TW201621001A - Substrate having antifouling film - Google Patents

Abstract

This substrate has an antifouling film, an adhesive layer, and a protective film in order, respectively, on a main surface of a transparent substrate, and is used after the adhesive layer and the protective film are removed. The optical film thickness of the antifouling film is 10-50 nm in a state where the substrate has the adhesive layer and the protective film, and the optical film thickness of the antifouling film is 3-30 nm after the adhesive layer and the protective film are removed from the substrate.

Description

Base with anti-fouling film

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

A touch panel for a smart phone, a personal computer (PC), a car navigation device, or the like is touched by a human finger during use, and thus it is easy to adhere to stains caused by fingerprints, sebum, sweat, and the like. Moreover, if the stains adhere, they are not easily peeled off, and the difference between the portion to which the stain adheres and the portion to which the stain is not adhered is different depending on the scattering or reflection of light. Therefore, the touch panel to which the stains are attached has a problem of impairing visibility or appearance. Further, the same problem has been pointed out in display glass, optical components, sanitary equipment, and the like.

In order to eliminate such a problem, a method of forming a substrate on which an antifouling film containing a fluorine-containing hydrolyzable cerium compound is formed is used in a portion where a finger of a person of the parts or equipment contacts. For the antifouling film formed on the substrate, high water repellency and oil repellency are required in order to suppress the adhesion of the stain, and the abrasion resistance against the wiping of the adhered stain is required.

As the above-mentioned antifouling film having water repellency and oil repellency, for example, Patent Document 1 discloses a polymer which uses a polymer of a fluorine-containing oxygen alkyl group to modify a decane and a fluorine-containing oxygen alkyl group. A hardened film formed by a mixture and a glass substrate with a cured film. Further, Patent Document 2 discloses a glass substrate with an antifouling film obtained by dry-coating a fluorine-containing dry coating agent diluted with a diluent containing a specific composition into a fluorine-containing dry coating agent.

When manufacturing the glass substrate with the antifouling film as described above, in order to prevent it from being transported The damage of the glass substrate to which the antifouling film is attached is performed by providing a protective film on the surface of the antifouling film formed on the glass substrate via the adhesive layer. The adhesive layer and the protective film are removed when the glass substrate with the antifouling film is applied to the article.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-136833

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-244470

The glass substrate with the antifouling film previously has the following conditions: 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, resulting in water repellency and dialing of the glass substrate with the antifouling film. Antifouling properties such as oiliness or abrasion resistance are lowered.

An object of the present invention is to provide a substrate with an antifouling film which is excellent in antifouling property and abrasion resistance after removing an adhesive layer and a protective film.

The base system with an antifouling film of the present invention is provided with an antifouling film, an adhesive layer, and a protective film on the main surface of the transparent substrate, and the user is removed from the adhesive layer and the protective film, and the adhesive layer and the above-mentioned adhesive layer are provided. The anti-fouling film in the state of the protective film has an optical film thickness of 10 nm to 50 nm, and the anti-fouling film after removing the adhesive layer and the protective film has an optical film thickness of 3 nm to 30 nm.

Further, in the base system with an antifouling film of the present invention, an antifouling film, an adhesive layer, and a protective film are sequentially provided on the main surface of the transparent substrate, and the adhesive layer and the protective film are removed and the user is removed, and the adhesive layer is removed. And the optical film thickness of the anti-fouling film after the protective film is 3 nm to 30 nm, and {(the optical film thickness of the anti-fouling film in the state in which the adhesive layer and the protective film are provided) - (removing the adhesive layer and The optical film thickness of the anti-fouling film after the protective film is) × 100 / (the above-mentioned prevention in the state of having the above-mentioned adhesive layer and the protective film) The optical film thickness of the film (%) indicates a rate of change of 10 to 60%.

The present invention can provide a substrate with an antifouling film which is excellent in antifouling property and abrasion resistance after removing an adhesive layer and a protective film.

1‧‧‧Substrate with antifouling film

2‧‧‧Transparent substrate

3, 3a‧‧‧ antifouling film

4‧‧‧Adhesive layer

5‧‧‧Protective film

20‧‧‧Vacuum evaporation device

21‧‧‧heating container

22‧‧‧Pipe

23‧‧‧Management

24‧‧‧Variable valve

25‧‧‧ Film Thickness Gauge

32‧‧‧Transportation Department

33‧‧‧vacuum chamber

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a substrate to which an antifouling film of the present invention is applied.

Fig. 2 is a cross-sectional view showing the antifouling film after removing the adhesive layer and the protective film.

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

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

[Substrate with antifouling film]

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a substrate to which an antifouling film of the present invention is applied. The base 1 (also referred to as an antifouling body) to which the antifouling film is attached in the embodiment includes a transparent substrate 2 and an antifouling film 3 formed on the main surface of the transparent substrate 2. Further, the substrate 1 to which the antifouling film is attached is provided with an adhesive layer 4 which is removably provided on the surface of the antifouling film 3, and a protective film 5 which is removably provided on the surface of the adhesive layer 4. Further, the optical film thickness of the anti-fouling film 3 in the state in which the adhesive layer 4 and the protective film 5 are provided, in other words, the anti-fouling film 3 before the removal of the adhesive layer 4 and the protective film 5 is 10 nm to 50 nm.

The base 1 to which the antifouling film is attached is used by removing the adhesive layer 4 and the protective film 5. Fig. 2 is a cross-sectional view showing the antifouling film 3a after the adhesive layer 4 and the protective film 5 are removed. In FIG. 2, the optical film thickness of the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 is 3 nm to 30 nm. The optical film thickness of the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 is smaller than the optical film thickness of the anti-fouling film 3 before the adhesive layer 4 and the protective film 5 are removed.

Further, in the substrate 1 to which the antifouling film is attached, the antifouling film 3, the adhesive layer 4, the protective film 5, and the antireflection film described later may be provided on at least one main surface of the transparent substrate 2, and may be provided as needed. On the two main faces of the transparent substrate 2.

The antifouling film 3 is formed, for example, by a hydrolysis-condensation reaction on the main surface of the transparent substrate 2 on the main surface of the transparent substrate 2, and has antifouling properties such as water repellency or oil repellency. In the present specification, the fluorine-containing hydrolyzable ruthenium compound refers to a compound having a hydrolyzable decyl group having a hydrolyzable group or atom bonded to a ruthenium atom and further having a fluorinated organic group bonded to the ruthenium atom. . Further, the hydrolyzable group or atom which is bonded to a ruthenium atom to form a hydrolyzable decyl group is referred to as a hydrolyzable group.

In other words, the hydrolyzable decyl group of the fluorine-containing hydrolyzable hydrazine compound is hydrolyzed to a stanol group, and further, the decyl alcohol is dehydrated and condensed based on the fluorinated hydrolyzable hydrazine compound to form a decane represented by -Si-O-Si-. The key, thereby forming the antifouling film 3. Most of the fluorine-containing organic group bonded to the ruthenium atom constituting the siloxane chain is present in the vicinity of the surface of the anti-fouling film 3 due to the affinity of the fluorine-containing hydrolyzable ruthenium compound and the transparent substrate 2. Therefore, the surface of the antifouling film 3 exhibits water repellency or oil repellency by the action of the fluorine-containing organic group. Further, for example, when a glass substrate is used as the transparent substrate 2, the stanol group of the fluorine-containing hydrolyzable ruthenium compound formed by hydrolysis undergoes dehydration condensation reaction with the hydroxyl group present on the surface of the transparent substrate 2, and the antifouling film 3 is formed on the transparent substrate 2 via a decane bond.

Further, in order to protect the anti-fouling film 3, the protective film 5 is provided on the anti-fouling film 3 formed in this manner via the 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 the adhesive layer 4 and the protective film 5 are removed, it is unavoidable that the fluorine-containing hydrolyzable cerium compound constituting a part of the surface of the anti-fouling film 3 is removed from the anti-staining film 3 together with the adhesive layer 4.

Therefore, the antifouling film 3 is formed so that the optical film thickness of the antifouling film 3 at the time of formation, in other words, the optical film thickness of the antifouling film 3 before removing the adhesive layer 4 and the protective film 5 becomes 10 nm - 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 film thickness, and the adhesive layer 4 and the protective film 5 are removed, the surface of the antifouling film 3 is formed and is not transparent. The base 2 is then removed by adhering the fluorine-containing hydrolyzable cerium compound to the adhesive layer 4. As a result of removing a part of the fluorine-containing hydrolyzable ruthenium 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 is 3 nm to 30 nm.

Previously, the optical film thickness of the antifouling film before removing the adhesive layer and the protective film was set to the optimum film thickness of the antifouling film at the time of use, in other words, the optimum film for the antifouling film after removing the adhesive layer and the protective film. thick. That is, the optical film thickness of the antifouling film before removing the adhesive layer and the protective film is an optimum film thickness. Further, since the fluorine-containing hydrolyzable ruthenium compound constituting the surface of the antifouling film is removed from the transparent substrate together with the adhesive layer, there is a case where the optical film thickness of the antifouling film after removing the adhesive layer and the protective film is smaller than the optimum film. The anti-fouling property or the abrasion resistance of the anti-fouling film is deteriorated. On the other hand, the antifouling film 3 constituting the base material 1 with the antifouling film of the present embodiment is set such that the optical film thickness of the antifouling film 3a after the adhesion layer 4 and the protective film 5 are removed is optimized. That is, the optical film thickness of the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 is an optimum film thickness. Further, even if part of the fluorine-containing hydrolyzable cerium compound constituting the anti-fouling film 3 is removed together with the adhesive layer 4, since the optical film thickness of the anti-fouling film 3a is optimal, the anti-fouling film 3a can maintain good anti-fouling. Sexual or wear resistance.

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

(transparent substrate)

The transparent substrate 2 constituting the substrate 1 to which the antifouling film is attached is generally not particularly limited as long as it is a transparent material required to impart antifouling properties based on the antifouling film 3. For example, it is preferably made of glass, resin, or Those combinations (composites, laminates, etc.). In addition, the form of the transparent substrate 2 is not particularly limited, and for example, it may be a plate shape having rigidity, a film shape having flexibility, or the like.

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

Further, as the polymer film used as the transparent substrate 2 in the form of a film, for example, polyparaphenylene is exemplified. A polyester film such as ethylene dicarboxylate, a polyolefin film such as polypropylene, a polyvinyl chloride film, an acrylic resin film, a polyether ruthenium film, a polyarylate film, or a polycarbonate film.

Further, examples of the glass substrate used as the transparent substrate 2 include a common glass containing cerium oxide as a main component, and for example, a soda lime silicate glass, an aluminosilicate glass, a borosilicate glass, or an alkali-free glass. Glass substrate such as quartz glass.

In the case where glass is used as the material of the transparent substrate 2, the composition of the glass is preferably a composition which can be formed or strengthened by chemical strengthening treatment, and preferably contains sodium. As such a glass, for example, aluminosilicate glass, sodium calcium silicate glass, borosilicate glass, lead glass, alkali bismuth glass, aluminoborosilicate glass, or the like is preferable.

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

(i) containing 50 to 80% of SiO ₂ , 2 to 25% of Al ₂ O ₃ , 0 to 10% of Li ₂ O, 0 to 18% of Na ₂ O, in terms of composition represented by mole %, 0~10% K ₂ O, 0~15% MgO, 0~5% CaO and 0~5% ZrO ₂ glass

(ii) containing 50 to 74% of SiO ₂ , 1 to 10% of Al ₂ O ₃ , 6 to 14% of Na ₂ O, 3 to 11% of K ₂ O, in terms of composition represented by mole %, 2~15% of MgO, 0~6% of CaO and 0~5% of ZrO ₂ , and the total content of SiO ₂ and Al ₂ O ₃ is 75% or less, and the total content of Na ₂ O and K ₂ O is The total content of 12~25%, MgO and CaO is 7~15% glass

(iii) containing 68 to 80% of SiO ₂ , 4 to 10% of Al ₂ O ₃ , 5 to 15% of Na ₂ O, 0 to 1% of K ₂ O, in terms of composition represented by mole %, 4~15% of MgO and 0~1% of ZrO ₂ glass

(iv) containing 67 to 75% of SiO ₂ , 0 to 4% of Al ₂ O ₃ , 7 to 15% of Na ₂ O, and 1 to 9% of K ₂ O, in terms of composition represented by mole %, 6~14% of MgO and O~1.5% of ZrO ₂ , and the total content of SiO ₂ and Al ₂ O ₃ is 71 to 75%, and the total content of Na ₂ O and K ₂ O is 12 to 20%. Glass containing less than 1% CaO in the case of CaO

Further, as a composition of the glass used as the material of the transparent substrate 2, the following composition of the glass (both soda-calcium silicate glass) may be mentioned.

(v) 65 to 75% of SiO ₂ , 0.1 to 5% of Al ₂ O ₃ , 1 to 15% of MgO, 1 to 15% of CaO, and Na ₂ O, based on the composition expressed by mole % And the total content of K ₂ O and Na ₂ O and K ₂ O is 10 to 18% of glass.

(vi) Containing 65 to 72% of SiO ₂ , 2 to 7% of Al ₂ O ₃ , 5 to 15% of MgO, 3 to 9% of CaO, and 13 to 18%, based on the composition expressed by mole % Na ₂ O, 0~1% K ₂ O, 0-0.2% TiO ₂ , 0.01-0.15% Fe ₂ O ₃ and 0.02-0.4% SO ₃ , and (Na ₂ O and K ₂ O The total amount of the material / (the content of Al ₂ O ₃ ) is glass of 3.5 to 6.0.

(vii) Containing 60 to 72% of SiO ₂ , 1 to 10% of Al ₂ O ₃ , 5 to 12% of MgO, 0.1 to 5% of CaO, and 13 to 19%, based on the composition expressed by mole % Na ₂ O and 0 to 5% of K ₂ O, and (the content of RO) / (the total content of RO and R ₂ O) is 0.20 to 0.42 (wherein RO represents an alkaline earth metal oxide, R ₂ O A glass representing an alkali metal oxide).

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

SiO ₂ forms a component of the skeleton of the glass. Moreover, it is a component which reduces the occurrence of cracks when the surface of the glass is left with damage (indentation), and is a component which reduces the rate of destruction when leaving an indentation on the surface of the glass after chemical strengthening, and also reduces the component of the coefficient of thermal expansion. . The content of SiO ₂ is preferably 50% or more, more preferably 60% or more, further preferably 64% or more, and particularly preferably 66% or more. When the content of SiO ₂ is 50% or more, the stability as a glass or the deterioration of acid resistance, weather resistance, and chipping resistance can be avoided. On the other hand, the content of SiO ₂ is preferably 80% or less, more preferably 75% or less, still more preferably 70% or less. When the content of SiO ₂ is 80% or less, the decrease in the meltability due to the increase in the viscosity of the glass can be avoided.

The Al ₂ O ₃ system is a component which is effective for improving ion exchange performance and chipping resistance, and is a component which increases the surface compressive stress, and is also a component which does not easily increase the thermal expansion coefficient of the glass transition point or more. The content of Al ₂ O ₃ is preferably 0.1% or more, more preferably 2% or more, further preferably 3% or more, and particularly preferably 5% or more. Further, the content of Al ₂ O ₃ is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less. When the content of Al ₂ O ₃ is 0.1% or more, ion exchange performance and chipping resistance can be improved. On the other hand, when the content of Al ₂ O ₃ is 20% or less, the decrease in the meltability due to the increase in the viscosity of the glass can be avoided.

The MgO-based component which stabilizes the glass is also a component necessary for moderately maintaining the coefficient of thermal expansion. 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). Further, the content of MgO is preferably 15% or less, more preferably 14% or less, 13% or less, 12% or less, 11% or less, or 10% or less (particularly preferably 10% or less). When the content of MgO is 1% or more, the meltability at a high temperature becomes good, and devitrification is less likely to occur. On the other hand, when the content of MgO is 15% or less, devitrification is less likely to occur, and a sufficient ion exchange rate can be obtained.

CaO is a component which enhances the meltability of glass, and is also a component which is effective for maintaining a thermal expansion coefficient moderately. 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, still more preferably 5% or less. When the content of CaO is 0.05% or more, the meltability can be improved, and the surface compressive stress layer can be deepened by the content of CaO being 10% or less.

Na ₂ O forms a component of the surface compressive stress layer by ion exchange, and is also a component which enhances the meltability of the glass. Since Na ₂ O is a component which can increase the thermal expansion coefficient even if the density of the glass is low, it is effective for adjusting the thermal expansion coefficient. The content of Na ₂ O is preferably 10% or more, more preferably 11% or more, still more preferably 12% or more, and particularly preferably 13% or more. On the other hand, the content of Na ₂ O is preferably 19% or less, more preferably 18% or less, further preferably 16% or less, and particularly preferably 15% or less. When the content of Na ₂ O is 10% or more, the desired surface compressive stress layer can be formed by ion exchange, and the content of Na ₂ O is 19% or less, thereby avoiding reduction in weather resistance and acid resistance, and self-pressure. The cracks are cracked.

K ₂ O may be contained as needed, and its content is preferably 0.1% or more. When the content of K ₂ O is 0.1% or more, the meltability at a high temperature of the glass and a moderate thermal expansion coefficient can be maintained. The content of K ₂ O is more preferably 0.5% or more, further preferably 1% or more, and particularly preferably 2% or more. Further, the content of K ₂ O is preferably 8% or less. When the content of K ₂ O is 8% or less, the density of the glass becomes small, and the weight of the glass becomes small. The content of K ₂ O is more preferably 6% or less, further preferably 4% or less.

Fe ₂ O ₃ is a component that enhances the meltability of glass. Generally, Fe ₂ O ₃ in the glass absorbs visible light, but in the case of a glass having a thin thickness, since light absorption is reduced, it is less likely to be a problem. Further, Fe has an effect of increasing the high-temperature thermal expansion coefficient (αmax). Further, since Fe is a component of the absorption heat ray, it has the effect of promoting the heat convection of the glass melt to improve the homogeneity of the glass, and to prevent the high temperature of the bottom brick of the melting furnace, thereby prolonging the life of the furnace, and the like. The melting process of the plate glass is preferably included in the composition. The content of Fe ₂ O ₃ is preferably 0.005% or more, more preferably 0.01% or more, further preferably 0.03% or more, and particularly preferably 0.06% or more. On the other hand, if it is excessively contained, the color tone based on Fe ₂ O ₃ becomes a problem, and therefore, the content of Fe ₂ O ₃ is preferably less than 0.2%, more preferably less than 0.15%, and further preferably less than 0.12, especially better than 0.095.

The method for producing the glass substrate is not particularly limited, and it can be produced by continuously feeding a desired glass raw material into a melting furnace, preferably heating and melting the glass raw material at 1,500 to 1600 ° C, and then clarifying. The molten glass is supplied to a forming apparatus to be formed into a plate shape and subjected to slow cooling.

Further, the method of forming the glass substrate is not particularly limited, and for example, a down-draw method (for example, an overflow down-draw method, a flow-down method, a re-drawing method, etc.), a float method, a rolling method, and a press can be used. Forming method such as law.

The thickness of the transparent substrate 2 can be appropriately selected depending on the use. For example, when the transparent substrate 2 such as a resin substrate or a glass substrate is in the form of a plate, the thickness of the transparent substrate 2 is preferably 0.1 to 5 mm, more preferably 0.2 to 2 mm. In particular, in the case where a glass substrate is used as the transparent substrate 2 for chemical strengthening treatment to be described later, or when it is intended to reduce the weight, in order to be effective The chemical strengthening treatment or weight reduction is performed, and the thickness of the glass substrate is preferably 5 mm or less, more preferably 3 mm or less. In the case of a touch panel for a portable electronic device such as a smart phone or a tablet PC, since the weight is particularly important, the thickness of the glass substrate is preferably 1 mm or less, and particularly preferably 0.7 mm or less. On the other hand, in the case of a touch panel for a vehicle-mounted electronic device such as a car navigation system, since the rigidity is more important in terms of weight reduction, the thickness of the glass substrate is preferably 0.7 mm or more, and particularly preferably 1.0. Mm or more.

Further, 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, more preferably 75 to 150 μm.

In the case where a glass substrate is used as the transparent substrate 2, the surface of the glass substrate can be subjected to surface treatment by oxygen plasma. Further, a ruthenium oxide film may be formed on the main surface of the glass substrate by sputtering or the like. In the case where the anti-glare treatment or the chemical strengthening treatment to be described later is to be performed, it is preferred to carry out the treatment after the anti-glare treatment or the chemical strengthening treatment.

(anti-glare treatment)

In order to impart anti-glare property to the base 1 to which the antifouling film is attached, it is preferable that the main surface of the transparent base 2 has an uneven shape.

As a method of forming the uneven shape, an anti-glare treatment can be utilized. The antiglare treatment is not particularly limited. For example, when a glass substrate is used as the transparent substrate 2, the surface of the glass substrate may be chemically or physically surface-treated to form a bump having a desired surface roughness. The method of shape.

As a method of performing an anti-glare treatment chemically, the method of performing a freezing process is mentioned, for example. The freezing treatment can be carried out, for example, by immersing the glass substrate as the object to be treated in a mixed solution of hydrogen fluoride and ammonium fluoride.

Further, as a method of physically performing the anti-glare treatment, for example, a so-called sandblasting treatment in which a crystalline cerium oxide powder or a tantalum carbide powder is blown to the main surface of the glass substrate by pressurized air or a crystal is adhered thereto may be used. Water for brush with cerium oxide powder, strontium carbide powder, etc. Wet and use a wet brush to polish the main surface of the glass substrate.

Among them, since the freezing treatment as the chemical surface treatment is less likely to cause microcracks on the surface of the object to be processed, it is less likely to cause a decrease in mechanical strength, and therefore it can be preferably used as a method of subjecting the glass substrate to surface treatment.

In order to align the surface shape, it is preferred to etch the main surface of the glass substrate thus subjected to the anti-glare treatment chemically or physically. As the etching treatment, for example, a method of chemically etching the glass substrate by immersing it in an aqueous solution of hydrogen fluoride, that is, an etching solution, 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, it is possible to suppress partial precipitation of the surface of the glass substrate due to the reaction of a cationic component such as Na ions and K ions contained in the glass substrate with hydrogen fluoride, and to uniformly etch the surface of the glass substrate. .

In the case of performing the etching treatment, the etching amount can be adjusted by changing the concentration of the etching solution or the immersion time (hereinafter also referred to as "etching time") of the glass substrate in the etching solution. Thereby, the haze value of the surface of the glass substrate having the uneven shape (hereinafter also referred to as "anti-glare-treated surface") can be adjusted to a desired value. Further, in the case where the anti-glare treatment is performed by physical surface treatment such as sand blasting, the transparent substrate 2 may be cracked, but the crack may be removed by an etching treatment. The depth of the crack in the surface is preferably at most 5 μm or less, and more preferably at most 3 μm. If it is in this range, the fall of the fracture strength by the in-plane crack can be fully suppressed. The depth of the crack in the plane can be measured in the following manner. First, a plurality of transparent sheets (for example, five sheets) having the same properties are prepared. Then, the main surface of each transparent substrate was polished by gradually changing the amount of polishing using cerium oxide abrasive grains. The amount of polishing is, for example, 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm. Thereafter, when a main surface of the transparent substrate is slightly etched using a 1 mol% aqueous HF solution, it is easy to confirm the residual crack. The crack depth was determined by confirming how many μm of the crack was left by polishing using an optical microscope (VK-X120 manufactured by KEYENCE Corporation). That is, if there is no crack trace when the amount of polishing is 5 μm, the crack depth is 5 μm. under. Further, by the etching treatment, the effect of suppressing glare of the substrate 1 to which the antifouling film is attached can be obtained.

Thus, as the shape of the main surface of the glass substrate after the anti-glare treatment and the etching treatment, the surface roughness (root mean square roughness (RMS)) is preferably 0.01 to 0.5 μm, more preferably 0.01 to 0.3 μm. Further preferably, it is 0.01 to 0.2 μm. By setting the surface roughness (RMS) to the above range, the haze value of the glass substrate after the anti-glare treatment can be adjusted to 3 to 30%. As a result, excellent anti-glare property can be imparted to the obtained base material 1 to which the antifouling film is attached.

Further, the surface roughness (RMS) can be measured in accordance with the method specified in JIS B 0601: (2001). Specifically, a measurement method of the surface roughness (RMS) is used, and a laser microscope (VK-9700, manufactured by KEYENCE Co., Ltd.) is used to set a field of view of 300 μm × 200 μm on the measurement surface of the glass substrate after the antiglare treatment. , to determine the height information of the glass substrate. The surface roughness (RMS) can be calculated by performing a critical correction on the measured value and determining the root mean square of the obtained height. As a critical value, 0.08 mm is preferably used.

Further, the haze value is a value measured in accordance with the method specified in JIS K 7136.

Further, after the antiglare treatment and the etching treatment, the surface of the glass substrate 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 shape of the pores thus observed is preferably 1 μm or more and 10 μm or less. By being in such a range, both anti-glare and anti-glare properties can be achieved.

In the case where a glass substrate is used as the transparent substrate 2, in order to increase the strength of the obtained substrate 1 with the antifouling film, it is preferred to subject the main surface of the glass substrate or the antiglare-treated surface to a chemical strengthening treatment.

The method of the chemical strengthening treatment is not particularly limited, and an ion exchange treatment is performed on the main surface of the glass substrate or the anti-glare-treated surface, and a surface layer in which compressive stress remains is formed on the surfaces. Specifically, at the temperature below the glass transition point, an alkali metal ion (for example, Li ion, Na ion) having a small ionic radius contained in the vicinity of the main surface or the anti-glare treatment surface of the glass substrate is replaced with an ionic radius. Larger alkali metal ions (for example, relative to Li The child is a Na ion or a K ion, and is a K ion with respect to the Na ion. Thereby, the compressive stress remains on the main surface of the glass substrate or the anti-glare treatment surface, thereby increasing the strength of the glass substrate.

(anti-reflection film)

The base 1 to which the antifouling film is attached may also have an antireflection film between the transparent substrate 2 and the antifouling film 3. When the transparent substrate 2 has the above-described uneven shape, the antireflection film is preferably provided on the antiglare treatment surface.

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

The antireflection film may include a high refractive index layer and a low refractive index layer each of one layer, or may include two or more high refractive index layers and a low refractive index layer. In the case where the antireflection film includes two or more high refractive index layers and a low refractive index layer, it is preferable to alternately laminate the high refractive index layer and the low refractive index layer.

In particular, in order to improve the antireflection performance, the antireflection film is preferably a laminate in which a plurality of layers are laminated. For example, the laminate preferably has two or more layers and six or less layers, more preferably two or more layers. Layers below 4 layers. The laminate here is preferably a laminate in which a high refractive index layer and a low refractive index layer are laminated, and it is preferable that the total number of layers of each of the high refractive index layer and the low refractive index layer is in the above range.

The material of the high refractive index layer or the low refractive index layer is not particularly limited, and may be selected in consideration of the degree of required antireflection performance or productivity. As a material constituting the high refractive index layer, for example, it is preferably selected from the group consisting of niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), and nitriding. One or more of 矽(SiN). As a material constituting the low refractive index layer, a material selected from cerium oxide (SiO ₂ ), a mixed oxide containing Si and Sn, a material containing a mixed oxide of Si and Zr, and a mixture containing Si and Al are preferably used. One or more of the oxide materials.

More preferably, the high refractive index layer is a hafnium oxide layer, a hafnium oxide layer or a tantalum nitride layer from the viewpoint of productivity or refractive index, and the low refractive index layer is a hafnium oxide layer.

The method of forming the antireflection film into a film is not particularly limited, and various film formation methods can be utilized. It is particularly preferable to form a film by pulse sputtering, AC (alternating current) sputtering, and digital sputtering. By setting these methods, a dense film can be obtained, and durability can be ensured.

For example, in the case of film formation by pulse sputtering, the transparent substrate 2 is disposed in a chamber of a mixed gas atmosphere of an inert gas and oxygen, and the target is selected in a desired composition, and the antireflection film is formed into a film. .

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

The pressure in the chamber caused by the mixed gas of the inert gas and the oxygen gas is not particularly limited, and the surface roughness of the antireflection film can be easily set to the above preferred range by setting it to 0.5 Pa or less. This is because if the pressure in the chamber based on the mixed gas of the inert gas and the oxygen gas is 0.5 Pa or less, the average free path of the film-forming molecules can be ensured, and the film-forming molecules can have more energy to reach the transparent substrate 2. Therefore, the re-disposition of the film-forming molecules can be promoted, thereby obtaining a film which is relatively dense and has a smooth surface. The lower limit of the pressure in the chamber based on the mixed gas of the inert gas and the oxygen is not particularly limited, and is preferably, for example, 0.1 Pa or more.

(anti-fouling film)

The base 1 to which the antifouling film is attached is provided with the antifouling film 3 on the main surface of the transparent substrate 2. When the anti-reflection film is formed on the main surface or the anti-glare treatment surface of the transparent substrate 2, the anti-fouling film 3 is preferably formed on the surface of the anti-reflection film. Further, in the case where a glass substrate which has been subjected to a surface treatment such as an anti-glare treatment or a chemical strengthening treatment and which does not form an anti-reflection film is used as the transparent substrate 2, the anti-fouling film 3 is preferably formed on the surface which has been subjected to the surface treatment. .

As a method of forming the antifouling film 3, as an example, the following method etc. are mentioned: A composition of a perfluoroalkyl group, for example, a fluoroalkyl group-containing decane coupling agent such as a perfluoro(polyoxyalkylene) chain fluoroalkyl group, by spin coating method, dip coating method, casting method, slit a method of applying heat treatment after application to the main surface of the transparent substrate 2 by a coating method, a spray coating method, or the like; and vacuum-vaporating the raw material of the anti-fouling film 3 by vapor-depositing the main surface of the transparent substrate 2 Plating method, etc. In order to obtain the antifouling film 3 having high adhesion, it is preferably formed by a vacuum evaporation method. The formation of the antifouling film 3 by the vacuum deposition method is preferably carried out using a composition for forming a film containing a fluorine-containing hydrolyzable ruthenium compound.

The composition for forming a film-form is a composition containing a fluorine-containing hydrolyzable cerium compound, and is not particularly limited as long as it is a composition capable of forming the anti-fouling film 3 by a vacuum deposition method. The composition for forming a film may contain any component other than the fluorine-containing hydrolyzable ruthenium compound, or may be composed only of a fluorine-containing hydrolyzable ruthenium compound. The optional component can be used in a range that does not inhibit the effects of the present invention, and examples thereof include a hydrolyzable hydrazine compound having no fluorine atom (hereinafter referred to as "non-fluorinated hydrolyzable hydrazine compound"), a catalyst, and the like.

In addition, when the fluorine-containing hydrolyzable ruthenium compound and the non-fluorohydrolyzable ruthenium compound are optionally blended in the film-forming composition, each compound may be formulated in the original state, or a partially hydrolyzed condensate thereof may be used. The form is configured. Further, it may be formulated in a film-forming composition in the form of a mixture of each compound and a partially hydrolyzed condensate thereof.

In the case where two or more kinds of the fluorine-containing hydrolyzable ruthenium compounds are used in combination, the respective compounds may be blended in the film-forming composition in the original state, or may be blended in the form of a partially hydrolyzed condensate of each. Further, it may be formulated in the form of a partially hydrolyzed co-condensate of two or more kinds of compounds. Further, a mixture of the compounds, the partially hydrolyzed condensate, and the partially hydrolyzed cocondensate may be blended. Among them, the partially hydrolyzed condensate and the partially hydrolyzed co-condensate used are those which can be subjected to vacuum evaporation. In addition, the fluorine-containing hydrolyzable hydrazine compound contains such a partially hydrolyzed condensate and a partially hydrolyzed co-condensate in addition to the compound itself.

(fluorine-containing hydrolyzable hydrazine compound)

The fluorine-containing hydrolyzable ruthenium compound to be used for the formation of the antifouling film 3 is not particularly limited as long as it has antifouling properties such as water repellency and oil repellency.

Specifically, a fluorine-containing hydrolyzable ruthenium compound having at least one selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group is mentioned. These groups are present in the form of a fluorine-containing organic group bonded via a linking group or directly bonded to a hydrazine atom of a hydrolyzable decyl group. Further, the perfluoropolyether group means a divalent group 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 cerium compound is preferably from 2,000 to 10,000, more preferably from 3,000 to 5,000. When the number average molecular weight (Mn) of the fluorine-containing hydrolyzable cerium 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. Further, the number average molecular weight (Mn) in the present specification means the one measured by gel permeation chromatography.

As described above, in the antifouling film 3 obtained by reacting the fluorine-containing hydrolyzable ruthenium 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, whereby the antifouling film 3 It has anti-staining properties such as water repellency and oil repellency. Specific examples of the fluorine-containing hydrolyzable ruthenium compound having the above-mentioned group include compounds represented by the following formulas (I) to (V).

In the formula (I), R ^f1 is a linear perfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X ¹ is a hydrolyzable group (for example, an amine group or an alkoxy group) Or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like), m is an integer of 1 to 50, preferably 1 to 30, and n is 0. ~2, preferably an integer of 1 to 2, p is 1 to 10, preferably an integer of 1 to 8.

In the formula (I), the carbon number of R ^f1 is preferably from 1 to 4. Further, R ^{1 is} preferably a methyl group. The hydrolyzable group represented by X ¹ is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group or an ethoxy group.

C _q F _2q+1 CH ₂ CH ₂ Si(NH ₂ ) ₃ (II)

In the formula (II), q is an integer of 1 or more, preferably 2 to 20. The compound represented by the formula (II) is exemplified by n-trifluoro(1,1,2,2-tetrahydro)propyloxazane (n-CF ₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ ), Fluorine (1,1,2,2-tetrahydro)pentyloxazane (nC ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ ) or the like.

C _r F _2r+1 CH ₂ CH ₂ Si(OCH ₃ ) ₃ (III)

In the formula (III), r is an integer of 1 or more, preferably 1 to 20. The compound represented by the formula (III) is exemplified by 2-(perfluorooctyl)ethyltrimethoxydecane (nC ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ).

In the formula (IV), R ^f2 is represented by -(OC ₃ F ₆ ) _s -(OC ₂ F ₄ ) _t -(OCF ₂ ) _u - (s, t, and u are each independently an integer of 0 to 200) a divalent linear perfluoropolyether group, wherein R ² and R ³ are each independently a hydrocarbon group having a carbon number of 1 to 8 (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl) Wait). X ² and X ³ are each independently a hydrolyzable group (for example, an amine group, an alkoxy group, a decyloxy group, an alkenyloxy group, an isocyanate group or the like) or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) ), d and e are each an integer of 1 to 2, and c and f are each independently an integer of 1 to 5, preferably 1 to 2, and a and b are each independently an integer of 2 to 3.

In R ^f2 , s+t+u is preferably from 20 to 300, more preferably from 25 to 100. Further, R ² and R ^{3 are} preferably a methyl group, an ethyl group or a butyl group. The hydrolyzable group represented by X ² and X ³ is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group or an ethoxy group. Further, a and b are each preferably 3.

F-(CF ₂ ) _v -(OC ₃ F ₆ ) _w -(OC ₂ F ₄ ) _y -(OCF ₂ ) _z (CH ₂ ) _h O(CH ₂ ) _i Si(X ⁴ ) _3-k (R4 ) _k .........(V)

In the formula (V), v is an integer from 1 to 3, w, y, and z are each independently an integer from 0 to 200, h is an integer from 1 to 2, i is an integer from 2 to 20, and X ⁴ is hydrolyzable. Further, R ⁴ is 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 from 20 to 300, more preferably from 25 to 100. Further, i is preferably 2 to 10. X ^{4 is} preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group or an ethoxy group. R ^{4 is} preferably an alkyl group having 1 to 10 carbon atoms.

Further, the commercially available fluorine-containing hydrolyzable ruthenium compound having at least one selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group is preferably KP-801. (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), X-71 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-178 (trade name, Shin-Etsu Chemical Co., Ltd.) Manufactured, KY-185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-195 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-197 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL (registered trademark) DSX (trade name, manufactured by DAIKIN INDUSTRIES Co., Ltd.), S-550 (trade name, manufactured by Asahi Glass), and the like. Among the above, KY-185, KY-195, OPTOOL DSX, and S-550 are more preferable.

In the case where a commercially available fluorine-containing hydrolyzable ruthenium compound is supplied together with a solvent, the fluorine-containing hydrolyzable ruthenium compound is used by removing the solvent. The composition for forming a film is prepared by mixing the above-mentioned fluorine-containing hydrolyzable ruthenium compound with an optional component added as needed, and is subjected to vacuum deposition.

The composition for forming a film comprising the fluorine-containing hydrolyzable cerium compound is adhered The antifouling film 3 is formed by reacting on the main surface of the transparent substrate 2. Further, known methods, conditions, and the like can be applied to specific vacuum vapor deposition methods, reaction conditions, and the like. For example, such an antifouling film 3 can be formed by a manufacturing method described later.

The optical film thickness of the antifouling film 3 at the time of formation is preferably from 10 nm to 50 nm, more preferably from 10 to 30 nm. By setting the optical film thickness of the anti-fouling film 3 at the time of formation to the above range, the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 can maintain good antifouling property and abrasion resistance.

(adhesive layer)

The base 1 to which the antifouling film is attached is provided with an adhesive layer 4 which is removably provided on the surface of the antifouling film 3. As the material of the adhesive layer 4, it is preferable that the adhesive layer 4 can be easily removed from the anti-fouling film 3 when the adhesive layer 4 is removed. Examples of the material of the adhesive layer 4 include an acrylic adhesive, a polyurethane adhesive, and the like. These adhesives are also preferred from the viewpoint of adhesion or peelability.

Regarding the adhesion of the adhesive layer 4, the adhesion layer 4 is 180 with respect to the acrylic substrate from the viewpoint of controlling the removal amount of the fluorine-containing hydrolyzable ruthenium compound constituting the antifouling film 3 when the adhesive layer 3 is removed from the anti-fouling film 3. The degree of peeling adhesion (according to JIS Z 0237) is preferably 0.02 N/25 mm to 0.4 N/25 mm, more preferably 0.05 N/25 mm to 0.2 N/25 mm.

If the adhesive force of the adhesive layer 4 is less than 0.02 N/25 mm, 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 constituting the surface of the antifouling film 3 is present. The hydrolyzable cerium compound is likely to be unevenly removed as the antifouling film 4 is removed. Further, in the conveyance of the substrate 1 to which the antifouling film is attached, there is a possibility that the protective film 5 is peeled off from the adhesive layer 4, and the function of the protective film 5 to protect the antifouling film 3 may be impaired. Further, if the adhesive force of the adhesive layer 4 exceeds 0.4 N/25 mm, there is a possibility that the adhesion of the adhesive layer 4 to the antifouling film 3 is too strong, and when the adhesive layer 4 and the protective film 5 are removed, the antifouling film is formed. The fluorine-containing hydrolyzable ruthenium compound on the surface of 3 was removed as necessary. 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 anti-fouling film 3, so that defects such as stains may occur. Furthermore, in order to remove the protective film 5, it is necessary to In the case of the big force, there is a possibility that the adhesive layer 4 cannot be uniformly removed to cause uneven peeling.

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

(protective film)

The base 1 to which the antifouling film is attached is provided with a protective film 5 which is 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 made of a resin. Further, 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 laminated.

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

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

[Manufacturing method of substrate with antifouling film]

The method for manufacturing the substrate 1 with the antifouling film of the present invention has the following steps: a film forming step of forming the antifouling film 3 on the main surface of the transparent substrate 2; and an adhesive layer setting step of removing the adhesive layer 4 The protective film is disposed on the surface of the anti-fouling film 3; the protective film is disposed on the surface of the adhesive layer 4.

(film formation step)

In the film formation step, the composition containing the fluorine-containing hydrolyzable cerium compound is vapor-deposited on the main surface of the transparent substrate 2 and reacted to form the antifouling film 3. In the film forming step, the antifouling film 3 is formed on the main surface of the transparent substrate 2 with high adhesion, whereby the substrate 1 with the antifouling film obtained can simultaneously achieve excellent water repellency or oil repellency. Stain and high level of wear resistance Consumable.

In the film formation step, first, a composition containing a fluorine-containing hydrolyzable ruthenium compound is adhered to the main surface of the transparent substrate 2 to carry out a reaction. The anti-reflection film may be formed on the main surface of the transparent substrate 2. When the main surface of the transparent substrate 2 has an antireflection film, the composition containing the fluorine-containing hydrolyzable ruthenium compound is attached to the surface of the antireflection film and reacted. Further, when the glass substrate subjected to the surface treatment such as the anti-glare treatment or the chemical strengthening treatment is used as the transparent substrate 2, the composition containing the fluorine-containing hydrolyzable ruthenium compound is attached to the surface subjected to the surface treatment and reacted. .

The method of attaching the composition containing the fluorine-containing hydrolyzable ruthenium 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 of a fluorine-containing hydrolyzable ruthenium compound by a dry method, for example, Examples thereof include a vacuum deposition method, a CVD (chemical vapor deposition) method, and a sputtering method. The vacuum vapor deposition method is preferred in terms of suppressing the decomposition of the fluorine-containing hydrolyzable ruthenium compound in the film formation step and the easiness of the apparatus.

As a vacuum evaporation method, it can be subdivided into resistance heating method, electron beam heating method, high frequency induction heating method, reactive vapor deposition method, molecular beam epitaxy method, hot wall evaporation method, ion plating method, cluster ion beam Any method can be applied. The resistance heating method is preferred in terms of suppressing the decomposition of the fluorine-containing hydrolyzable ruthenium compound in the film formation step and the simplicity of the apparatus. The vacuum vapor deposition apparatus is not particularly limited, and a known apparatus can be used.

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

Hereinafter, a method of manufacturing the substrate 1 to which the antifouling film is attached will be described with reference to FIG. Here, a vacuum vapor deposition apparatus by a resistance heating method will be described. When the apparatus shown in FIG. 3 is used, the transparent substrate 2 is transported from the left side to the right side of the drawing by the transport unit 32, and the transparent substrate 2 is subjected to a film forming step in the vacuum chamber 33.

In the vacuum chamber 33 shown in FIG. 3, the film forming composition is adhered to the main surface of the transparent substrate 2 by a vacuum vapor deposition apparatus 20 by a resistance heating method.

The pressure in the vacuum chamber 33 is preferably maintained at 1 Pa or less, and more preferably 0.1 Pa or less from the viewpoint of production stability. When the pressure in the vacuum chamber 33 is 1 Pa or less, vacuum vapor deposition by a resistance heating method can be stably performed.

The vacuum vapor deposition apparatus 20 includes a heating container 21 that is disposed outside the vacuum chamber 33 and that heats the composition for forming a film, and a pipe 22 that connects the heating container 21 and the vacuum chamber 33, and the self-heating container The vapor of the composition for forming a film to be introduced 21 is supplied to the manifold 23, and the manifold 23 is connected to the pipe 22 in the vacuum chamber 33, and has a composition for forming a film for supplying the self-pipe 22. The steam is sprayed to the ejection opening of the main surface of the transparent substrate 2. Further, in the vacuum chamber 33, the transparent substrate 2 is held such that the ejection opening of the manifold 23 faces the main surface of the transparent substrate 2.

The heating container 21 has a heating unit that can heat the composition for forming a film as a vapor deposition source to a temperature at which evaporation can be performed. The heating temperature of the composition for forming a film can be appropriately selected depending on the type of the composition for forming a film. Specifically, it is preferably 30 to 400 ° C, and more preferably 50 to 300 ° C. When the heating temperature of the composition for forming a film is 30 ° C or more, the film formation rate becomes good. When the heating temperature of the composition for forming a film is 400° C. or lower, the decomposition of the fluorine-containing hydrolyzable cerium compound can be suppressed, and the antifouling film 3 having excellent antifouling properties can be formed on the main surface of the transparent substrate 2 .

Here, in the vacuum deposition, it is preferred to raise the composition for forming a film after the temperature of the composition for forming a film containing the fluorine-containing hydrolyzable cerium compound in the heating container 21 is raised to the vapor deposition starting temperature. A portion of the steam is pretreated to the outside of the system at a specific time. The fluorine-containing hydrolyzable ruthenium compound contained in the composition for forming a film has a high molecular weight and has a molecular weight distribution. Therefore, in the vapor of the composition for forming a film just before the vapor deposition start temperature, the content of the low molecular weight component which is easily vaporized increases, and depending on the case, the low boiling impurity component also increases. By performing the pretreatment, the resistance to the antifouling film 3 can be removed. The composition of the low-molecular weight component or the low-boiling impurity component which affects the long-term properties, and further, the composition of the raw material vapor supplied from the vapor deposition source can be stabilized. Thereby, the antifouling film 3 with high durability can be stably formed.

Specifically, a method of discharging the vapor of the initial film forming composition to the outside of the heating container 21 may be additionally provided in the upper portion of the heating container 21 with respect to the pipe 22 connected to the manifold 23 A pipe (not shown) for opening and closing the exhaust port is provided, and the steam is trapped outside the heating container 21.

Further, the temperature of the transparent substrate 2 at the time of vacuum evaporation is preferably room temperature (20 to 25 ° C) to 200 ° C. When the temperature of the transparent substrate 2 is 200 ° C or lower, the film formation speed becomes good. The upper limit of the temperature of the transparent substrate 2 is more preferably 150 ° C, and particularly preferably 100 ° C.

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

Moreover, in order to control the film formation speed, it is preferable to provide the variable valve 24 in the piping 22, and to control the opening degree of the variable valve 24 based on the detection value of the film thickness meter 25 provided in the vacuum chamber 33. By providing such a configuration, the amount of steam supplied to the film-forming composition containing the fluorine-containing hydrolyzable ruthenium compound on the main surface of the transparent substrate 2 can be controlled. Thereby, the antifouling film 3 having a desired thickness can be formed accurately on the main surface of the transparent substrate 2. Further, as the film thickness meter 25, a quartz crystal oscillator monitor or the like can be used. Further, when the film thickness is measured, for example, when the X-ray diffraction meter ATX-G (manufactured by RIGAKU Co., Ltd.) for thin film analysis is used as the film thickness meter 25, the interference of the reflected X-rays can be obtained by the X-ray reflectance method. The pattern is calculated based on the vibration period of the interference pattern.

In this manner, the composition for forming a film containing the fluorine-containing hydrolyzable ruthenium compound is adhered to the main surface of the transparent substrate 2. Further, after being attached or attached, the fluorine-containing hydrolyzable ruthenium compound is chemically bonded to the main surface of the transparent substrate 2 by a hydrolysis condensation reaction, and is in the molecule The azeotrope bond is carried out to thereby form the antifouling film 3.

The hydrolysis condensation reaction of the fluorine-containing hydrolyzable ruthenium compound is carried out simultaneously with the adhesion to the main surface of the transparent substrate 2, but in order to sufficiently promote the reaction, the transparent substrate 2 on which the antifouling film 3 is formed may be self-vacuum chamber as needed. After the chamber 33 is taken out, heat treatment using a hot plate or a constant temperature and humidity chamber is further performed. As a condition for the heat treatment, for example, the transparent substrate 2 is heated at a temperature of 80 to 200 ° C for 10 to 60 minutes.

Further, the film forming step may be performed in a state where the humidifying device or the like is connected to the chamber 33 to humidify the inside of the chamber 33. Further, the surface roughness (center line average roughness (Ra)) of the anti-fouling film 3 may be adjusted, for example, to the surface of the anti-fouling film 3 by etching with an acid treatment or an alkali treatment, for example, after the film formation step. Below 10 nm.

(adhesion layer setting step, protective film setting step)

Then, the protective film 5 is removably attached to the surface of the anti-fouling film 3 obtained as described above via the adhesive layer 4. The method of disposing the adhesive layer 4 on the surface of the antifouling film 3 and the method of disposing the protective film 5 on the surface of the adhesive layer 4 are not particularly limited, and may be carried out in the same step or separately. In the step of carrying out, for example, a protective film 5 (hereinafter also referred to as "protective film for attaching an adhesive layer") to which the adhesive layer 4 is provided in advance with the adhesion surface of the anti-fouling film 3 is placed on the anti-fouling film 3 The method of pressurization. The protective film of the adhesive layer on the anti-fouling film 3 can be continuously formed. In this case, the protective film of the adhesive layer is continuously supplied and loaded while the transparent substrate 2 is conveyed by using a laminator or the like. After being placed on the main surface of the fouling film 3, pressure is applied to adhere the protective film of the adhesive layer to the anti-fouling film 3. The laminating conditions at this time are not particularly limited. For example, the conveying speed of the transparent substrate 2 on which the antifouling film 3 is formed may be 1 mm/min to 5 mm/min, and the pressing force may be 1 kgf/cm ² to 10 kgf per linear pressure. It is carried out under m ² .

[Removal of adhesive layer and protective film]

The base 1 to which the antifouling film is attached 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 can be manually removed. It is removed using a peeling device or the like. Furthermore, the inventors of the present invention found that the value of the optical film thickness of the anti-fouling film 3a after peeling is not increased or decreased by the removal method.

Thus, the optical film thickness of the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 is 3 nm to 30 nm. When the optical film thickness of the anti-fouling film 3a after the removal of the adhesive layer 4 and the protective film 5 is less than 3 nm, the durability of the anti-fouling film 3a is remarkably deteriorated. Further, when the optical film thickness of the anti-fouling film 3a after removal is more than 30 nm, unevenness in haze due to uneven film thickness or aggregation of the anti-fouling film material occurs, and the appearance is perceived as optical. Unevenness results in loss of design or image display quality.

Moreover, it is preferable that the optical film thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 is changed from 10% to 60 with respect to the optical film thickness of the antifouling film 3 before the adhesive layer 4 and the protective film 5 are provided. %. Thereby, the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 has excellent antifouling property and has high abrasion resistance.

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

Rate of change of optical film thickness = {(optical film thickness of antifouling film 3) - (optical film thickness of antifouling film 3a)} × 100 / (optical film thickness of antifouling film 3) (%)... 1)

The base material 1 having the antifouling film of the antifouling film 3 obtained as described above is excellent in antifouling property such as water repellency or oil repellency, and can be tolerated even if it is wiped or the like against the stains which are repeatedly performed. Wear resistance. Further, since the base 1 with the antifouling film is provided with the adhesive layer 4 and the protective film 5 on the antifouling film 3, cracking or damage during transportation can be suppressed. Moreover, since the optical film thickness of the anti-fouling film 3a after removing the adhesive layer 4 and the protective film 5 becomes an optimum film thickness, the optical film thickness of the anti-fouling film 3 before the adhesive layer 4 and the protective film 5 are removed is removed. When it is set to the above range, the antifouling film 3a at the time of use has a sufficient optical film thickness, and is excellent in antifouling property such as water repellency and oil repellency, and has a high tolerance even for wiping of stains which are repeatedly performed. Wear resistance.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples. The evaluations in the examples and comparative examples were carried out by the following methods, respectively.

(friction durability (wear resistance))

First, a plain muslin cloth No. 3 was attached to the surface of a flat metal indenter having a bottom surface of 10 mm × 10 mm, and it was set as a friction element of a friction antifouling film.

Then, using the above friction element, the friction durability of the antifouling film was measured by a flat abrasion tester 3 (manufactured by Daiei Scientific Seiki Co., Ltd.). Specifically, the friction element is attached to the abrasion tester so that the bottom surface of the friction element comes into contact with the surface of the antifouling film formed on the transparent substrate, and the weight is placed so that the load on the friction element becomes 1000 g. The average speed is 6400mm/min, and the single-direction 40mm reciprocates the sliding friction element on the surface of the antifouling film. The contact angle of water on the surface of the antifouling film after the end of the rubbing number of 50,000 times was measured by sliding back and forth twice as the number of rubbing times. The water contact angle of the surface of the antifouling film was measured by using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.), and 1 μL of pure water was added dropwise to the antifouling film. The measurement site of the water contact angle on the surface of the antifouling film was set to 10 locations, and the arithmetic mean of the water contact angle measured at 10 sites was set as the friction durability. The decrease in the water contact angle before and after the removal of the protective film with the adhesive layer is less, and the reduction in friction durability is suppressed.

(Optical film thickness of antifouling film)

First, a method of measuring the optical film thickness of an antifouling film having a substrate to which an antifouling film is attached with an antifouling film will be described.

First, the refractive index of each layer constituting the antireflection film formed on the surface of the transparent substrate was measured. Then, a black tape is attached to the back surface of the transparent substrate to remove the back surface reflection of the transparent substrate. Then, the surface of the transparent substrate on which the antireflection film and the antifouling film were formed was measured for spectroscopic reflection spectrum by a spectrometer (Solid Spec-3700, manufactured by Shimadzu Corporation). Then, using the previously measured refractive index of each layer constituting the antireflection film and the thickness of each layer, assuming that the refractive index of the antifouling film is 1.35, the optical of the antifouling film is calculated by a dedicated soft body. Film thickness.

Next, a method of measuring the optical film thickness of the antifouling film which does not have the base material with the anti-reflection film attached to the 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 separately prepared, and an antifouling film is formed on the two transparent substrates under the same conditions. Thereafter, the spectroscopic reflectance spectrum of the surface of the transparent substrate on which the antireflection film and the antifouling film were formed was measured 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 above, and the refractive index of the antifouling film was 1.35, and the optical film thickness of the antifouling film was calculated by a dedicated soft body. This value is an optical film thickness of the anti-fouling film which is formed in the base body of the anti-reflection film which does not have an anti-reflection film which is formed in the transparent substrate which does not have the anti-reflection film on the same conditions.

Since the optical film thickness of the antifouling film is very thin from several nm to several 10 nm, it is difficult to accurately measure using a stylus type profiler, but it can be measured by a spectroscopic reflection spectrum or an ellipsometer. Further, even if the expensive apparatus as described above is not used, the optical film thickness of the antifouling film can be accurately measured by the following method. The reflection spectrum of the surface of the transparent substrate in the case where the antifouling film is formed on the surface of the transparent substrate through the antireflection film, and the reflection spectrum of the surface of the transparent substrate in the case where the antifouling film is directly formed on the surface of the transparent substrate without passing through the antireflection film. In contrast, the change in the reflectance spectrum with respect to the film thickness variation of the antifouling film increases. Therefore, as described above, by the method of forming the antifouling film under the same conditions by the transparent substrate on which the antireflection film is formed and the transparent substrate not formed with the antireflection film, the optical properties of the formed antifouling film can be accurately measured. Film thickness. In the examples and comparative examples, this method was employed.

(optical unevenness)

First, the substrate with the antifouling film is placed above the fluorescent lamp, and the position of the fluorescent lamp is adjusted so that the position of the substrate with the antifouling film becomes 1500 lux. Then, the light transmitted through the substrate to which the antifouling film was attached was observed, and whether the haze or the unevenness of the color tone was observed was visually observed, and the presence or absence of unevenness was determined.

[Example 1]

A substrate with an antifouling film was produced in the following order.

(1) Anti-glare treatment and etching treatment

Chemically strengthened glass (Dragontrail (registered trademark, hereinafter also referred to as "DT"), manufactured by Asahi Glass Co., Ltd.) was used as a transparent substrate. Then, the antiglare treatment by the freezing treatment was carried out on the surface of the transparent substrate in the following order. First, the acid-resistant protective film is bonded to the back side of the transparent substrate which is not subjected to the anti-glare treatment. Then, the transparent substrate was immersed in a 3% by weight hydrogen fluoride solution for 3 minutes to remove stains adhering to the surface of the transparent substrate. Then, the transparent substrate was immersed in a mixed solution of 15% by weight of hydrogen fluoride and 15% by weight of potassium fluoride for 3 minutes, and the surface of the side of the protective film to which the transparent substrate was not bonded was freeze-treated.

The transparent substrate after the above anti-glare 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 transparent substrate after the anti-glare treatment was immersed in molten potassium nitrate heated to 450 ° C for 2 hours, then pulled up, and slowly cooled to room temperature over 1 hour, thereby obtaining a chemically strengthened transparent substrate.

(3) Film formation of anti-reflection film (AR film)

The anti-reflection film was formed as follows on the chemically-strengthened transparent substrate on the side which was subjected to the anti-glare treatment.

The transparent substrate was immersed in an alkali solution (Sun Wash TL-75, manufactured by LION Co., Ltd.) for 4 hours. Then, a mixed gas of 10% by volume of oxygen mixed with argon gas was introduced into the vacuum chamber, and a cerium oxide target (NBO target, manufactured by AGC Ceramics Co., Ltd.) was used at a pressure of 0.3 Pa, a frequency of 20 kHz, and electric power. Pulse sputtering was performed under the conditions of a density of 3.8 W/cm ² and an inverted pulse width of 5 μsec, and a first high refractive index layer containing niobium having a thickness of 13 nm was formed on the surface of the transparent substrate.

Then, while introducing a mixed gas of 40% by volume of oxygen mixed with argon gas, the target was used, and the pulse was applied under the conditions of a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3.8 W/cm ² , and a reverse pulse width of 5 μsec. The first low refractive index layer containing cerium oxide having a thickness of 35 nm was formed on the first high refractive index layer by sputtering.

Then, a mixed gas of 10% by volume of oxygen mixed with argon gas was introduced, and a cerium oxide target (NBO target, manufactured by AGC Ceramics Co., Ltd.) was used at a pressure of 0.3 Pa, a frequency of 20 kHz, and a power density of 3.8 W/cm ^{2 .} Pulse sputtering was performed under the condition of a reverse pulse width of 5 μsec, and a second high refractive index layer containing niobium having a thickness of 115 nm was formed on the first low refractive index layer.

Then, while introducing a mixed gas of 40% by volume of oxygen mixed with argon gas, the target was used, and the pulse was applied under the conditions of a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3.8 W/cm ² , and a reverse pulse width of 5 μsec. On the second high refractive index layer, a second low refractive index layer containing cerium oxide having a thickness of 80 nm was formed on the second high refractive index layer.

Thus, an antireflection film in which a total of four layers of a niobium layer and a silica layer were laminated was formed.

(4) Formation of antifouling film (AFP film)

First, a fluorine-containing hydrolyzable ruthenium compound (KY-185, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a raw material of the anti-fouling film, is introduced into a heating container. Thereafter, the inside of the heating vessel was deaerated by a vacuum pump for 10 hours or more, and the solvent in the solution was removed to obtain a vapor containing a composition for forming a film containing a fluorine-containing hydrolyzable cerium compound. Then, the heating container in which the composition for forming a film was placed was heated to 270 °C. After reaching 270 ° C, this state was maintained for 10 minutes until the temperature was stable.

Then, the anti-reflection film laminated on the transparent substrate provided in the vacuum chamber is supplied with vapor from the nozzle for connecting the vacuum chamber and the heating container to form a film.

At this time, one side is measured by a quartz crystal oscillator monitor installed in the vacuum chamber. The film thickness was formed on one surface until the film thickness became 10 nm. Then, the supply of the film-forming composition was stopped at the time when the film thickness became 10 nm, and the transparent substrate was taken out from the vacuum chamber. The removed transparent substrate was placed on the hot plate with the back surface facing downward, and heat-treated at 150 ° C for 60 minutes in the air.

For the antifouling film formed in this manner, the friction durability and the optical film thickness were measured by the above method.

Further, a protective film with an adhesive layer (EC-9000AS, manufactured by SUMIRON Co., Ltd.) was provided on both surfaces of the transparent substrate on which the antifouling film was formed, which was obtained by using a laminating machine, and a substrate 1 with an antifouling film was produced. . The material constituting the adhesive layer of the protective film with the adhesive layer is an acrylic adhesive, and the 180-degree peeling adhesion of the adhesive layer to the acrylic substrate (according to JIS Z 0237) is 0.06 N/25 mm, and the protective film is poly(terephthalic acid). The ethylenediester (hereinafter also referred to as "PET") film has a thickness of 25 μm.

Thereafter, the protective film of the adhesive layer on the surface of the antifouling film was removed, and the antifouling film after removing the protective film of the adhesive layer was used to measure the rubbing durability, the optical film thickness, and the optical unevenness by the above method.

[Embodiment 2]

An antifouling film having an optical film thickness of 15 nm was formed on the 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 (EC-9000AS, manufactured by SUMIRON Co., Ltd.) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed, in the same manner as in Example 1, to produce a substrate 2 with an antifouling film. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Example 3]

An antifouling film having an optical film thickness of 25 nm was formed on the 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, an adhesive layer was provided on both sides of the transparent substrate on which the antifouling film was formed using the same laminating machine as in Example 1. A protective film (UA-3000AS, manufactured by SUMIRON Co., Ltd.) was used to manufacture a substrate 3 with an antifouling film. The material constituting the adhesive layer of the protective film with the adhesive layer is a polyurethane adhesive, and the 180-degree peeling adhesion of the adhesive layer to the acrylic substrate (according to JIS Z 0237) is 0.15 N/25 mm, and the protective film is The PET film has a thickness of 25 μm. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Example 4]

An antifouling film having an optical film thickness of 40 nm was formed on the 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, on both sides of the transparent substrate on which the antifouling film was formed, a protective film (RP-207, manufactured by Nitto Denko Corporation) with an adhesive layer was attached to the same laminating machine as in Example 1, and a substrate 4 with an antifouling film was produced. The material constituting the adhesive layer of the protective film with the adhesive layer is an acrylic adhesive, and the 180-degree peeling adhesion of the adhesive layer to the acrylic substrate (according to JIS Z 0237) is 0.1 N/25 mm, and the protective film is a PET film, and the protective film is protected. The thickness of the film was 25 μm. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Example 5]

An antifouling film having an optical film thickness of 10 nm was formed on a transparent substrate in the same manner as in Example 1 except that the antiglare treatment was not carried out. Further, on both sides of the transparent substrate on which the antifouling film was formed, a protective film (Y16FS, manufactured by Sun A Kaken Co., Ltd.) with an adhesive layer was attached to the same laminating machine as in Example 1, and a substrate 5 with an antifouling film was produced. The material constituting the adhesive layer of the protective film with the adhesive layer is an acrylic adhesive, and the 180-degree peeling adhesion of the adhesive layer to the acrylic substrate (according to JIS Z 0237) is 0.3 N/25 mm, and the protective film is a PET film, and the protective film is protected. The thickness of the film was 25 μm. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Embodiment 6]

A fluorine-containing hydrolyzable ruthenium compound (OPTOOL DSX, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as a raw material of the anti-fouling film, and an anti-glare treatment is not performed and an anti-reflection film is not formed, and An antifouling film having an optical film thickness of 30 nm was formed on a transparent substrate in the same manner as in Example 1. Further, on both sides of the transparent substrate on which the antifouling film was formed, a protective film (RP-207, manufactured by Nitto Denko Corporation) with an adhesive layer was attached to the same laminating machine as in Example 1, and a substrate 6 with an antifouling film was produced. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Embodiment 7]

An antifouling film having an optical film thickness of 20 nm was formed on the transparent substrate in the same manner as in Example 1 except that the antireflection film was not formed. Further, a protective film (EC-9000AS, manufactured by SUMIRON Co., Ltd.) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed, in the same manner as in Example 1, to produce a substrate 7 with an antifouling film. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Comparative Example 1]

An antifouling film having an optical film thickness of 10 nm was formed on the 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 with an adhesive layer (TG-3030, manufactured by SUMIRON Co., Ltd.) was provided on both surfaces of the transparent substrate on which the antifouling film was formed, using the same laminating machine as in Example 1, to manufacture a substrate with an antifouling film. 1C. The material constituting the adhesive layer of the protective film with the adhesive layer is an acrylic adhesive, and the 180-degree peeling adhesion of the adhesive layer to the acrylic substrate (according to JIS Z 0237) is 3.0 N/25 mm, and the protective film is a PET film, and the protective film is protected. The thickness of the film was 25 μm. The rubbing durability, optical film thickness, and optical unevenness of the antifouling film were measured in the same manner as in Example 1.

[Comparative Example 2]

An antifouling film having an optical film thickness of 60 nm was formed on the 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 (EC-9000AS, manufactured by SUMIRON Co., Ltd.) with an adhesive layer was provided on both surfaces of the transparent substrate on which the antifouling film was formed, in the same manner as in Example 1, to produce a substrate 2C with an antifouling film. The friction durability, optical film thickness, and optical properties of the antifouling film were measured in the same manner as in Example 1. Uneven.

The manufacturing conditions of the substrate 1 to 2C with the antifouling film and the frictional durability and optical of the antifouling film of the substrate 1 to 7 with the antifouling film produced in Examples 1 to 7 and the antifouling film produced in Comparative Examples 1 and 2 The measurement results of film thickness and optical unevenness are shown in Table 1. Moreover, the rate of change of the optical film thickness of the antifouling film calculated by the above formula (1) is shown in Table 1.

As shown in Table 1, it is understood that the optical film thickness of the antifouling film in the state in which the adhesive layer and the protective film are provided is 10 nm to 50 nm, and the optical film thickness of the antifouling film after removing the adhesive layer and the protective film is set to The base bodies 1 to 7 of the anti-fouling film of 3 nm to 30 nm can suppress the decrease in the abrasion resistance of the anti-fouling film caused by the removal of the adhesive layer and the protective film. Further, it is understood that the substrates 1 to 7 to which the antifouling film is attached have no optical unevenness and have excellent transparency.

1‧‧‧Substrate with antifouling film

2‧‧‧Transparent substrate

3‧‧‧Antifouling film

4‧‧‧Adhesive layer

5‧‧‧Protective film

Claims (7)

A substrate with an antifouling film, which is provided with an antifouling film, an adhesive layer, and a protective film on the main surface of the transparent substrate, and the user is removed from the adhesive layer and the protective film, and The anti-fouling film having the adhesive layer and the protective film has an optical film thickness of 10 nm to 50 nm, and the anti-fouling film after removing the adhesive layer and the protective film has an optical film thickness of 3 nm to 30 nm. A substrate with an antifouling film, which is provided with an antifouling film, an adhesive layer, and a protective film on the main surface of the transparent substrate, and the user is removed from the adhesive layer and the protective film, and The optical film thickness of the antifouling film after removing the adhesive layer and the protective film is 3 nm to 30 nm, and {(the optical film thickness of the antifouling film in the state in which the adhesive layer and the protective film are provided)- The optical film thickness of the anti-fouling film after the adhesive layer and the protective film is changed by ×100/ (the optical film thickness of the anti-fouling film in the state in which the adhesive layer and the protective film are provided) (%) The rate is 10~60%. The substrate of the antifouling film according to claim 1 or 2, wherein the adhesive layer has a 180-degree peeling adhesion (according to JIS Z 0237) with respect to the acrylic substrate of 0.02 N/25 mm to 0.4 N/25 mm. The substrate to which the antifouling film is attached according to any one of claims 1 to 3, wherein the transparent substrate is a glass substrate. The substrate to which the antifouling film is attached according to any one of claims 1 to 4, further comprising an antireflection film between the transparent substrate and the antifouling film. The substrate of the antifouling film according to any one of claims 1 to 5, wherein the transparent substrate is The main surface has a concave-convex shape. The substrate to which the antifouling film according to any one of claims 1 to 6, wherein the antifouling film is formed of a film forming composition containing a fluorine-containing hydrolyzable cerium compound.