickness of the transparent substrate 2 is preferably 50 to 200 μm, and more preferably 75 to 150 μm.

When a glass substrate is used as the transparent substrate 2, the main surface of the glass substrate may be subjected to surface treatment by oxygen plasma. Further, a silicon oxide film may be formed on the main surface of the glass substrate by sputtering or the like. When the antiglare treatment and the chemical strengthening treatment are performed as described below, these treatments are preferably performed after the antiglare treatment and the chemical strengthening treatment.

(anti-dazzle treatment)

In order to impart antiglare properties to the substrate 1 with an antifouling film, the main surface of the transparent substrate 2 preferably has a concavo-convex shape.

As a method of forming the concave-convex shape, an anti-glare treatment can be used. The antiglare treatment is not particularly limited, and for example, when a glass substrate is used as the transparent substrate 2, a method of forming an uneven shape having a desired surface roughness by chemically or physically surface-treating a main surface of the glass substrate can be used.

Examples of the method of performing the chemical antiglare treatment include a method of performing a sanding treatment (フロスト processing). The frosting treatment can be performed by, for example, immersing a glass substrate as a treatment object in a mixed solution of hydrogen fluoride and ammonium fluoride.

As a method of performing the physical antiglare treatment, for example, there is a method of blowing a crystalline silica powder, a silicon carbide powder, or the like to the main surface of the glass substrate with pressurized air, so-called blast treatment, wetting a brush to which the crystalline silica powder, the silicon carbide powder, or the like is attached with water, and rubbing the main surface of the glass substrate with the wetted brush.

Among them, the frosting treatment as the chemical surface treatment is preferably used as a method for surface treatment of a glass substrate because microcracks are less likely to occur on the surface of the treated body and a reduction in mechanical strength is less likely to occur.

In order to modify the surface shape, it is preferable to perform etching treatment on the main surface of the glass substrate subjected to the chemical or physical antiglare treatment. As the etching treatment, for example, a method of immersing the glass substrate in an etching solution which is an aqueous solution of hydrogen fluoride to perform chemical etching can be used. The etching solution may contain an acid such as hydrochloric acid, nitric acid, or citric acid in addition to hydrogen fluoride. By containing these acids, local generation of precipitates on the surface of the glass matrix due to the reaction between a cationic component such as Na ions or K ions contained in the glass matrix and hydrogen fluoride can be suppressed, and the surface of the glass matrix can be uniformly etched.

In the etching treatment, the etching amount can be adjusted by changing the concentration of the etching solution, the immersion time of the glass substrate in the etching solution (hereinafter also referred to as "etching time"), and the like. This makes it possible to adjust the haze value of the surface having irregularities (hereinafter also referred to as "antiglare surface") of the glass substrate to a desired value. In addition, when the antiglare treatment is performed by a physical surface treatment such as a sandblasting treatment, cracks may occur in the transparent substrate 2, but such cracks can be removed by an etching treatment. The depth of the crack in the plane is preferably 5 μm or less, more preferably 3 μm or less, at the maximum. When the amount is within this range, the reduction in fracture strength due to in-plane cracking can be sufficiently suppressed. The in-plane crack depth can be measured as follows. First, a plurality of (e.g., 5) transparent substrates having the same property are prepared. Next, the main surface of each transparent substrate was polished by using cerium oxide abrasive grains while changing the polishing amount stepwise. The polishing amount is, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm. Then, when the main surface of the transparent substrate is etched a little with a 1 mol% HF aqueous solution, the remaining cracks are easily observed. The crack depth was measured by confirming that the crack trace remained after polishing to several μm with an optical microscope (VK-X120 manufactured by KEYENCE). That is, if no crack trace remains when the polishing amount is 5 μm, the crack depth can be said to be 5 μm or less. Further, the effect of suppressing glare (ギラツキ) of the substrate 1 with the antifouling film can be obtained by the etching treatment.

In this manner, the shape of the main surface of the glass substrate after the antiglare treatment and the etching treatment is preferably 0.01 to 0.5 μm, more preferably 0.01 to 0.3 μm, and still more preferably 0.01 to 0.2 μm in surface roughness (root mean square Roughness (RMS)). When the surface Roughness (RMS) is in the above range, the haze value of the glass substrate after the antiglare treatment can be adjusted to 3 to 30%. As a result, excellent antiglare properties can be imparted to the substrate 1 with an antifouling film obtained.

Note that the surface Roughness (RMS) may be measured according to JIS B0601: (2001) the measurement was carried out by the method defined in (1). Specifically, a laser microscope (VK-9700, manufactured by KEYENCE) was used to measure the surface Roughness (RMS) of the glass substrate, which was a sample, with a visual field of 300 μm 200 μm set on the measurement surface of the glass substrate after the antiglare treatment, and the height information of the glass substrate was measured. The surface Roughness (RMS) can be calculated by correcting the measurement value by cutoff (cutoff) and obtaining the root mean square of the obtained height. As the cutoff value, 0.08mm is preferably used.

The haze value is a value measured according to the method defined in JIS K7136.

The surface of the glass substrate after the antiglare treatment and the etching treatment has an uneven shape, and when the uneven shape is observed from above the surface of the glass substrate, a circular hole is observed. The size (diameter) of the circular pores thus observed is preferably 1 μm to 10 μm. When the amount is in such a range, both antiglare properties and antiglare properties can be achieved.

When a glass substrate is used as the transparent substrate 2, it is preferable to perform chemical strengthening treatment on the main surface and the antiglare treated surface of the glass substrate in order to improve the strength of the substrate 1 with an antifouling film obtained.

The method of the chemical strengthening treatment is not particularly limited, and a surface layer in which a compressive stress remains is formed on the main surface of the glass substrate and the antiglare treated surface by performing an ion exchange treatment on these surfaces. Specifically, at a temperature equal to or lower than the glass transition point, alkali metal ions having a small ionic radius (for example, Li ions and Na ions) contained in the vicinity of the main surface and the antiglare surface of the glass substrate are replaced with alkali metal ions having a larger ionic radius (for example, Na ions and K ions for Li ions and K ions for Na ions). This causes a compressive stress to remain on the main surface or the antiglare treated surface of the glass substrate, thereby improving the strength of the glass substrate.

(anti-reflection film)

The substrate 1 with the antifouling film may be provided with an antireflection film between the transparent substrate 2 and the antifouling film 3. When the transparent substrate 2 has the above-described uneven shape, it is preferable to provide an antireflection film on the antiglare treated surface.

The structure of the antireflection film is not particularly limited as long as it can suppress reflection of light, and for example, a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550nm may be laminated.

The antireflection film may include 1 high refractive index layer and 1 low refractive index layer, respectively, or may include 2 or more high refractive index layers and 2 or more low refractive index layers, respectively. When the antireflection film includes 2 or more high refractive index layers and 2 or more low refractive index layers, the antireflection film is preferably in a form in which the high refractive index layers and the low refractive index layers are alternately laminated.

In particular, in order to improve the antireflection performance, the antireflection film is preferably a laminate in which a plurality of layers are laminated, and for example, the laminate is preferably a laminate in which 2 or more and 6 or less layers, and more preferably 2 or more and 4 or less layers are laminated. The laminate herein is preferably a laminate in which a high refractive index layer and a low refractive index layer are laminated, and the number of layers obtained by summing the numbers of layers of the high refractive index layer and the low refractive index layer is preferably in the above range.

The material of the high refractive index layer and the low refractive index layer is not particularly limited, and may be selected in consideration of the degree of antireflection performance required, productivity, and the like. As the material constituting the high refractive index layer, for example, a material selected from niobium oxide (Nb)₂O₅) Titanium oxide (TiO)₂) Zirconium oxide (ZrO)₂) Tantalum oxide (Ta)₂O₅) And silicon nitride (SiN). As the material constituting the low refractive index layer, it is preferable to use a material selected from silicon oxide (SiO)₂) And 1 or more of a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and a material containing a mixed oxide of Si and Al.

From the viewpoint of productivity and refractive index, it is more preferable that the high refractive index layer is a niobium oxide layer, a tantalum oxide layer, or a silicon nitride layer, and the low refractive index layer is a silicon oxide layer.

The method for forming the antireflection film is not particularly limited, and various film forming methods can be used. Particularly, the film formation is preferably performed by a method such as pulse sputtering, AC sputtering, or digital sputtering. By using these methods, a dense film can be formed, and durability can be ensured.

For example, when the film formation is performed by the pulse sputtering, the transparent substrate 2 is disposed in a chamber in a mixed gas atmosphere of an inert gas and an oxygen gas, and the target is selected so as to have a desired composition, thereby forming the antireflection film.

In this case, the gas type of the inert gas in the chamber is not particularly limited, and various inert gases such as argon gas and helium gas can be used.

The pressure in the chamber by the mixed gas of the inert gas and the oxygen gas is not particularly limited, but is preferably 0.5Pa or less because the surface roughness of the antireflection film can be easily made to be in the above-described preferred range. This is because if the pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is 0.5Pa or less, the mean free path of the film-forming molecules can be secured, and the film-forming molecules have more energy and reach the transparent substrate 2. Therefore, rearrangement of film-forming molecules is promoted, and a dense film having a smooth surface can be formed. The lower limit of the pressure in the chamber by the mixed gas of the inert gas and the oxygen gas is not particularly limited, and is preferably 0.1Pa or more, for example.

(antifouling film)

The substrate 1 with an antifouling film includes an antifouling film 3 on the main surface of a transparent substrate 2. When an antireflection film is formed on the main surface or the antiglare treated surface of the transparent substrate 2, the antifouling film 3 is preferably formed on the surface of the antireflection film. When a glass substrate having been subjected to a surface treatment such as an antiglare treatment or a chemical strengthening treatment and not having an antireflection film formed thereon is used as the transparent substrate 2, the antifouling film 3 is preferably formed on the surface subjected to the surface treatment.

Examples of the method for forming the antifouling film 3 include the following: a method in which a composition of a silane coupling agent having a perfluoroalkyl group, for example, a fluoroalkyl group such as a fluoroalkyl group containing a perfluoro (polyoxyalkylene) chain, is applied to the main surface of the transparent substrate 2 by spin coating, dip coating, casting, slit coating, spray coating, or the like, and then subjected to heat treatment; a vacuum vapor deposition method in which a raw material of the antifouling film 3 is vapor-deposited on the main surface of the transparent substrate 2 and then subjected to a heating treatment. In order to obtain the antifouling film 3 having high adhesion, it is preferable to form it by a vacuum deposition method. The formation of the antifouling film 3 by the vacuum deposition method is preferably performed using a film-forming composition containing a fluorine-containing hydrolyzable silicon compound.

The composition for forming the coating film is a composition containing a fluorine-containing hydrolyzable silicon compound, and is not particularly limited as long as it is a composition capable of forming the antifouling film 3 by a vacuum vapor deposition method. The composition for forming a coating film may contain any component other than the fluorine-containing hydrolyzable silicon compound, or may be composed of only the fluorine-containing hydrolyzable silicon compound. The optional component may be used in a range not to impair the effect of the present invention, and examples thereof include hydrolyzable silicon compounds having no fluorine atom (hereinafter referred to as "non-fluorine hydrolyzable silicon compounds") and catalysts.

When the fluorine-containing hydrolyzable silicon compound and an optional non-fluorine-containing hydrolyzable silicon compound are blended in the composition for forming a coating film, the respective compounds may be blended in the original state or may be blended in the form of a partial hydrolysis-condensation product thereof. The coating film-forming composition may be blended as a mixture of each compound and a partial hydrolysis-condensation product thereof.

When 2 or more fluorine-containing hydrolyzable silicon compounds are used in combination, each compound may be blended in the coating film-forming composition as it is, or may be blended in the form of a partial hydrolysis condensate of each compound, or may be blended in the form of a partial hydrolysis co-condensate of 2 or more compounds. Further, a mixture of these compounds, a partial hydrolysis-condensation product, and a partial hydrolysis-co-condensation product may be blended. The partial hydrolytic condensate and the partial hydrolytic cocondensate used herein have a polymerization degree of such an extent that vacuum deposition is possible. The fluorine-containing hydrolyzable silicon compound includes such a partial hydrolysis condensate and partial hydrolysis co-condensate in addition to the compound itself.

(fluorine-containing hydrolyzable silicon Compound)

The fluorine-containing hydrolyzable silicon compound used for forming the antifouling film 3 is not particularly limited as long as the antifouling film 3 has antifouling properties such as water repellency and oil repellency.

Specifically, there may be mentioned a fluorine-containing hydrolyzable silicon compound having 1 or more groups selected from a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group. These groups are present in the form of a fluorine-containing organic group bonded to the silicon atom of the hydrolyzable silyl group through a linking group or directly bonded to the silicon atom of the hydrolyzable silyl group. The perfluoropolyether group means a group having a valence of 2 having a structure in which a perfluoroalkylene group and an etheric oxygen atom are alternately bonded. The number average molecular weight (Mn) of the fluorine-containing hydrolyzable silicon compound is preferably 2000 to 10000, more preferably 3000 to 5000. When the number average molecular weight (Mn) of the fluorine-containing hydrolyzable silicon compound is within the above range, the antifouling property of the antifouling film 3 can be sufficiently exhibited, and the abrasion resistance is also excellent. The number average molecular weight (Mn) in the present specification means a number average molecular weight measured by gel permeation chromatography.

As described above, in the antifouling film 3 obtained by reacting the fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2, the fluorine-containing organic group is present in the vicinity of the surface of the antifouling film 3, and the antifouling film 3 has antifouling properties such as water repellency and oil repellency. Specific examples of the fluorine-containing hydrolyzable silicon compound having the group described above include compounds represented by the following formulas (I) to (V).

In the formula (I), R^f1A linear perfluoroalkyl group (as an alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, etc.) having 1 to 16 carbon atoms, R¹Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.), X¹Is a hydrolyzable group (e.g., amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), m is an integer of 1 to 50, preferably 1 to 30, n is an integer of 0 to 2, preferably 1 to 2, and p is an integer of 1 to 10, preferably 1 to 8.

In the formula (I), R^f1The number of carbon atoms of (2) is preferably 1 to 4. In addition, R¹Methyl is preferred. As X¹The hydrolyzable group is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group.

C_qF_2q+1CH₂CH₂Si(NH₂)₃…(II)

In the formula (II), q is an integer of 1 or more, preferably 2 to 20. As the compound represented by the formula (II), n-trifluoro (1,1,2, 2-tetrahydro) propylsilazane (n-CF) can be exemplified₃CH₂CH₂Si(NH₂)₃) N-heptafluoro (1,1,2, 2-tetrahydro) pentylsilazane (n-C)₃F₇CH₂CH₂Si(NH₂)₃) And the like.

C_rF_2r+1CH₂CH₂Si(OCH₃)₃…(III)

In the formula (III), r is an integer of 1 or more, preferably 1 to 20. As the compound represented by the formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane (n-C) can be exemplified₈F₁₇CH₂CH₂Si(OCH₃)₃) And the like.

In the formula (IV), R^f2Is- (OC)₃F₆)_s－(OC₂F₄)_t－(OCF₂)_uA 2-valent linear perfluoropolyether group represented by (s, t, u are each independently an integer of 0 to 200), R²、R³Each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.). X²、X³Each independently a hydrolyzable group (e.g., amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), d, e each independently an integer of 1 to 2, c, f each independently an integer of 1 to 5, preferably 1 to 2, a andb is an integer of 2 to 3.

R^f2In the formula, s + t + u is preferably 20 to 300, and more preferably 25 to 100. In addition, R²、R³Methyl, ethyl, butyl are preferred. As X²、X³The hydrolyzable group is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group. In addition, a and b are each preferably 3.

F－(CF₂)_v－(OC₃F₆)_w－(OC₂F₄)_y－(OCF₂)_z(CH₂)_hO(CH₂)_iSi(X⁴)_3－k(R⁴)_k………(V)

In the formula (V), V is an integer of 1-3, w, y and z are each independently an integer of 0-200, h is an integer of 1-2, i is an integer of 2-20, and X is⁴Is a hydrolyzable group, R⁴Is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w + y + z is preferably 20 to 300, more preferably 25 to 100. In addition, i is preferably 2 to 10. X⁴The alkoxy group having 1 to 6 carbon atoms is preferable, and methoxy group and ethoxy group are more preferable. R⁴Preferably an alkyl group having 1 to 10 carbon atoms.

Further, as commercially available fluorine-containing hydrolyzable silicon compounds having 1 or more kinds of groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group, KP-801 (trade name, manufactured by shin-Etsu chemical industries), X-71 (trade name, manufactured by shin-Etsu chemical industries), KY-130 (trade name, manufactured by shin-Etsu chemical industries), KY-178 (trade name, manufactured by shin-Etsu chemical industries), KY-185 (trade name, manufactured by shin-Etsu chemical industries), KY-195 (trade name, manufactured by shin-Etsu chemical industries), KY-197 (trade name, manufactured by shin-Etsu chemical industries), OPTOOL (registered trade name), S-550 (trade name, manufactured by Asahi Nitro). Among the above commercially available products, KY-185, KY-195, OPTOOL DSX and S-550 are more preferable.

When a commercially available fluorinated hydrolyzable silicon compound is supplied together with a solvent, the fluorinated hydrolyzable silicon compound is used without removing the solvent. The composition for forming a coating film is prepared by mixing the fluorine-containing hydrolyzable silicon compound and optional components added as needed, and is subjected to vacuum deposition.

The antifouling film 3 is formed by allowing the coating film-forming composition containing the fluorine-containing hydrolyzable silicon compound to adhere to the main surface of the transparent substrate 2 and react with the main surface. As for specific vacuum deposition methods, reaction conditions, and the like, known methods, conditions, and the like can be applied. Such an antifouling film 3 can be formed by a production method described later, for example.

The optical thickness of the antifouling film 3 at the time of formation is preferably 10nm to 50nm, more preferably 10 to 30 nm. When the optical film thickness of the antifouling film 3 during formation is set to the above range, the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 can maintain good antifouling property and wear resistance.

(adhesive layer)

The substrate 1 with the antifouling film includes an adhesive layer 4 provided removably on the surface of the antifouling film 3. As the material of the adhesive layer 4, a material from which the adhesive layer 4 can be easily removed from the antifouling film 3 when the adhesive layer 4 is removed is preferable. Examples of the material of the adhesive layer 4 include an acrylic adhesive and a urethane adhesive. These adhesives are also preferable from the viewpoint of adhesiveness and releasability.

The adhesive force of the adhesive layer 4 is preferably 0.02N/25mm to 0.4N/25mm, more preferably 0.05N/25mm to 0.2N/25mm, in terms of controlling the amount of the fluorine-containing hydrolyzable silicon compound constituting the antifouling film 3 removed from the antifouling film 3 (in accordance with JIS Z0237), from the viewpoint of controlling the removal amount of the adhesive layer 4 from the antifouling film 3.

If the adhesive force of the adhesive layer 4 is less than 0.02N/25mm, the protective film 5 cannot be uniformly adhered to the antifouling film 3, and when the adhesive layer 4 and the protective film 5 are removed, the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film 3 may be unevenly removed along with the antifouling film 4. Further, the protective film 5 may be peeled off from the adhesive layer 4 during the conveyance of the substrate 1 with the antifouling film, and the function of the protective film 5 for protecting the antifouling film 3 may be impaired. If the adhesive force of the adhesive layer 4 exceeds 0.4N/25mm, the adhesive force of the adhesive layer 4 to the antifouling film 3 may be too strong, and the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film 3 may be removed more than necessary when the adhesive layer 4 and the protective film 5 are removed. Further, when the adhesive layer 4 and the protective film 5 are removed, a part of the adhesive layer 4 is not removed and remains on the surface of the antifouling film 3, and thus, defects such as fouling may occur. Further, a large force is required to remove the protective film 5, and the adhesive layer 4 may not be uniformly removed, thereby causing uneven peeling.

The thickness of the adhesive layer 4 is preferably 5 μm to 50 μm from the viewpoint of adhesion and peelability of the antifouling film 3 and the protective film 5.

(protective film)

The substrate 1 with the antifouling film is provided with a protective film 5 removably provided on the surface of the adhesive layer 4. The protective film 5 is not particularly limited as long as it is a film-like protective film made of resin. The protective film 5 may have a single-layer structure or a multilayer structure in which a plurality of layers such as an antistatic layer, a hard coat layer, and an easy-adhesion layer are stacked.

As the protective film 5, for example, a polyester film such as polyethylene terephthalate, a polyethylene film, a polyolefin film such as polypropylene, a polyvinyl chloride film, or the like can be used. Among these films, a polyester film is preferable in terms of adhesion to the adhesive layer 4, durability, and optical characteristics.

The thickness of the protective film 5 is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 75 μm, for example. If the thickness of the protective film 5 is less than 5 μm, the antifouling film 3 may not be sufficiently protected, and if the thickness of the protective film 5 exceeds 100 μm, the cost may increase.

[ method for producing substrate with antifouling film ]

The method for producing the substrate 1 with the antifouling film of the present invention comprises the steps of: a film forming step of forming an antifouling film 3 on the main surface of the transparent substrate 2; an adhesive layer providing step of removably providing the adhesive layer 4 on the surface of the antifouling film 3; and a protective film setting step of removably setting the protective film 5 on the surface of the adhesive layer 4.

(film Forming Process)

The film formation step is a step of forming the antifouling film 3 by vapor depositing a composition containing a fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2 and reacting the composition. In the film forming step, the antifouling film 3 is formed on the main surface of the transparent substrate 2 with high adhesion, and the substrate 1 with the antifouling film obtained therefrom can have both excellent antifouling properties such as water repellency and oil repellency and high-level abrasion resistance.

In the film forming step, first, a composition containing a fluorine-containing hydrolyzable silicon compound is attached to the main surface of the transparent substrate 2 and reacted. The antireflection film described above may be formed on the main surface of the transparent substrate 2. When the antireflection film is provided on the main surface of the transparent substrate 2, a composition containing a fluorine-containing hydrolyzable silicon compound is attached to the surface of the antireflection film and reacted. When the glass substrate subjected to the surface treatment such as the antiglare treatment or the chemical strengthening treatment is used as the transparent substrate 2, the composition containing the fluorine-containing hydrolyzable silicon compound is attached to the surface subjected to the surface treatment and reacted.

The method for adhering the composition containing the fluorine-containing hydrolyzable silicon compound to the main surface of the transparent substrate 2 is not particularly limited as long as it is a method generally used for forming a layer containing the fluorine-containing hydrolyzable silicon compound by a dry method, and examples thereof include a vacuum deposition method, a CVD method, a sputtering method, and the like. The vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing hydrolyzable silicon compound in the film formation step and the viewpoint of the simplicity of the apparatus.

Vacuum deposition methods include resistance heating, electron beam heating, high-frequency induction heating, reactive deposition, molecular beam epitaxy, hot wall deposition, ion plating, and cluster ion beam, and any method can be used. The resistance heating method is preferable from the viewpoint of suppressing decomposition of the fluorine-containing hydrolyzable silicon compound in the film formation step and the viewpoint of simplicity of the apparatus. The vacuum deposition apparatus is not particularly limited, and a known apparatus can be used.

Fig. 3 is a view schematically showing an apparatus that can be used in an embodiment of the method for producing the substrate 1 with an antifouling film according to the present invention. The apparatus shown in FIG. 3 is an apparatus for vapor-depositing a composition containing a fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2.

Hereinafter, a method for producing the substrate 1 with the antifouling film will be described with reference to fig. 3. Here, a vacuum deposition apparatus based on the resistance heating method will be described. When the apparatus shown in fig. 3 is used, the deposition step is performed on the transparent substrate 2 in the vacuum chamber 33 while the transparent substrate 2 is conveyed from the left side to the right side in the figure by the conveying section 32.

In the vacuum chamber 33 shown in fig. 3, the coating film-forming composition is attached to the main surface of the transparent substrate 2 by using the vacuum vapor deposition apparatus 20 based on the resistance heating method.

From the viewpoint of production stability, the pressure in the vacuum chamber 33 is preferably maintained at 1Pa or less, more preferably 0.1Pa or less. If the pressure in the vacuum chamber 33 is 1Pa or less, vacuum deposition by the resistance heating method can be stably performed.

The vacuum deposition apparatus 20 includes: a heating vessel 21 which is provided outside the vacuum chamber 33 and heats the composition for forming a coating film; a pipe 22 for connecting the heating vessel 21 to the vacuum chamber 33 and supplying the vapor of the composition for forming a coating introduced from the heating vessel 21 to the manifold 23; and a manifold 23 connected to the pipe 22 in the vacuum chamber 33, and having an injection port for injecting the vapor of the composition for forming a coating supplied from the pipe 22 onto the main surface of the transparent substrate 2. In the vacuum chamber 33, the transparent substrate 2 is held so that the injection ports of the manifolds 23 face the main surface of the transparent substrate 2.

The heating container 21 has a heating section capable of heating the coating film forming composition as a vapor deposition source to a vaporizable temperature. The heating temperature of the composition for forming a coating film may be appropriately selected depending on the kind of the composition for forming a coating film, and specifically, is preferably 30 to 400 ℃, and particularly preferably 50 to 300 ℃. When the heating temperature of the composition for forming a coating film is 30 ℃ or higher, the film forming rate is improved. When the heating temperature of the coating film-forming composition is 400 ℃ or lower, decomposition of the fluorine-containing hydrolyzable silicon compound is suppressed, and the antifouling film 3 having excellent antifouling property can be formed on the main surface of the transparent substrate 2.

Here, in the vacuum vapor deposition, it is preferable to perform a pretreatment of raising the temperature of the composition for forming a film containing a fluorine-containing hydrolyzable silicon compound in the heating vessel 21 to a vapor deposition start temperature and then discharging a part of the vapor of the composition for forming a film to the outside of the system for a predetermined time. The fluorine-containing hydrolyzable silicon compound contained in the composition for forming a coating film has a high molecular weight and a molecular weight distribution. Therefore, the content of the low-molecular-weight component that is easily vaporized in the vapor of the film-forming composition at the stage just before the vapor deposition start temperature increases, and in some cases, the content of the low-boiling impurity component also increases. By performing this pretreatment, low molecular weight components, low boiling point impurity components, and the like that affect the durability of the antifouling film 3 can be removed, and the composition of the raw material vapor supplied from the vapor deposition source can be stabilized. This enables stable formation of the antifouling film 3 having high durability.

Specifically, the following methods can be used: a pipe (not shown) connected to an openable/closable exhaust port for discharging vapor of the initial film-forming composition to the outside of the heating container 21 is provided separately from the pipe 22 connected to the manifold 23 at the upper portion of the heating container 21, and the vapor is collected outside the heating container 21.

The temperature of the transparent substrate 2 during vacuum deposition is preferably room temperature (20 to 25 ℃) to 200 ℃. When the temperature of the transparent substrate 2 is 200 ℃ or lower, the film formation rate becomes good. The upper limit of the temperature of the transparent substrate 2 is more preferably 150 c, and particularly preferably 100 c.

In order to prevent the condensation of the vapor of the composition for forming a coating film supplied from the heating container 21, the manifold 23 preferably includes a heater portion. In order to prevent the steam supplied from the heating container 21 from condensing in the pipe 22, the pipe 22 is preferably designed to be heated together with the heating container 21.

In order to control the film formation rate, it is preferable to provide the variable valve 24 in the pipe 22 and control the opening degree of the variable valve 24 based on the detection value of the film thickness gauge 25 provided in the vacuum chamber 33. With such a configuration, the amount of steam supplied to the coating film-forming composition containing the fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2 can be controlled. This enables the antifouling film 3 having a desired thickness to be accurately formed on the main surface of the transparent substrate 2. As the film thickness meter 25, a quartz crystal resonator monitor or the like can be used. Further, for the measurement of the film thickness, for example, when an X-ray diffractometer ATX-G (manufactured by RIGAKU corporation) for thin film analysis is used as the film thickness meter 25, an interference pattern reflecting X-rays can be obtained by an X-ray reflectance method and calculated from the oscillation period of the interference pattern.

In this manner, the coating film-forming composition containing the fluorine-containing hydrolyzable silicon compound adheres to the main surface of the transparent substrate 2. Further, at the same time as or after the attachment, the fluorine-containing hydrolyzable silicon compound is chemically bonded to the main surface of the transparent substrate 2 by a hydrolysis condensation reaction and siloxane bonding is performed between molecules, thereby forming the antifouling film 3.

The hydrolytic condensation reaction of the fluorine-containing hydrolyzable silicon compound proceeds on the main surface of the transparent substrate 2 while adhering thereto, but in order to sufficiently promote the reaction, the transparent substrate 2 on which the antifouling film 3 is formed may be taken out from the vacuum chamber 33 and then subjected to a heat treatment using a hot plate or a constant temperature and humidity bath as necessary. The conditions for the heat treatment are, for example, heating the transparent substrate 2 at a temperature of 80 to 200 ℃ for 10 to 60 minutes.

The film forming step may be performed in a state where a humidifying device or the like is connected to the chamber 33 to humidify the chamber 33. After the film formation step, the surface of the antifouling film 3 may be etched by, for example, acid treatment or alkali treatment to adjust the surface roughness (center line average roughness (Ra)) of the antifouling film 3 to, for example, 10nm or less.

(adhesive layer-providing step, protective film-providing step)

Next, the protective film 5 is removably attached to the surface of the stain-proofing film 3 obtained as described above via the adhesive layer 4. The method of removably providing the adhesive layer 4 on the surface of the antifouling film 3 and the method of removably providing the protective film 5 on the surface of the adhesive layer 4 are not particularly limited, and may be performed in the same step or in different steps,for example, a method may be used in which a protective film 5 (hereinafter, also referred to as "protective film with an adhesive layer") having an adhesive layer 4 provided in advance on the surface to be attached to the antifouling film 3 is placed on the antifouling film 3 and then pressurized. The adhesive-layer-provided protective film on the antifouling film 3 may be continuously provided, and in this case, the adhesive-layer-provided protective film is continuously supplied while the transparent substrate 2 is conveyed by using a laminator or the like, placed on the main surface of the antifouling film 3, and then pressurized to adhere the adhesive-layer-provided protective film to the antifouling film 3. The lamination conditions in this case are not particularly limited, and for example, the transport speed of the transparent substrate 2 on which the antifouling film 3 is formed may be 1mm/min to 5mm/min, and the pressurization pressure may be 1kgf/cm in a linear pressure (wired pressure)²～10kgf/m²The process is carried out.

[ removal of adhesive layer and protective film ]

The substrate 1 with the antifouling film is used by removing the adhesive layer 4 and the protective film 5 provided above. The method for removing the adhesive layer 4 and the protective film 5 is not particularly limited, and the removal may be performed manually or by using a peeling device or the like. The present inventors have found that the optical film thickness of the antifouling film 3a after peeling does not increase or decrease depending on the removal method.

The optical thickness of the antifouling film 3a after the removal of the adhesive layer 4 and the protective film 5 is 3nm to 30 nm. When the optical thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 is less than 3nm, the durability of the antifouling film 3a is significantly deteriorated. When the optical thickness of the removed antifouling film 3a exceeds 30nm, unevenness in haze due to unevenness in film thickness or aggregation of antifouling film materials occurs, and the appearance is perceived as optical unevenness, which deteriorates design properties and image display quality.

Preferably, the optical film thickness of the antifouling film 3a after the removal of the adhesive layer 4 and the protective film 5 has a rate of change of 10% to 60% with respect to the optical film thickness of the antifouling film 3 before the provision of the adhesive layer 4 and the protective film 5. Thus, the antifouling film 3a after the removal of the adhesive layer 4 and the protective film 5 has excellent antifouling property and high abrasion resistance.

Here, the rate of change of the optical thickness of the antifouling film 3a with respect to the antifouling film 3 is a value obtained by the following equation.

The rate of change in optical film thickness { (optical film thickness of antifouling film 3) - (optical film thickness of antifouling film 3 a) } × 100/(optical film thickness of antifouling film 3) (%) … (1)

The substrate 1 with a stain-proofing film having the stain-proofing film 3 obtained as described above is excellent in stain-proofing properties such as water repellency and oil repellency, and has high abrasion resistance capable of withstanding repeated wiping of stains. Further, since the base 1 with the antifouling film includes the adhesive layer 4 and the protective film 5 on the antifouling film 3, cracking and damage during transportation can be suppressed. Further, since the optical film thickness of the antifouling film 3 before the removal of the adhesive layer 4 and the protective film 5 is set to the above range so that the optical film thickness of the antifouling film 3a after the removal of the adhesive layer 4 and the protective film 5 is an optimum film thickness, the antifouling film 3a in use has a sufficient optical film thickness, is excellent in antifouling properties such as water repellency and oil repellency, and has high abrasion resistance such as resistance to repeated wiping of stains.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The evaluation in examples and comparative examples was performed by the following methods, respectively.

(Friction durability (abrasion resistance))

First, a friction block of a friction antifouling film was produced by attaching a plain-weave cotton fine cloth (coated flatware り cloth-golden cloth) No. 3 on the surface of a flat metal indenter having a bottom surface of 10mm X10 mm.

Next, the friction durability of the antifouling film was measured by a flat surface abrasion tester 3 (manufactured by gorgeous scientific instruments) using the above-mentioned friction block. Specifically, the friction block was mounted on a wear tester so that the bottom surface of the friction block was in contact with the surface of the antifouling film formed on the transparent substrate, and the friction block was placed on the wear tester so that the weight applied to the friction block was 1000g, and was slid back and forth on the surface of the antifouling film at an average speed of 6400mm/min and a single pass of 40 mm. The number of rubbing times was 2 times for 1 reciprocating sliding, and the contact angle of water on the surface of the antifouling film after 50000 times of rubbing was measured. The water contact angle of the surface of the antifouling film was measured by dropping 1. mu.L of pure water onto the antifouling film using an automatic contact angle meter DM-501 (manufactured by Kyowa Kagaku Co., Ltd.). The measurement sites of the water contact angle of the antifouling film surface were 10 sites, and the arithmetic mean of the water contact angles measured at the 10 sites was regarded as the rubbing durability. The lower the reduction rate of the water contact angle before and after removal of the protective film with an adhesive layer, the more suppressed the reduction of the friction durability.

(optical film thickness of antifouling film)

First, a method for measuring the optical film thickness of an anti-fouling film of an anti-reflection film-equipped substrate will be described.

First, the refractive index of each layer constituting the antireflection film formed on the surface of the transparent substrate is measured. Next, a black tape was attached to the back surface of the transparent base, and the back surface reflection of the transparent base was removed. Then, the spectroscopic reflection spectrum of the surface of the transparent substrate on which the antireflection film and the antifouling film were formed was measured by a spectrophotometer (SolidSpec-3700, Shimadzu corporation). Then, using the refractive index of each layer constituting the antireflection film and the thickness of each layer measured in advance, the optical film thickness of the antifouling film was calculated by dedicated software assuming that the refractive index of the antifouling film was 1.35.

Next, a method for measuring the optical film thickness of the anti-fouling film-equipped substrate having no anti-reflection film will be described.

A transparent substrate on which an antireflection film is formed and a transparent substrate on which an antireflection film is not formed are prepared, and an antifouling film is formed on both transparent substrates under the same conditions. Then, the surface of the transparent substrate on which the antireflection film and the antifouling film were formed was measured for the spectral reflectance spectrum by the same spectrometer as described above. The refractive index of each layer constituting the antireflection film and the thickness of each layer were used in the same manner as described above, and the optical film thickness of the antifouling film was calculated by dedicated software assuming that the refractive index of the antifouling film was 1.35. This value is defined as the optical film thickness of the anti-fouling film formed under the same conditions on the anti-reflection film-free substrate of the transparent substrate on which the anti-reflection film is not formed.

Since the optical film thickness of the antifouling film is extremely thin, it is difficult to accurately measure the film with a stylus type level difference meter, but the film can be measured with spectroscopic reflection spectroscopy or an ellipsometer. The optical film thickness of the antifouling film can be accurately measured by the following method without using an expensive apparatus as described above. The change in the reflection spectrum with respect to the variation in the film thickness of the anti-fouling film is larger in the reflection spectrum of the surface of the transparent substrate when the anti-fouling film is formed on the surface of the transparent substrate through the anti-reflection film than in the reflection spectrum of the surface of the transparent substrate when the anti-fouling film is directly formed on the surface of the transparent substrate without the anti-reflection film through the anti-reflection film. Therefore, as described above, the optical film thickness of the formed anti-fouling film can be accurately measured by the method of forming the anti-fouling film on the transparent substrate on which the anti-reflection film is formed and the transparent substrate on which the anti-reflection film is not formed under the same condition. In the examples and comparative examples, this method was employed.

(optical unevenness)

First, the substrate with the antifouling film was disposed above the fluorescent lamp, and the position of the fluorescent lamp was adjusted so that the position of the substrate with the antifouling film was 1500 lux. Then, the light transmitted through the substrate with the antifouling film was observed, and whether or not the haze and the color unevenness occurred was visually checked to determine whether or not the unevenness occurred.

[ example 1]

The substrate with the antifouling film was produced by the following procedure.

(1) Anti-glare treatment and etching treatment

Chemically strengthened glass (dragonttail (registered trademark, hereinafter also referred to as "DT") manufactured by asahi glass company) was used as a transparent substrate. Then, the surface of the transparent substrate is subjected to an antiglare treatment by a frosting treatment by the following procedure. First, an acid-resistant protective film is bonded to the back surface of the transparent base, which is the side not subjected to the antiglare treatment. Next, the transparent substrate was immersed in a 3 wt% hydrogen fluoride solution for 3 minutes to remove the dirt adhering to the surface of the transparent substrate. Next, the transparent substrate was immersed in a mixed solution of 15 wt% hydrogen fluoride and 15 wt% potassium fluoride for 3 minutes, and the surface of the transparent substrate, which was not coated with the protective film, was frosted.

The transparent substrate after the antiglare treatment was immersed in a 10% hydrogen fluoride solution for 6 minutes (etching time 6 minutes), whereby the haze value was adjusted to 25%.

(2) Chemical strengthening treatment

The anti-glare treated transparent substrate was immersed in molten potassium nitrate heated to 450 ℃ for 2 hours, then lifted, and gradually cooled to room temperature for 1 hour, thereby obtaining a chemically strengthened transparent substrate.

(3) Formation of anti-reflection film (AR film)

An antireflection film is formed on the surface of the chemically strengthened transparent substrate on which the antiglare treatment is performed as follows.

The transparent substrate was immersed in an alkaline solution (Sun Wash TL-75, manufactured by LION K.K.) for 4 hours. Then, a mixed gas in which 10 vol% of oxygen was mixed with argon gas was introduced into the vacuum chamber, and a niobium oxide target (NBO target, manufactured by AGC ceramics) was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm²Pulse sputtering was performed under the condition of an inversion pulse width of 5 μ sec, and a 1 st high refractive index layer made of niobium oxide (niobia) was formed on the surface of the transparent substrate to a thickness of 13 nm.

Next, a silicon target was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm while introducing a mixed gas in which 40 vol% of oxygen was mixed with argon gas²And pulse sputtering was performed under the condition of an inverted pulse width of 5 μ sec to form a 1 st low refractive index layer made of silicon oxide (silica) having a thickness of 35nm on the 1 st high refractive index layer.

Next, a mixed gas in which 10 vol% of oxygen was mixed with argon gas was introduced, and a niobium oxide target (NBO target, manufactured by AGC ceramics) was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm²Pulse sputtering was performed under the condition of an inversion pulse width of 5 μ sec, and a 2 nd high refractive index layer made of niobium oxide (niobia) was formed on the 1 st low refractive index layer to a thickness of 115 nm.

Next, a silicon target was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm while introducing a mixed gas in which 40 vol% of oxygen was mixed with argon gas²Pulse sputtering was performed under the condition of an inverted pulse width of 5 μ sec to form a 2 nd high refractive index layerA2 nd low refractive index layer made of silicon oxide (silica) was formed to a thickness of 80 nm.

Thus, an antireflection film was formed in which a niobium oxide (niobia) layer and a silicon oxide (silica) layer were laminated in 4 layers.

(4) Formation of anti-fouling film (AFP film)

First, a fluorine-containing hydrolyzable silicon compound (KY-185, manufactured by shin-Etsu chemical Co., Ltd.) as a raw material of an antifouling film was introduced into a heating vessel. Then, the inside of the heating vessel was degassed by a vacuum pump for 10 hours or more to remove the solvent in the solution, thereby obtaining a vapor of the composition for forming a coating film containing a fluorine-containing hydrolyzable silicon compound. Subsequently, the heating vessel containing the composition for forming a coating was heated to 270 ℃. After reaching 270 ℃, the state was maintained for 10 minutes until the temperature stabilized.

Then, vapor of the composition for forming a coating is supplied from a nozzle connecting the vacuum chamber and the heating container to the antireflection film laminated on the transparent substrate in the vacuum chamber, thereby forming a film.

At this time, film formation was performed until the film thickness became 10nm while measuring the film thickness by a quartz crystal resonator monitor provided in the vacuum chamber. Then, the supply of the composition for forming a coating was stopped at a point when the film thickness became 10nm, and the transparent substrate was taken out from the vacuum chamber. The transparent substrate taken out was placed on a hot plate with the back surface facing downward, and heat-treated at 150 ℃ for 60 minutes in the atmosphere.

The antifouling film thus formed was measured for its frictional durability and optical film thickness by the methods described above.

Further, a protective film (EC-9000 AS, manufactured by SUMIRON corporation) with an adhesive layer was provided on both surfaces of the transparent substrate with the antifouling film formed thereon obtained above using a laminator to manufacture a substrate 1 with an antifouling film. The material of the adhesive layer constituting the protective film with the adhesive layer was an acrylic adhesive, the 180-degree peel adhesion (according to JIS Z0237) of the adhesive layer to an acrylic substrate was 0.06N/25mm, the protective film was a polyethylene terephthalate (hereinafter also referred to as "PET") film, and the thickness of the protective film was 25 μm.

Then, the adhesive layer-attached protective film on the surface of the antifouling film was removed, and the antifouling film after removal of the adhesive layer-attached protective film was measured for friction durability, optical film thickness, and optical unevenness by the above-described method.

[ example 2]

An antifouling film having an optical film thickness of 15nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed and the antireflection film was not formed. Further, AS in example 1, adhesive layer-attached protective films (EC-9000 AS, manufactured by SUMIRON corporation) were provided on both surfaces of the transparent substrate on which the antifouling film was formed, and a substrate 2 with an antifouling film was manufactured. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

[ example 3]

An antifouling film having an optical film thickness of 25nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed and the antireflection film was not formed. Further, a protective film (UA-3000 AS, manufactured by SUMIRON corporation) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed using the same laminator AS in example 1, thereby producing a substrate 3 with an antifouling film. The material of the adhesive layer constituting the protective film with the adhesive layer was a polyurethane adhesive, the 180-degree peel adhesion (according to JIS Z0237) of the adhesive layer to an acrylic substrate was 0.15N/25mm, the protective film was a PET film, and the thickness of the protective film was 25 μm. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

[ example 4]

An antifouling film having an optical film thickness of 40nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed and the antireflection film was not formed. Further, a protective film (RP-207, manufactured by ritto electrical corporation) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed using the same laminator as in example 1, thereby producing a substrate 4 with an antifouling film. The material of the adhesive layer constituting the protective film with the adhesive layer was an acrylic adhesive, the 180-degree peel adhesion (according to JIS Z0237) of the adhesive layer to an acrylic substrate was 0.1N/25mm, the protective film was a PET-based film, and the thickness of the protective film was 25 μm. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

[ example 5]

An antifouling film having an optical thickness of 10nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed. Further, a protective film with an adhesive layer (Y16FS, manufactured by Sun a chemical and research) was provided on both surfaces of the transparent substrate on which the antifouling film was formed using the same laminator as in example 1, thereby producing a substrate 5 with an antifouling film. The material of the adhesive layer constituting the protective film with the adhesive layer was an acrylic adhesive, the 180-degree peel adhesion (according to JIS Z0237) of the adhesive layer to an acrylic substrate was 0.3N/25mm, the protective film was a PET-based film, and the thickness of the protective film was 25 μm. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

[ example 6]

An anti-fouling film having an optical thickness of 30nm was formed on a transparent substrate in the same manner as in example 1, except that a fluorine-containing hydrolyzable silicon compound (OPTOOL DSX, manufactured by shin-Etsu chemical Co., Ltd.) was used as a raw material of the anti-fouling film, and no anti-glare treatment was performed and no anti-reflection film was formed. Further, a protective film (RP-207, manufactured by ritto electrical corporation) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed using the same laminator as in example 1, thereby producing a substrate 6 with an antifouling film. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

[ example 7]

An antifouling film having an optical thickness of 20nm was formed on a transparent substrate in the same manner as in example 1, except that the antireflection film was not formed. Further, AS in example 1, protective films with adhesive layers (EC-9000 AS, manufactured by SUMIRON corporation) were provided on both surfaces of the transparent substrate on which the antifouling film was formed, and a substrate 7 with an antifouling film was manufactured. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

Comparative example 1

An antifouling film having an optical film thickness of 10nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed and the antireflection film was not formed. Further, a protective film (TG-3030, manufactured by SUMIRON corporation) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed using the same laminator as in example 1, thereby producing a substrate 1C with an antifouling film. The material of the adhesive layer constituting the protective film with the adhesive layer was an acrylic adhesive, the 180-degree peel adhesion (according to JIS Z0237) of the adhesive layer to an acrylic substrate was 3.0N/25mm, the protective film was a PET-based film, and the thickness of the protective film was 25 μm. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

Comparative example 2

An antifouling film having an optical film thickness of 60nm was formed on a transparent substrate in the same manner as in example 1, except that the antiglare treatment was not performed and the antireflection film was not formed. Further, AS in example 1, adhesive layer-attached protective films (EC-9000 AS, manufactured by SUMIRON corporation) were provided on both surfaces of the transparent substrate on which the antifouling film was formed, and a substrate 2C with an antifouling film was manufactured. The antifouling film was measured for its frictional durability, optical film thickness and optical unevenness in the same manner as in example 1.

The production conditions of substrates 1 to 7 with antifouling films produced in examples 1 to 7 and substrates 1C to 2C with antifouling films produced in comparative examples 1 to 2, the friction durability of the antifouling films, the optical film thickness, and the measurement results of optical unevenness are shown in table 1. Table 1 shows the rate of change in the optical film thickness of the antifouling film calculated by the above formula (1).

[ Table 1]

As shown in table 1, it is understood that the substrates 1 to 7 with the antifouling films, in which the optical thickness of the antifouling film in the state of including the adhesive layer and the protective film is 10nm to 50nm and the optical thickness of the antifouling film after removing the adhesive layer and the protective film is 3nm to 30nm, can suppress the decrease in the abrasion resistance of the antifouling film due to the removal of the adhesive layer and the protective film. Further, it is found that the substrates 1 to 7 with the antifouling film have excellent transparency without optical unevenness.

Description of the symbols

1 … substrate with antifouling film, 2 … transparent substrate, 3a … antifouling film, 4 … adhesive layer, 5 … protective film.

Claims

1. A substrate with a stain-proofing film, which is characterized in that the substrate with the stain-proofing film is used by sequentially providing the stain-proofing film, an adhesive layer and a protective film on the main surface of a transparent substrate and removing the adhesive layer and the protective film,

the adhesive layer is formed of an acrylic adhesive or a polyurethane adhesive,

the antifouling film is formed from a composition for forming a coating film containing a fluorine-containing hydrolyzable silicon compound,

the optical thickness of the antifouling film in the state of being provided with the adhesive layer and the protective film is 10nm to 50nm,

the thickness of the adhesive layer is 5-50 μm when the adhesive layer and the protective film are provided,

the optical film thickness of the antifouling film after removing the adhesive layer and the protective film is 3nm to 30nm,

the 180-degree peel adhesion of the adhesive layer to an acrylic substrate is 0.02N/25mm to 0.4N/25mm in accordance with JIS Z0237.

2. A substrate with a stain-proofing film, which is characterized in that the substrate with the stain-proofing film is used by sequentially providing the stain-proofing film, an adhesive layer and a protective film on the main surface of a transparent substrate and removing the adhesive layer and the protective film,

the adhesive layer is formed of an acrylic adhesive or a polyurethane adhesive,

a change rate represented by { (optical film thickness of the antifouling film in a state where the adhesive layer and the protective film are provided) - (optical film thickness of the antifouling film after the adhesive layer and the protective film are removed) } × 100/(optical film thickness of the antifouling film in a state where the adhesive layer and the protective film are provided) (%) is 10 to 60%,

3. The substrate with an antifouling film according to claim 1 or 2, wherein said transparent substrate is a glass substrate.

4. The substrate with a stain-proofing film according to claim 1 or 2, further comprising an antireflection film between the transparent substrate and the stain-proofing film.

5. The substrate with an antifouling film according to claim 1 or 2, wherein the main surface of the transparent substrate has a concavo-convex shape.