KR102378656B1 - Substrate having antifouling film - Google Patents

Abstract

A state in which an antifouling film, an adhesive layer, and a protective film are sequentially provided on a main surface of a transparent substrate, and the antifouling film forming substrate is used by removing the adhesive layer and the protective film, wherein the adhesive layer and the protective film are provided An antifouling film-forming substrate having an optical film thickness of 10 nm to 50 nm, and an optical film thickness of the antifouling film after removal of the adhesive layer and the protective film, of 3 nm to 30 nm.

Description

Antifouling film-forming gas {SUBSTRATE HAVING ANTIFOULING FILM}

The present invention relates to an antifouling film-forming gas.

BACKGROUND ART A touch panel used in a smart phone, a tablet PC, a car navigation device, or the like, is easily attached to contaminants such as fingerprints, sebum, sweat, etc. because a human finger touches the touch panel during use. In addition, these contaminants do not come off easily when attached, and the difference between a portion to which the contaminants are attached and a portion not to which the contaminants are attached is conspicuous due to a difference in scattering or reflection of light. Therefore, the touch panel to which these contaminants adhered had a problem that visibility and aesthetics were impaired. Moreover, the same problem was pointed out also in display glass, an optical element, a sanitary appliance, etc.

In order to solve such a problem, the method of using the base|substrate which formed the antifouling|stain-resistant film which consists of a fluorine-containing hydrolyzable silicon compound in the part in which a human finger in these parts or equipment is used is known. The antifouling film formed on the base is required to have high water repellency and oil repellency in order to suppress the adhesion of contaminants, and also abrasion resistance against the erosion of the adhering contaminants.

As the antifouling film having water repellency and oil repellency, for example, in Patent Document 1, a cured film formed using a 9:1 mixture of a fluorooxyalkylene group-containing polymer-modified silane and a fluorooxyalkylene group-containing polymer; and A cured film-forming glass substrate is disclosed. Moreover, Patent Document 2 discloses an antifouling film-forming glass substrate obtained by dry coating a fluorine-containing dry coating agent diluted with a diluent for a fluorine-containing dry coating agent having a specific composition.

In order to prevent damage to the antifouling film-forming glass substrate when transporting the glass substrate for forming an antifouling film as described above after production, a protective film is provided on the surface of the antifouling film formed on the glass substrate through an adhesive layer. . The adhesive layer and protective film are removed when the antifouling film-forming glass substrate is used in the product.

Japanese Patent Laid-Open No. 2013-136833 Japanese Laid-Open Patent Publication No. 2013-244470

In the conventional glass substrate for forming an antifouling film, when the adhesive layer and the protective film are removed, a part of the antifouling film together with the adhesive layer is peeled off from the glass substrate, so that the antifouling film forming glass substrate has antifouling properties such as water repellency and oil repellency, and abrasion resistance. There were cases where it deteriorated.

An object of the present invention is to provide an antifouling film-forming substrate having excellent antifouling properties and abrasion resistance after removal of the adhesive layer and the protective film.

The antifouling film-forming substrate of the present invention is an antifouling film-forming substrate that is sequentially provided with an antifouling film, an adhesive layer, and a protective film on a main surface of a transparent substrate, and is used by removing the adhesive layer and the protective film, wherein the adhesive The optical film thickness of the said antifouling film in the state provided with a layer and the said protective film is 10 nm - 50 nm, and the optical film thickness of the said antifouling film after removing the said adhesion layer and the said protective film is 3 nm - 30 nm.

In addition, the antifouling film-forming substrate of the present invention is provided with an antifouling film, an adhesive layer, and a protective film sequentially on a main surface of a transparent substrate, and is used by removing the adhesive layer and the protective film, The optical film thickness of the antifouling film after removing the adhesion layer and the protective film is 3 nm to 30 nm, {(optical film thickness of the antifouling film in a state including the adhesion layer and the protective film) - (the adhesion The rate of change given in the optical film thickness of the antifouling film after removing the layer and the protective film) } x 100/(the optical film thickness of the antifouling film in the state including the adhesive layer and the protective film) (%) is 10 to 60 % am.

It is possible to provide an antifouling film-forming substrate having excellent antifouling properties and abrasion resistance after removing the adhesive layer and the protective film.

1 : is sectional drawing which shows one Embodiment of the antifouling|stain-resistant film-forming base|substrate 1 of this invention.
It is sectional drawing which shows the antifouling|stain-resistant film after removing an adhesion layer and a protective film.
3 : is a figure which shows typically the apparatus which can be used for one Embodiment of the manufacturing method of the antifouling|stain-resistant film-forming base|substrate 1 of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated. The present invention is not limited to the following embodiments. Various modifications and substitutions can be added to the following embodiments without departing from the scope of the present invention.

[Antifouling film-forming gas (1)]

1 : is sectional drawing which shows one Embodiment of the antifouling|stain-resistant film-forming base|substrate 1 of this invention. An antifouling film-forming base 1 (also referred to as an antifouling body) of the embodiment includes a transparent base 2 and an antifouling film 3 formed on a main surface of the transparent base 2 . Further, the antifouling film-forming substrate 1 includes an adhesive layer 4 removably provided on the surface of the antifouling film 3 , and a protective film 5 removably provided on the surface of the adhesion layer 4 . . And the optical film thickness of the antifouling film 3 in the state provided with the adhesion layer 4 and the protective film 5, in other words, the antifouling film before removing the adhesion layer 4 and the protective film 5 ( The optical film thickness of 3) is 10 nm - 50 nm.

The antifouling film-forming substrate 1 is used by removing the adhesive layer 4 and the protective film 5 . 2 : is sectional drawing which shows the antifouling|stain-resistant film 3a after removing the adhesion layer 4 and the protective film 5. As shown in FIG. In FIG. 2, the optical film thickness of the antifouling|stain-resistant film 3a after removing the adhesion layer 4 and the protective film 5 is 3 nm - 30 nm. Compared to the optical film thickness of the antifouling film 3 before removing the adhesion layer 4 and the protective film 5, the optical film thickness of the antifouling film 3a after removing the adhesion layer 4 and the protective film 5 is small

In addition, in the antifouling film forming base 1, the antifouling film 3, the adhesive layer 4, the protective film 5, and the antireflection film mentioned later are formed on at least one main surface of the transparent base 2, What is necessary is just to be sufficient, and you may form in both main surfaces of the transparent base 2 as needed.

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

That is, the hydrolyzable silyl group of the fluorine-containing hydrolyzable silicon compound becomes a silanol group by hydrolysis, and further, the silanol group undergoes dehydration condensation between the fluorine-containing hydrolyzable silicon compound to form a siloxane bond represented by -Si-O-Si- By producing the antifouling film 3, the antifouling film 3 is formed. Most of the fluorine-containing organic groups bonded to the silicon atoms constituting the siloxane bond exist in the vicinity of the surface of the antifouling film 3 due to the affinity between the fluorine-containing hydrolyzable silicon compound and the transparent gas 2 . Therefore, water repellency and oil repellency are expressed on the surface of the antifouling film 3 by the action of this fluorine-containing organic group. Further, for example, when a free substrate is used as the transparent substrate 2 , the silanol group of the fluorinated hydrolyzable silicon compound produced by hydrolysis is dehydrated and condensed with the hydroxyl group present on the surface of the transparent substrate 2 . Upon reaction, the antifouling film 3 is formed on the transparent substrate 2 via a siloxane bond.

And on the antifouling film 3 formed in this way, the protective film 5 is provided through the adhesion layer 4 in order to protect the antifouling film 3 . When the antifouling film-forming base 1 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, the fluorine-containing hydrolyzable silicon compound constituting a part of the surface of the antifouling film 3 is removed from the antifouling film 3 together with the adhesive layer 4 can't avoid being

Then, 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 adhesion layer 4 and the protective film 5 may be set to 10 nm - 50 nm An antifouling film 3 is formed. When the adhesion layer 4 and the protective film 5 are provided on the surface of the antifouling film 3 which has such an optical film thickness, and the adhesion layer 4 and the protective film 5 are removed, the antifouling film 3 ), the fluorine-containing hydrolyzable silicon compound that is not adhered to the transparent substrate 2, which constitutes the vicinity of the surface, adheres to the adhesive layer 4 and is removed. As a result of removing a part of the fluorine-containing hydrolyzable silicon compound constituting the antifouling film 3, the optical film thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 is 3 nm to 30 becomes nm.

Conventionally, the optical film thickness of the antifouling film|membrane before removing an adhesion layer and a protective film was set to the optimal film thickness of the antifouling film|membrane after removing the adhesion layer and protective film in other words at the time of use. That is, the optical film thickness of the antifouling|stain-resistant film before removing an adhesion layer and a protective film was an optimal film thickness. And, since the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film is removed from the transparent gas together with the adhesive layer, the optical film thickness of the antifouling film after removing the adhesive layer and the protective film is smaller than the optimum film thickness, and the antifouling property of the antifouling film However, there was a case where the abrasion resistance deteriorated. On the other hand, in the antifouling film 3 constituting the antifouling film forming base 1 of the present embodiment, the optical film thickness of the antifouling film 3a after removing the adhesive layer 4 and the protective film 5 is optimal. is set to be That is, the optical film thickness of the antifouling film 3a after removing the adhesion layer 4 and the protective film 5 is an optimal film thickness. And even if a part of the fluorine-containing hydrolyzable silicon compound constituting the antifouling film 3 is removed together with the adhesive layer 4, since the optical film thickness of the antifouling film 3a is optimal, the antifouling film 3a is Good antifouling and abrasion resistance can be maintained.

Hereinafter, each element which comprises the antifouling|stain-resistant film-forming base|substrate 1 of embodiment is demonstrated.

(transparent gas)

The transparent substrate 2 constituting the antifouling film-forming substrate 1 is not particularly limited as long as it is made of a transparent material that is generally required to provide antifouling properties by the antifouling film 3, for example, glass, resin, or It is preferable to consist of those combinations (composite material, laminated material, etc.). Moreover, it does not specifically limit also about the form of the transparent base 2, For example, it can be set as the plate shape which has rigidity, the film shape which has flexibility, etc.

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

Further, as the polymer film used as the film-like transparent substrate 2, for example, a polyester film such as polyethylene terephthalate, a polyolefin film such as polypropylene, a polyvinyl chloride film, an acrylic resin film, polyether A sulfone film, a polyarylate film, a polycarbonate film, etc. are mentioned.

In addition, as the glass substrate used as the transparent substrate 2, as an example, common glass containing silicon dioxide as a main component, for example, soda lime silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, quartz glass, etc. The glass gas formed is mentioned.

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

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. As a composition of glass, the composition of the following glass (all are aluminosilicate glass.) is mentioned, for example.

(i) A composition expressed in mol%, SiO ₂ 50 to 80%, Al ₂ O ₃ 2 to 25%, Li ₂ O 0 to 10%, Na ₂ O 0 to 18%, K ₂ O Glass containing 0 to 10% of MgO, 0 to 15% of MgO, 0 to 5% of CaO, and 0 to 5% of ZrO ₂

(ii) a composition expressed in mol%, SiO ₂ 50 to 74%, Al ₂ O ₃ 1 to 10%, Na ₂ O 6 to 14%, K ₂ O 3 to 11%, MgO 2 -15%, 0-6% of CaO, and 0-5% _of ZrO2 are contained, the sum _{total of} content _of SiO2 and Al2O3 is 75% or less, and the sum total _of content of Na2O and K2O is ₁₂ Glass whose total content of ∼25% and MgO and CaO is 7∼15%

(iii) A composition expressed in mol%, SiO ₂ 68 to 80%, Al ₂ O ₃ 4 to 10%, Na ₂ O 5 to 15%, K ₂ O 0 to 1%, MgO 4 Glass containing _∼15 % and 0-1% of ZrO2

(iv) a composition expressed in mol%, 67 to 75% _of SiO2, 0-4% _of Al2O3, 7-15% _of Na2O, 1-9% _of K2O, ₆ % of MgO It contains -14% and 0-1.5% _of ZrO2, the sum _total of content _of SiO2 and Al2O3 is 71-75%, the sum _{total of} content _of Na2O and K2O is 12-20%, CaO Glass with a CaO content of less than 1% when containing

Moreover, as a composition of the glass used as a material of the transparent base 2, the following glass compositions (all are soda-lime silicate glass.) are also mentioned.

(v) a composition expressed in mol%, SiO ₂ 65 to 75%, Al ₂ O ₃ 0.1 to 5%, MgO 1 to 15%, CaO 1 to 15%, Na ₂ O and K ₂ O Glass containing and whose _total content _of Na2O and K2O is 10 to 18%.

(vi) a composition expressed in mol%, 65 to 72% of SiO2, _2-7 % _of Al2O3, 5-15% of MgO, _3-9 % of CaO, 13-18 _of Na2O %, K ₂ O 0 to 1%, TiO ₂ 0 to 0.2%, Fe ₂ O ₃ 0.01 to 0.15% and SO ₃ 0.02 to 0.4%, (Na ₂ O and K ₂ O content of _The glass whose total)/(content of Al2O3) is _3.5-6.0 .

(vii) A composition expressed in mol%, SiO ₂ 60 to 72%, Al ₂ O ₃ 1 to 10%, MgO 5 to 12%, CaO 0.1 to 5%, Na ₂ O 13 to 19 % and 0 to 5% of K ₂ O, and (content of RO)/(sum of content of RO and R ₂ O) is 0.20 to 0.42 (wherein, RO is an alkaline earth metal oxide, R ₂ O is an alkali metal Oxide is indicated.) Phosphorus glass.

Hereinafter, it shows by mol% display about content of each component contained in glass.

SiO ₂ is a component constituting the skeleton of glass. In addition, it is a component that reduces the occurrence of cracks when a scratch (indentation) occurs on the glass surface, a component that reduces the fracture rate when an indentation is made on the glass surface after chemical strengthening, and is a component that reduces the coefficient of thermal expansion . Content _of SiO2 becomes like this. Preferably it is 50 % or more, More preferably, it is 60 % or more, More preferably, it is 64 % or more, Especially preferably, it is 66 % or more. When content _of SiO2 is 50 % or more, the fall of stability as glass, acid resistance, weather resistance, and chipping resistance can be avoided. _On the other hand, content of SiO2 becomes like this. Preferably it is 80 % or less, More preferably, it is 75 % or less, More preferably, it is 70 % or less. When content _of SiO2 is 80 % or less, the fall of the meltability by viscosity increase of glass can be avoided.

Al ₂ O ₃ is an effective component in order to improve ion exchange performance and chipping resistance, is a component which increases surface compressive stress, and is also a component which makes it difficult to increase the coefficient of thermal expansion above a glass transition point. Content of Al2O3 becomes like this. Preferably it is 0.1 % or more, More preferably, it is ₂ % or more, More preferably, it is ₃ % or more, Especially preferably, it is 5 % or more. Moreover, content _of Al2O3 becomes like this. Preferably it is ₂₀ % or less, More preferably, it is 15 % or less, More preferably, it is 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 content of Al2O3 is ₂₀ % or less, the fall of the meltability by the viscosity increase of glass can be avoided.

MgO is a component which stabilizes glass, and is also a component required in order to maintain a thermal expansion coefficient moderately. The content of MgO is preferably 1% or more, more preferably 2% or more, 3% or more, 4% or more, 5% or more, and 8% or more (8% or more is particularly preferable). The content of MgO is preferably 15% or less, more preferably 14% or less, 13% or less, 12% or less, 11% or less, and 10% or less (10% or less is particularly preferable). When content of MgO is 1 % or more, solubility in high temperature becomes favorable and devitrification does not occur easily. On the other hand, when content of MgO is 15 % or less, devitrification hardly occurs is maintained and sufficient ion exchange rate is obtained.

CaO is a component which improves the meltability of glass, and in order to maintain a thermal expansion coefficient moderately, it is also an effective component. Content of CaO becomes like this. Preferably it is 0.05 % or more, More preferably, it is 0.1 % or more, More preferably, it is 1 % or more, Especially preferably, it is 4 % or more. On the other hand, content of CaO becomes like this. Preferably it is 10 % or less, More preferably, it is 8 % or less, More preferably, it is 5 % or less. When content of CaO is 0.05 % or more, meltability can be improved, and when content of CaO is 10 % or less, a surface compressive stress layer can be deepened.

Na2O is a component which forms a surface compressive _- stress layer by ion exchange, and is also a component which improves the meltability of glass. Since Na2O is a component from which a thermal expansion coefficient becomes large even if the density _of glass is low, in order to adjust a thermal expansion coefficient, it is effective. Content _of Na2O becomes like this. Preferably it is 10 % or more, More preferably, it is 11 % or more, More preferably, it is 12 % or more, Especially preferably, it is 13 % or more. _On the other hand, content of Na2O becomes like this. Preferably it is 19 % or less, More preferably, it is 18 % or less, More preferably, it is 16 % or less, Especially preferably, it is 15 % or less. When the content of Na ₂ O is 10% or more, a desired surface compressive stress layer can be formed by ion exchange, and when the content of Na ₂ O is 19% or less, the weather resistance and acid resistance fall, and cracks due to indentation are generated. can be avoided.

_Although K2O can be contained as needed, 0.1 % or more of the content is preferable. When content _of K2O is 0.1 % or more, the solubility in high temperature of glass and a moderate thermal expansion coefficient can be maintained. Content _of K2O becomes like this. More preferably, it is 0.5 % or more, More preferably, it is 1 % or more, Especially preferably, it is 2 % or more. Moreover, as for content of K2O, ₈ % or less is preferable. When content of K2O is ₈ % or less, the density of glass becomes small and the weight of glass becomes small. Content _of K2O becomes like this. More preferably, it is 6 % or less, More preferably, it is 4 % or less.

Fe ₂ O ₃ is a component that improves the meltability of glass. Usually, Fe ₂ O ₃ in glass absorbs visible light, but in the case of thin glass, light absorption is less, so it is not a problem. In addition, Fe has an effect of increasing the high-temperature coefficient of thermal expansion (?max). In addition, since Fe is a component that absorbs heat rays, it promotes thermal convection of the glass melt to improve the homogeneity of the glass, and prevents the heating of the bottom brick of the melting kiln to increase the kiln life. It is preferable to contain in the composition in the melting process of the plate glass manufactured using Content _of Fe2O3 becomes like this _. Preferably it is 0.005 % or more, More preferably, it is 0.01 % or more, More preferably, it is 0.03 % or more, Especially preferably, it is 0.06 % or more. On the other hand, when it contains excessively, since the color taste by Fe ₂ O ₃ becomes a problem, the content of Fe ₂ O ₃ is preferably less than 0.2%, more preferably less than 0.15%, and further less than 0.12%. Preferably, less than 0.095% is particularly preferable.

The manufacturing method of the glass substrate is not particularly limited, and a desired glass material is put into a continuous melting furnace, the glass material is heated and melted preferably at 1500 to 1600° C., clarified, and then the molten glass is supplied to a forming apparatus It can manufacture by shape|molding in plate shape and slow cooling.

In addition, it does not specifically limit as a shaping|molding method of a glass substrate, For example, a down-draw method (For example, overflow down-draw method, a slot-down method, a lid-draw method, etc.), a float method, the roll-out method, press A molding method such as a method can be used.

The thickness of the transparent base 2 can be suitably selected according to a use. For example, when the transparent substrate 2, such as a resin substrate and a glass substrate, is plate-shaped, it is preferable that it is 0.1-5 mm, and, as for the thickness of the transparent substrate 2, it is more preferable that it is 0.2-2 mm. In particular, when a glass substrate is used as the transparent substrate 2 and a chemical strengthening treatment described later is performed or when weight reduction is aimed, in order to effectively perform a chemical strengthening treatment and weight reduction, the thickness of the glass substrate is 5 mm It is preferable that it is less than, and it is more preferable that it is 3 mm or less. When used for touch panels for portable electronic devices such as smart phones and tablet PCs, since weight reduction is particularly important, the thickness of the glass substrate is more preferably 1 mm or less, and particularly preferably 0.7 mm or less. On the other hand, when used for a touch panel for in-vehicle electronic devices such as a car navigation system, since rigidity is more important than weight reduction, the thickness of the glass substrate is more preferably 0.7 mm or more, and particularly preferably 1.0 mm or more.

Moreover, when the transparent substrate 2 is a film form, such as a polymer film, it is preferable that it is 50-200 micrometers, and, as for the thickness of the transparent substrate 2, it is more preferable that it is 75-150 micrometers.

When using a glass substrate as the transparent substrate 2, the surface treatment by oxygen gas plasma may be given to the main surface of the glass substrate. In addition, a silicon oxide film may be formed on the main surface of the glass substrate by sputtering or the like. When performing the anti-glare treatment or chemical strengthening process mentioned later, it is preferable to perform these processes after an anti-glare treatment or a chemical strengthening process.

(Anti-glare treatment)

The main surface of the transparent substrate 2 preferably has an uneven shape in order to impart anti-glare properties to the antifouling film-forming substrate 1 .

An anti-glare treatment can be used as a method of forming the concave-convex shape. The anti-glare treatment is not particularly limited. For example, when a glass substrate is used as the transparent substrate 2, the main surface of the glass substrate is chemically or physically subjected to surface treatment to form an uneven shape having a desired surface roughness. method can be used.

As a method of chemically performing an anti-glare process, the method of performing a frost process is mentioned, for example. The frost treatment can be performed, for example, by immersing the free gas as a target object in a mixed solution of hydrogen fluoride and ammonium fluoride.

In addition, as a method of physically performing the anti-glare treatment, for example, a so-called sand blasting treatment in which crystalline silicon dioxide powder, silicon carbide powder, etc. are sprayed onto the main surface of a glass substrate with pressurized air, crystalline silicon dioxide powder, carbonization A method, such as a method in which a brush to which silicon powder or the like is adhered, is wetted with water, and the wet brush is rubbed on the main surface of the glass substrate, or the like can be used.

Among them, the frost treatment, which is a chemical surface treatment, is preferably used as a method for surface-treating a glass substrate, since microcracks on the surface of the object to be treated are less likely to occur and a decrease in mechanical strength is less likely to occur. .

Thus, it is preferable to perform an etching process in order to make a surface shape even with respect to the main surface of the glass substrate which gave the anti-glare process chemically or physically. As the etching treatment, for example, a method of chemically etching the glass substrate by immersing it in an etching solution that is an aqueous solution of hydrogen fluoride can be used. In addition to hydrogen fluoride, an etching solution may contain acids, such as hydrochloric acid, nitric acid, and a citric acid. By containing these acids, the local generation of precipitates on the surface of the free gas due to the reaction of hydrogen fluoride with cation components such as Na ions and K ions contained in the free gas can be suppressed, and the free gas can be suppressed. The surface of the can be etched uniformly.

When performing an etching process, the etching amount can be adjusted by changing the density|concentration of an etching solution, the immersion time of the glass gas to the etching solution (it is also referred to as "etching time" hereafter), etc. Thereby, the haze value of the surface (henceforth an "anti-glare treatment surface") which has the uneven|corrugated shape of a glass substrate can be adjusted to a desired value. Moreover, when an antiglare treatment is performed by physical surface treatment, such as a sandblasting process, although cracks may generate|occur|produce in the transparent substrate 2, such a crack can be removed by an etching process. The longest in-plane crack depth is preferably 5 µm or less, more preferably 3 µm or less. When it exists in this range, reduction of the crack strength by an in-plane crack can fully be suppressed. In-plane crack depth can be measured as follows. First, a plurality of transparent substrates having the same properties (for example, 5 sheets) are prepared. Next, the main surface of each transparent substrate is polished by using cerium oxide abrasive grains to change the polishing amount in stages. The polishing amount is set to, for example, 1 µm, 2 µm, 3 µm, 4 µm, or 5 µm. Then, when a small amount etches the main surface of a transparent substrate using a 1 mol% HF aqueous solution, it will become easy to confirm the crack which remains. The crack depth can be measured by confirming with an optical microscope (VK-X120 by Keyence Corporation) how many micrometers this crack trace remains until it grind|polishes. That is, if no crack marks remain at the polishing amount of 5 µm, the crack depth can be said to be 5 µm or less. Moreover, the effect of suppressing the glare of the antifouling|stain-resistant film formation base 1 by an etching process can also be acquired.

In this way, as the shape of the main surface of the glass substrate after the anti-glare treatment and the etching treatment are performed, the surface roughness (mean-square roughness (RMS)) is preferably 0.01 to 0.5 µm, more preferably 0.01 to 0.3 µm, , more preferably 0.01 to 0.2 µm. When surface roughness (RMS) is an above-described range, the haze value of the glass substrate after an anti-glare treatment can be adjusted to 3 to 30 %. As a result, excellent anti-glare properties can be imparted to the obtained antifouling film-forming substrate 1 .

In addition, the surface roughness (RMS) can be measured based on the method prescribed|regulated by JISB0601:(2001). As a measuring method of surface roughness (RMS), specifically, using a laser microscope (VK-9700, manufactured by Keyence Corporation), a viewing range of 300 µm × 200 µm is measured on the measurement surface of the glass substrate after the anti-glare treatment as the sample. Set and measure the height information of the glass substrate. Surface roughness (RMS) is computable by performing cutoff correction about a measured value, and calculating|requiring the square average of the obtained height. It is preferable to use 0.08 mm as a cut-off value.

In addition, a haze value is the value measured based on the method prescribed|regulated by JISK7136.

Moreover, the surface of the glass substrate after the anti-glare treatment and the etching treatment has been performed has an uneven shape, and when the uneven shape is observed from above the surface of the glass substrate, it appears as a circular hole. The size (diameter) of the circular holes observed in this way is preferably 1 µm or more and 10 µm or less. By being in such a range, glare prevention and anti-glare property can be made compatible.

When a glass substrate is used as the transparent substrate 2, in order to increase the strength of the obtained antifouling film-forming substrate 1, it is preferable to chemically strengthen the main surface or the anti-glare treatment surface of the glass substrate.

It does not specifically limit as the method of a chemical strengthening process, By giving an ion exchange process to the main surface of a glass substrate or an anti-glare treatment surface, the surface layer in which a compressive stress remains is formed in these surfaces. Specifically, at a temperature below the glass transition point, alkali metal ions with a small ionic radius (eg, Li ions, Na ions) contained in the vicinity of the main surface of the glass substrate or the anti-glare treatment surface have a larger ionic radius. It is substituted with an alkali metal ion (for example, Na ion or K ion for Li ion, K ion for Na ion). Thereby, compressive stress remains on the main surface or anti-glare treatment surface of a glass substrate, and the intensity|strength of a glass substrate improves.

(Anti-reflection film)

The antifouling film-forming substrate 1 may include an antireflection film between the transparent substrate 2 and the antifouling film 3 . When the transparent base 2 has the said uneven|corrugated shape, it is preferable that an antireflection film is provided on the anti-glare treatment surface.

The configuration of the antireflection film is not particularly limited as long as it is a configuration capable of suppressing light reflection, and for example, a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550 nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550 nm It can be set as the structure which laminated|stacked.

Although the antireflection film may contain one each of a high-refractive-index layer and a low-refractive-index layer, it may also contain two or more layers of a high-refractive-index layer and a low-refractive-index layer, respectively. When the antireflection film includes two or more layers of a high refractive index layer and a low refractive index layer, respectively, it is preferable that the high refractive index layer and the low refractive index layer are alternately laminated.

In particular, in order to improve the antireflection performance, the antireflection film is preferably a laminate in which a plurality of layers are laminated, for example, the laminate is preferably in two or more layers and 6 or less layers laminated, and two or more layers. It is more preferable that four or less layers are laminated|stacked. It is preferable that the laminated body here is the laminated body which laminated|stacked the high refractive index layer and the low refractive index layer, and it is preferable that what summed up the number of each layer of a high refractive index layer and a low refractive index layer is the said 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 required degree of antireflection performance, productivity, and the like. Examples of the material constituting the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), and silicon nitride (SiN). It is preferable to use one or more selected types. As a material constituting the low refractive index layer, silicon oxide (SiO ₂ ), a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and a material containing a mixed oxide of Si and Al It is preferable to use one or more selected types.

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

The method of forming an antireflection film into a film is not specifically limited, Various film forming methods can be used. In particular, it is preferable to form a film by a method such as pulse sputtering, AC sputtering, or digital sputtering. By setting it as these methods, a dense film|membrane can be made and durability can be ensured.

For example, when film-forming by pulse sputtering, the transparent gas 2 is arrange|positioned in the chamber of the mixed gas atmosphere of an inert gas and oxygen gas, a target is selected so that it may become a desired composition, and an antireflection film is formed into a film.

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

Although the pressure in the chamber by the mixed gas of an inert gas and oxygen gas is not specifically limited, By setting it as 0.5 Pa or less, since the surface roughness of an antireflection film can be easily made into the said preferable range, it is preferable. In this case, if the pressure in the chamber by the mixed gas of the inert gas and oxygen gas is 0.5 Pa or less, the average free path of the film-forming molecules is ensured, and the film-forming molecules reach the transparent gas 2 with more energy. Accordingly, rearrangement of the film-forming molecules is promoted to produce a film having a relatively dense and smooth surface. Although the lower limit of the pressure in the chamber by the mixed gas of an inert gas and oxygen gas is not specifically limited, For example, it is preferable that it is 0.1 Pa or more.

(Anti-fouling curtain)

The antifouling film-forming base 1 is provided with the antifouling film 3 on the main surface of the transparent base 2 . When the antireflection film is formed on the main surface or the antiglare treatment surface of the transparent substrate 2, the antifouling film 3 is preferably formed on the surface of the antireflection film. In addition, when using a glass substrate that has been subjected to surface treatment such as anti-glare treatment or chemical strengthening treatment as the transparent substrate 2 and is not formed with an anti-reflection film, the anti-fouling film 3 is formed on the surface subjected to these surface treatments. It is preferable to be

As a method of forming the antifouling film 3, as an example, a composition of a silane coupling agent having a perfluoroalkyl group, for example, a fluoroalkyl group such as a fluoroalkyl group containing a perfluoro(polyoxyalkylene) chain. is applied to the main surface of the transparent substrate 2 by a spin coating method, a dip coating method, a casting method, a slit coating method, a spray coating method, etc. 2) vapor deposition on the main surface and then heat-treating vacuum deposition, etc. are mentioned. In order to obtain the antifouling|stain-resistant film 3 with high adhesiveness, it is preferable to form by the vacuum vapor deposition method. It is preferable to perform formation of the antifouling|stain-resistant film 3 by a vacuum vapor deposition method using the composition for film formation containing the fluorine-containing hydrolysable silicon compound.

The composition for film formation is not particularly limited as long as it is a composition containing a fluorine-containing hydrolyzable silicon compound and can form the antifouling film 3 by vacuum vapor deposition. The composition for film formation may contain arbitrary components other than a fluorine-containing hydrolysable silicon compound, and may be comprised only with a fluorine-containing hydrolysable silicon compound. Examples of optional components include hydrolyzable silicon compounds (hereinafter referred to as "non-fluorine hydrolysable silicon compounds"), catalysts, etc. which are used in the range which does not impair the effect of this invention and do not have a fluorine atom.

In addition, when a fluorine-containing hydrolyzable silicon compound and optionally a non-fluorine hydrolysable silicon compound are blended into the film-forming composition, each compound may be blended as it is or may be blended as a partial hydrolysis-condensation product thereof. Moreover, you may mix|blend in the composition for film formation as a mixture of each compound and its partial hydrolysis-condensation product.

Further, when two or more fluorine-containing hydrolyzable silicon compounds are used in combination, each compound may be blended in the film-forming composition as it is, or blended as individual partial hydrolysis-condensation products, or two or more kinds of compounds You may mix|blend as a partial hydrolysis cocondensate. Moreover, you may mix|blend the mixture of these compounds, a partial hydrolysis-condensation product, and a partial hydrolysis-cocondensation product. However, the partial hydrolysis-condensation product and partial hydrolysis-cocondensation product to be used shall have a degree of polymerization such that vacuum vapor deposition is possible. In addition, in addition to the compound itself, the fluorine-containing hydrolyzable silicon compound includes such partial hydrolysis-condensation products and partial hydrolysis-cocondensation products.

(fluorinated hydrolyzable silicon compound)

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

Specific examples include fluorine-containing hydrolyzable silicon compounds having at least one group selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group. These groups exist as fluorine-containing organic groups bonded or directly bonded to the silicon atom of the hydrolyzable silyl group via a linking group. In addition, the perfluoropolyether group means the divalent group which has a structure in which the perfluoroalkylene group and the etheric oxygen atom couple|bonded alternately. It is preferable that it is 2000-10000, and, as for the number average molecular weight (Mn) of a fluorine-containing hydrolysable silicon compound, it is more preferable that it is 3000-5000. When the number average molecular weight (Mn) of the fluorine-containing hydrolyzable silicon compound is within the above range, the antifouling property of the antifouling film 3 is sufficiently expressed, and the abrasion resistance is also excellent. In addition, the number average molecular weight (Mn) in this specification means what was measured by the gel permeation chromatograph.

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

[Formula 1]

In formula (I), R ^f1 is a linear perfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group, for example, a methyl group, an 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 (eg, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), X ¹ is a hydrolyzable group (eg, an amino group) , alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), m is 1 to 50, preferably 1 to 30 Integer, n is 0-2, Preferably it is an integer of 1-2, p is an integer of 1-10, Preferably it is an integer of 1-8.

In formula (I), as for carbon number of R ^f1 , 1-4 are preferable. Moreover, as for R< ¹ >, a methyl group is preferable. 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 formula (II), q is 1 or more, Preferably it is an integer of 2-20. Examples of the compound represented by the formula (II) include n-trifluoro(1,1,2,2-tetrahydro)propylsilazane (n-CF ₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ ), n-hepta Floro (1,1,2,2-tetrahydro)pentylsilazane (nC ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ ) and the like can be exemplified.

Cr F _{2r +1} CH ₂ CH ₂ Si(OCH ₃ ) ₃ … (III)

In formula (III), r is 1 or more, Preferably it is an integer of 1-20. Examples of the compound represented by the formula (III) include 2-(perfluorooctyl)ethyltrimethoxysilane (nC ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ) and the like.

[Formula 2]

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

R ^{f2 WHEREIN} : It is preferable that it is 20-300, and, as for s+t+u, it is more preferable that it is 25-100. Moreover, as for R< ² >, R< ³ >, a methyl group, an ethyl group, and a butyl group are preferable. 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. Moreover, as for a and b, 3 are preferable respectively.

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 (R ⁴ ) _k . (V)

In formula (V), v is an integer of 1-3, w, y, and z are each independently an integer of 0-200, h is an integer of 1-2, i is an integer of 2-20, X ⁴ is a hydrolyzable group, R ⁴ is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2; It is preferable that it is 20-300, and, as for w+y+z, it is more preferable that it is 25-100. Moreover, it is preferable that i is 2-10. A C1 ^- C6 alkoxy group is preferable and, as for X4, a methoxy group and an ethoxy group are more preferable. R ⁴ is preferably an alkyl group having 1 to 10 carbon atoms.

Further, as a commercially available fluorine-containing hydrolyzable silicon compound having at least one group selected from the group consisting of perfluoropolyether group, perfluoroalkylene group, and perfluoroalkyl group, KP-801 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ); KY-195 (trade name, manufactured by Shin-Etsu Chemical Industries, Ltd.), KY-197 (trade name, manufactured by Shin-Etsu Chemical Industries, Ltd.), Offtool (registered trademark) DSX (trade name, manufactured by Daikin Industries, Ltd.), S-550 (trade name, manufactured by Asahi Glass) ) and the like are preferred. Among the above, KY-185, KY-195, Offtool DSX, and S-550 are more preferable.

In addition, when a commercially available fluorine-containing hydrolysable silicon compound is supplied together with a solvent, the fluorine-containing hydrolyzable silicon compound is used after removing the solvent. The film-forming composition is prepared by mixing the fluorine-containing hydrolyzable silicon compound with optional components added as needed, and subjected to vacuum vapor deposition.

The antifouling film 3 is formed by making the film-forming composition containing such a fluorine-containing hydrolyzable silicon compound adhere to the main surface of the transparent substrate 2 and react. In addition, with respect to a specific vacuum deposition method or reaction conditions, well-known methods, conditions, etc. are applicable. For example, such an antifouling film 3 can be formed by the manufacturing method mentioned later.

10 nm - 50 nm are preferable and, as for the optical film thickness of the antifouling|stain-resistant film 3 at the time of formation, 10-30 nm is more preferable. By making the optical film thickness of the antifouling film 3 at the time of formation into the said range, the antifouling film 3a after removing the adhesion layer 4 and the protective film 5 can maintain favorable antifouling property and abrasion resistance.

(adhesive layer)

The antifouling film-forming base 1 is provided with the adhesive layer 4 provided on the surface of the antifouling film 3 so that it can be removed. As the material of the adhesive layer 4 , when the adhesive layer 4 is removed, it is preferable that the adhesive layer 4 is easily removed from the antifouling film 3 . As a material of such an adhesive layer 4, an acryl-type adhesive, a polyurethane-type adhesive, etc. are mentioned. These adhesives are preferable also from a viewpoint of adhesiveness and peelability.

The adhesive force of the adhesive layer 4 is, from the viewpoint of controlling the removal amount of the fluorinated hydrolyzable silicon compound constituting the antifouling film 3 when the adhesive layer 4 is removed from the antifouling film 3 , the adhesive layer 0.02 N/25 mm - 0.4 N/25 mm are preferable and, as for the 180 degree peel adhesive force with respect to the acrylic base of (4) (JIS Z0237 conformance), 0.05 N/25 mm - 0.2 N/25 mm are more preferable.

When the adhesive force of the adhesive layer 4 is less than 0.02 N/25 mm, the protective film 5 does not adhere to the antifouling film 3 uniformly, and when the adhesive layer 4 and the protective film 5 are removed, There is a possibility that the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film 3 is non-uniformly removed by the antifouling film 4 . Moreover, the protective film 5 may peel from the adhesive layer 4 during conveyance of the antifouling film-forming base 1, and the protective film 5 has a possibility that the function as protection of the antifouling film 3 may be impaired. there is. Moreover, when the adhesive force of the adhesive layer 4 exceeds 0.4 N/25 mm, the adhesive force with respect to the antifouling film 3 of the adhesive layer 4 is too strong, and the adhesive layer 4 and the protective film 5 are removed. In this case, there is a possibility that the fluorine-containing hydrolyzable silicon compound constituting the surface of the antifouling film 3 is removed more than necessary. Moreover, when the adhesive layer 4 and the protective film 5 are removed, since a part of the adhesive layer 4 cannot be removed but remains on the surface of the antifouling|stain-resistant film 3, defects, such as contamination, may be caused. . Moreover, in order to remove the protective film 5, a large force is needed, and the adhesion layer 4 cannot be removed uniformly, but peeling nonuniformity may generate|occur|produce.

It is preferable that the thickness of the adhesion layer 4 is 5 micrometers - 50 micrometers from a viewpoint of the adhesiveness and peelability of the antifouling|stain-resistant film 3 and the protective film 5.

(protective film)

The antifouling film-forming base 1 is provided with the protective film 5 provided on the surface of the adhesion layer 4 so that it can be removed. As the protective film 5, if it is a resin film-form thing, it will not restrict|limit especially. Moreover, the single-layer structure may be sufficient as the protective film 5, and the multilayer structure in which several layers, such as an antistatic layer, a hard-coat layer, and an easily bonding layer, were laminated|stacked may be sufficient as it.

As the protective film 5, polyester films, such as polyethylene terephthalate, polyolefin films, such as a polyethylene film, polypropylene, polyvinyl chloride film, etc. can be used, for example. Among these, a polyester-type film is preferable from a viewpoint of adhesiveness with the adhesion layer 4, durability, and an optical characteristic.

The thickness of the protective film 5 is not specifically limited, For example, it is preferable that they are 5 micrometers - 100 micrometers, and it is more preferable that they are 10 micrometers - 75 micrometers. When the thickness of the protective film 5 is less than 5 µm, the antifouling film 3 cannot be sufficiently protected in some cases, and when the thickness of the protective film 5 exceeds 100 µm, an increase in cost may be caused. .

[Method for producing antifouling film-forming substrate (1)]

The manufacturing method of the antifouling film-forming base 1 of this invention removes the film-forming process of forming the antifouling film 3 on the main surface of the transparent base 2, and the adhesive layer 4 on the surface of the antifouling film 3 It has the adhesion layer installation process provided so that it is possible, and the protective film installation process which installs the protective film 5 on the surface of the adhesion layer 4 so that removal is possible.

(film forming process)

The film forming step is a step of forming the antifouling film 3 by depositing and reacting a composition containing a fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2 . In the film forming step, the antifouling film 3 is formed with high adhesion on the main surface of the transparent substrate 2 , so that the obtained antifouling film forming substrate 1 has excellent antifouling properties such as water repellency and oil repellency, and wear resistance at a high level. compatibility with

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

The method for attaching the composition containing the fluorine-containing hydrolyzable silicon compound to the main surface of the transparent substrate 2 is not particularly limited as long as it is a method commonly used for forming a layer of the fluorinated hydrolysable silicon compound by a dry method, For example, a vacuum vapor deposition method, a CVD method, a sputtering method, etc. are mentioned. The vacuum vapor deposition method is preferable from the viewpoint of suppressing decomposition of the fluorine-containing hydrolyzable silicon compound during the film formation step and the convenience of the apparatus.

The vacuum deposition method can be subdivided into a resistance heating method, an electron beam heating method, a high frequency induction heating method, a reactive deposition method, a molecular beam epitaxy method, a hot wall deposition method, an ion plating method, a cluster ion beam method, etc., but any method can be applied. there is. The resistance heating method is preferable from the viewpoint of suppressing decomposition of the fluorine-containing hydrolyzable silicon compound during the film forming step and the convenience of the apparatus. There is no restriction|limiting in particular as a vacuum vapor deposition apparatus, A well-known apparatus can be used.

3 : is a figure which shows typically the apparatus which can be used for one Embodiment of the manufacturing method of the antifouling|stain-resistant film-forming base|substrate 1 of this invention. The apparatus shown in FIG. 3 is an apparatus for depositing a composition containing a fluorine-containing hydrolyzable silicon compound on the main surface of the transparent substrate 2 .

Hereinafter, the manufacturing method of the antifouling|stain-resistant film-forming base|substrate 1 is demonstrated, referring FIG. Here, the vacuum vapor deposition apparatus by the resistance heating method is demonstrated. When the apparatus shown in FIG. 3 is used, the film forming process is carried out to the transparent substrate 2 in the vacuum chamber 33 while the transparent substrate 2 is conveyed by the conveying unit 32 from the left to the right in the drawing. is carried out for

In the vacuum chamber 33 shown in FIG. 3, the composition for film formation is made to adhere to the main surface of the transparent base 2 using the vacuum vapor deposition apparatus 20 by the resistance heating method.

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

The vacuum vapor deposition apparatus 20 is provided outside the vacuum chamber 33 and connects the heating container 21 which heats the composition for film formation, the heating container 21, and the vacuum chamber 33, The heating container 21 ) pipe 22 for supplying the vapor of the composition for film formation introduced from A manifold 23 having an injection port for injecting the vapor of the transparent gas 2 to the main surface is provided. Moreover, in the vacuum chamber 33, the transparent gas 2 is hold|maintained so that the injection port of the manifold 23 and the main surface of the transparent gas 2 may oppose.

The heating container 21 has a heating part which can heat the composition for film formation which is a vapor deposition source to the temperature which can vaporize. Although the heating temperature of the composition for film formation is suitably selected according to the kind of composition for film formation, 30 degreeC - 400 degreeC are specifically preferable, and 50 degreeC - 300 degreeC are especially preferable. A film-forming rate becomes favorable as the heating temperature of the composition for film formation is 30 degreeC or more. When the heating temperature of the composition for film formation is 400° C. or less, decomposition of the fluorinated hydrolyzable silicon compound can be suppressed, and a good antifouling film 3 having antifouling properties can be formed on the main surface of the transparent substrate 2 .

Here, during vacuum deposition, the temperature of the film-forming composition containing the fluorine-containing hydrolyzable silicon compound in the heating vessel 21 is raised to a vapor deposition start temperature, and then a part of the vapor of the film-forming composition is discharged to the outside of the system for a predetermined period of time. It is preferable to perform pre-treatment. The fluorine-containing hydrolyzable silicon compound contained in the film-forming composition has a high molecular weight and has a molecular weight distribution. Therefore, in the vapor of the composition for film formation at a stage in which the vapor deposition start temperature has just been reached, the content of the low molecular weight component that is easily vaporized increases, and in some cases, the low boiling impurity component also increases. By performing this pretreatment, low molecular weight components, low boiling impurity components, etc. that affect the durability of the antifouling film 3 can be removed, and furthermore, the composition of the raw material vapor supplied from the vapor deposition source can be stabilized. Thereby, it becomes possible to form the antifouling|stain-resistant film 3 with high durability stably.

Specifically, in the upper part of the heating container 21, separately from the pipe 22 connected to the manifold 23, in order to discharge the vapor|steam of the composition for initial stage film formation to the outside of the heating container 21, it opens and closes freely. A method such as forming a pipe (not shown) connected to an exhaust port capable of being discharged and trapping the steam out of the heating vessel 21 can be used.

Moreover, it is preferable that the temperature of the transparent substrate 2 at the time of vacuum deposition is room temperature (20-25 degreeC) - 200 degreeC. When the temperature of the transparent substrate 2 is 200 degrees C or less, the film-forming rate becomes favorable. As for the upper limit of the temperature of the transparent substrate 2, 150 degreeC is more preferable, and 100 degreeC is especially preferable.

Moreover, it is preferable that the manifold 23 is equipped with the heater part in order to prevent that the vapor|steam of the composition for film formation supplied from the heating container 21 is condensed. Moreover, in order to prevent the vapor|steam supplied from the heating vessel 21 from being condensed in the piping 22, it is preferable to design the piping 22 so that it may be heated together with the heating vessel 21. As shown in FIG.

In addition, in order to control the film-forming speed, a variable valve 24 is provided in the pipe 22 , and the opening degree of the variable valve 24 is based on a value detected by a film thickness gauge 25 formed in the vacuum chamber 33 . It is desirable to control By forming such a structure, it becomes possible to control the amount of vapor|steam of the composition for film formation containing the fluorine-containing hydrolyzable silicon compound supplied to the main surface of the transparent base 2 . Thereby, the antifouling|stain-resistant film 3 which has a desired thickness with high precision on the main surface of the transparent base 2 can be formed. In addition, as the film thickness meter 25, a crystal vibrator monitor etc. can be used. Furthermore, the measurement of the film thickness is, for example, when an X-ray diffractometer ATX-G for thin film analysis (manufactured by RIGAKU) is used as the film thickness meter 25, the interference pattern of reflected X-rays by the X-ray reflectance method. , and can be calculated from the oscillation period of the interference pattern.

In this way, the film-forming composition containing the fluorine-containing hydrolyzable silicon compound adheres to the main surface of the transparent substrate 2 . In addition, the fluorine-containing hydrolyzable silicon compound undergoes a hydrolytic condensation reaction at the same time or after adhesion to chemically bond to the main surface of the transparent substrate 2 and form an antifouling film 3 by siloxane bonding between molecules.

The hydrolysis-condensation reaction of this fluorinated hydrolyzable silicon compound proceeds on the main surface of the transparent substrate 2 at the same time as adhesion. After taking out (2) from the vacuum chamber 33, you may further perform the heat processing using a hot plate or a constant temperature and humidity chamber. As conditions for heat processing, the transparent substrate 2 is heated at the temperature of 80-200 degreeC for 10 to 60 minutes, for example.

In addition, the film-forming process may connect a humidifier etc. to the chamber 33, and you may perform it in the state which humidified the inside of the chamber 33. In addition, after the film forming step, the surface of the antifouling film 3 is etched by, for example, acid treatment or alkali treatment to obtain the surface roughness (center line average roughness (Ra)) of the antifouling film 3, For example, you may adjust to 10 nm or less.

(Adhesive layer installation process, protective film installation process)

Next, on the surface of the antifouling|stain-resistant film 3 obtained by making it above, the protective film 5 is made to removably adhere through the adhesion layer 4 . The method for removably providing the adhesive layer 4 on the surface of the antifouling film 3 and the method for removably installing the protective film 5 on the surface of the adhesive layer 4 are not particularly limited, the same process may be carried out or may be carried out in a separate process, for example, a protective film 5 having an adhesive layer 4 on the surface to be adhered to the antifouling film 3 in advance (hereinafter, “protective film with an adhesive layer”) It is also called.) can be used by placing it on the antifouling film 3 and then pressurizing it. Adhesive layer installation on antifouling film 3 Installation of a protective film may be performed continuously, and in this case, it adheres to the main surface of the antifouling film 3, conveying the transparent base 2 using a laminating machine etc. After continuously supplying and placing a layer installation protective film, it pressurizes and makes an adhesion layer installation protective film adhere to the antifouling|stain-resistant film 3 . The lamination conditions at this time are not specifically limited, For example, the conveyance speed of the transparent substrate 2 in which the antifouling|stain-resistant film 3 was formed is 1 mm/min - 5 mm/min, and a pressing force is 1 kgf in linear pressure. It can carry out at /cm<2>-10kgf/m<2>.

[Removal of adhesive layer and protective film]

The antifouling film-forming substrate 1 is used after the adhesive layer 4 and the protective film 5 provided above are removed. The removal method of the adhesion layer 4 and the protective film 5 is not specifically limited, You may remove manually, and may be removed using a peeling apparatus etc. Moreover, the present inventors discovered that the value of the optical film thickness of the antifouling|stain-resistant film 3a after peeling did not go up and down depending on the removal method.

In this way, the optical film thickness of the antifouling|stain-resistant film 3a after removing the adhesion layer 4 and the protective film 5 is 3 nm - 30 nm. When the optical film thickness of the antifouling film 3a after removal of the adhesion layer 4 and the protective film 5 is less than 3 nm, durability of the antifouling film 3a deteriorates remarkably. Moreover, when the optical film thickness of the antifouling film 3a after removal exceeds 30 nm, the nonuniformity of the haze by film thickness nonuniformity or the aggregation of an antifouling film material arises, and it perceives as an optical nonuniformity in an external appearance, and designability. or the quality of the image display is impaired.

Moreover, the optics of the antifouling film 3a after removing the adhesion layer 4 and the protective film 5 with respect to the optical film thickness of the antifouling film 3 before installing the adhesion layer 4 and the protective film 5. It is preferable that the rate of change of the film thickness is 10% to 60%. Thereby, the antifouling|stain-resistant film 3a after removing the adhesion layer 4 and the protective film 5 is equipped with the outstanding 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 calculated|required 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)} x 100/(optical film thickness of antifouling film 3) (%)... (One)

The antifouling film-forming substrate 1 having the antifouling film 3 obtained as described above is excellent in antifouling properties such as water repellency and oil repellency, and has high abrasion resistance that can withstand repeated erosion of contamination and the like. Moreover, since the antifouling|stain-resistant film-forming base 1 is equipped with the adhesion layer 4 and the protective film 5 on the antifouling|stain-resistant film 3, the crack and the generation|occurrence|production of a flaw at the time of conveyance can be suppressed. Moreover, so that the optical film thickness of the antifouling film 3a after removing the adhesion layer 4 and the protective film 5 may become an optimal film thickness, the antifouling film before removing the adhesion layer 4 and the protective film 5 ( Since the optical film thickness of 3) is within the above range, the antifouling film 3a at the time of use has a sufficient optical film thickness, is excellent in antifouling properties such as water repellency and oil repellency, and is also effective in eliminating repeated contamination. It has a high wear resistance that can withstand it.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. Evaluation in an Example and a comparative example was performed by the following method, respectively.

(friction durability (wear resistance))

First, a plain weave cotton cloth No. 3 was attached to the surface of a flat metal indenter having a bottom surface of 10 mm × 10 mm, and the antifouling film was rubbed as a friction member.

Next, the friction durability of the antifouling film was measured with a plane wear tester model 3 (manufactured by Taiei Scientific Seonggi Seisakusho) using the above friction element. Specifically, the friction member is mounted on a wear tester so that the bottom surface of the friction member is in contact with the surface of the antifouling film formed on the transparent substrate, and a weight is placed so that the weight of the friction member is 1000 g, an average speed of 6400 mm/min, one way The friction element was reciprocally slid against the antifouling film surface at 40 mm. The number of times of abrasion was changed from one reciprocating sliding to two, and the contact angle of water on the surface of the antifouling film after completion of 50000 times of abrasion was measured. The measurement of the water contact angle on the surface of the antifouling film was performed by dropping 1 µl of pure water to the antifouling film using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science). The measurement points of the water contact angle in the antifouling film surface were made into 10 points, and the arithmetic average of the water contact angles measured at 10 points|pieces was made into friction durability. The decrease in friction durability is suppressed, so that there are few reduction rates of the water contact angle before and behind the removal of an adhesive layer installation protective film.

(Optical film thickness of antifouling film)

First, the measuring method of the optical film thickness of the antifouling|stain-resistant film in the antifouling|stain-resistant film-forming base 1 provided with an antireflection film is demonstrated.

First, the refractive index of each layer constituting the antireflection film formed on the surface of the transparent substrate was measured. Then, the black tape was pasted on the back surface of the transparent base, and the back surface reflection of the transparent base was removed. Thereafter, the spectral reflection spectrum was measured with a spectrometer (SolidSpec-3700, manufactured by Shimadzu Corporation) on the surface of the transparent substrate on which the antireflection film and the antifouling film are formed. Then, using the previously measured refractive index of each layer constituting the antireflection film and the thickness of each layer, the refractive index of the antifouling film was assumed to be 1.35, and the optical film thickness of the antifouling film was calculated by dedicated software.

Next, the measuring method of the optical film thickness of the antifouling|stain-resistant film in the antifouling|stain-resistant film-forming base 1 which is not provided with the antireflection film is demonstrated.

A transparent substrate having an antireflection film and a transparent substrate not having an antireflection film were prepared, respectively, and an antifouling film was formed on both transparent substrates under the same conditions. Thereafter, the spectral reflection spectrum was measured with the same spectrometer as described above for the surface of the transparent substrate on which the antireflection film and the antifouling film were formed. Similarly to the above, using the refractive index of each layer constituting the antireflection film and the thickness of each layer, the refractive index of the antifouling film was assumed to be 1.35, and the optical film thickness of the antifouling film was calculated by dedicated software. This value was made into the optical film thickness of the antifouling|stain-resistant film in the anti-fouling|stain-resistant film-forming base|substrate 1 provided with the antireflection film formed in the transparent base|substrate which did not form the antireflection film under the same conditions.

Since the optical film thickness of the antifouling film is very thin, ranging from several nm to several tens of nm, it is difficult to accurately measure it with a stylus-type step meter, but it can be measured with a spectral reflection spectrum or an ellipsometer. In addition, the optical film thickness of the antifouling film can be accurately measured by the following method even without using an expensive device as described above. The reflection spectrum of the surface of the transparent substrate when the antifouling film is formed on the surface of the transparent substrate through the antireflection film is compared with the reflection spectrum of the surface of the transparent substrate when the antifouling film is directly formed on the surface of the transparent substrate without the antireflection film interposed therebetween. , the change in the reflection spectrum with respect to the fluctuation of the film thickness of the antifouling film becomes large. Therefore, as described above, the optical film thickness of the formed antifouling film can be accurately measured by the method of forming the antifouling film on the transparent substrate on which the antireflection film is formed and the transparent substrate on which the antireflection film is not formed under the same conditions. there is. In Examples and Comparative Examples, this method was employed.

(optical non-uniformity)

First, the antifouling-film-forming base 1 was arrange|positioned on the fluorescent lamp, and the position of the fluorescent lamp was adjusted so that it might become 1500 lux at the position of the antifouling-film-forming base 1 . Next, the light which passed through the antifouling|stain-resistant film-forming base 1 was observed, and whether haze or the nonuniformity of a color taste had been visually observed was judged whether the nonuniformity existed.

[Example 1]

According to the following procedure, the antifouling|stain-resistant film-forming base|substrate (1) was manufactured

(1) Anti-glare treatment and etching treatment

Chemically tempered glass (Dragon Trail (registered trademark, hereinafter also referred to as "DT"), manufactured by Asahi Glass Co., Ltd.) was used as the transparent substrate. And according to the following procedure, the glare-proof process by a frost process was given to the surface of a transparent base|substrate. First, the acid-resistant protective film was pasted together on the back surface which is the side to which the anti-glare treatment of a transparent base|substrate was not performed. Next, the transparent substrate was immersed in a 3 wt% hydrogen fluoride solution for 3 minutes to remove contaminants adhering to the surface of the transparent substrate. Next, the transparent substrate was immersed in a mixed solution of 15% by weight hydrogen fluoride and 15% by weight potassium fluoride for 3 minutes, and a frost treatment was performed on the surface of the transparent substrate on which the protective film was not bonded.

The haze value was adjusted to 25% by immersing the transparent substrate after the said anti-glare treatment in a 10% hydrogen fluoride solution for 6 minutes (etching time 6 minutes).

(2) chemical strengthening treatment

The transparent gas after the antiglare treatment was immersed in potassium nitrate heated and melted at 450°C for 2 hours, then pulled up, and then slowly cooled to room temperature for 1 hour to obtain a chemically strengthened transparent gas.

(3) Formation of an antireflection film (AR film)

With respect to the transparent substrate chemically strengthened above, an anti-reflection film was formed on the surface, which was subjected to anti-glare treatment, as follows.

The transparent gas was immersed in an alkaline solution (Sanwash TL-75, manufactured by Lion Corporation) for 4 hours. Thereafter, a niobium oxide target (NBO target, manufactured by AGC Ceramics) was used while introducing a mixed gas obtained by mixing argon gas with 10% by volume of oxygen gas in a vacuum chamber, at a pressure of 0.3 Pa, a frequency of 20 kHz, Pulse sputtering was performed under the conditions of a power density of 3.8 W/cm 2 and an inversion pulse width of 5 µsec to form a first high refractive index layer made of niobium oxide (niobia) having a thickness of 13 nm on the surface of the transparent substrate.

Next, a silicon target is used while introducing a mixed gas obtained by mixing argon gas with 40% by volume of oxygen gas, and pulses 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 an inversion pulse width of 5 µsec. Sputtering was performed to form the 1st low-refractive-index layer which consists of 35 nm-thick silicon oxide (silica) on the 1st high refractive index layer.

Next, a pressure of 0.3 Pa, a frequency of 20 kHz, and a power density of 3.8 W/cm 2 using a niobium oxide target (NBO target, manufactured by AGC Ceramics) while introducing a mixed gas obtained by mixing 10% by volume of oxygen gas with argon gas , pulse sputtering was performed under the condition of a reversal pulse width of 5 µsec to form a second high refractive index layer made of niobium oxide (niobia) having a thickness of 115 nm on the first low refractive index layer.

Next, a silicon target is used while introducing a mixed gas obtained by mixing argon gas with 40% by volume of oxygen gas, and pulses 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 an inversion pulse width of 5 µsec. Sputtering was performed to form the 2nd low-refractive-index layer which consists of 80 nm-thick silicon oxide (silica) on the 2nd high refractive index layer.

In this way, an antireflection film in which a total of four layers of a niobium oxide (niobia) layer and a silicon oxide (silica) layer were laminated was formed.

(4) Formation of antifouling film (AFP film)

First, as a raw material for the antifouling film, a fluorine-containing hydrolyzable silicon compound (KY-185, manufactured by Shin-Etsu Chemical Co., Ltd.) was introduced into a heating vessel. Thereafter, the inside of the heating vessel was degassed with a vacuum pump for 10 hours or more to remove the solvent in the solution to obtain a vapor of a composition for film formation containing a fluorine-containing hydrolyzable silicon compound. Next, the heating container containing the composition for film formation was heated to 270 degreeC. After reaching 270°C, the state was maintained for 10 minutes until the temperature stabilized.

And with respect to the antireflection film laminated|stacked on the transparent substrate provided in the vacuum chamber, the vapor|steam of the composition for film formation was supplied from the nozzle which connected the vacuum chamber and the heating vessel, and it formed into a film.

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

For the antifouling film thus formed, friction durability and optical film thickness were measured by the method described above.

Further, using a laminating machine, an adhesive layer-attached protective film (EC-9000AS, manufactured by Sumiron Corporation) was provided on both surfaces of the transparent substrate on which the antifouling film obtained above was formed, and the antifouling film-forming substrate 1 was produced. did Adhesive layer installation The material of the adhesive layer constituting the protective film is an acrylic adhesive, the 180 degree peel adhesive force of the adhesive layer to the acrylic substrate (based on JIS Z 0237) is 0.06 N/25 mm, and the protective film is polyethylene terephthalate (hereinafter, “ PET".) The thickness of the system film and the protective film is 25 µm.

Thereafter, the antifouling film provided with an adhesive layer on the surface of the antifouling film was removed, and the antifouling film after removing the adhesive layer provided protective film was measured for friction durability, optical film thickness, and optical non-uniformity by the method described above.

[Example 2]

An anti-fouling film with an optical film thickness of 15 nm was formed on the transparent substrate in the same manner as in Example 1 except that the anti-glare treatment was not performed and the anti-reflection film was not formed. Further, in the same manner as in Example 1, an adhesive layer-attached protective film (EC-9000AS, manufactured by Sumiron Corporation) was provided on both surfaces of the transparent substrate on which the antifouling film was formed, and the antifouling film-forming substrate 2 was produced. did It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Example 3]

An antifouling film with 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, on both surfaces of the transparent substrate on which the antifouling film was formed, a protective film with an adhesive layer (UA-3000AS, manufactured by Sumiron Co., Ltd.) was installed using the same laminating machine as in Example 1, and the antifouling film forming substrate 3 was formed. prepared. Adhesive layer installation The material of the adhesive layer constituting the protective film is a polyurethane-based adhesive, the 180-degree peel adhesive force of the adhesive layer to the acrylic substrate (based on JIS Z 0237) is 0.15 N/25 mm, the protective film is a PET-based film, and a protective film is 25 μm thick. It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Example 4]

An antifouling film with an optical film thickness of 40 nm was formed on the transparent substrate in the same manner as in Example 1 except that the anti-glare treatment was not performed and the anti-reflection film was not formed. Further, on both surfaces of the transparent substrate on which the antifouling film was formed, a protective film with an adhesive layer (RP-207, manufactured by Nitto Denko Co., Ltd.) was installed using the same laminating machine as in Example 1 to prepare an antifouling film forming substrate (4). . Adhesive layer installation The material of the adhesive layer constituting the protective film is an acrylic adhesive, the 180 degree peel adhesive force of the adhesive layer to the acrylic substrate (based on JIS Z 0237) is 0.1 N/25 mm, and the protective film is a PET-based film and a protective film. The thickness is 25 μm. It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Example 5]

Except not having performed the anti-glare treatment, it carried out similarly to Example 1, and formed the antifouling|stain-resistant film with an optical film thickness of 10 nm on the transparent substrate. Further, on both surfaces of the transparent substrate on which the antifouling film was formed, a protective film with an adhesive layer (Y16FS, manufactured by San-ei Kaken) was installed using the same laminating machine as in Example 1 to prepare an antifouling film-forming substrate 5 . Adhesive layer installation The material of the adhesive layer constituting the protective film is an acrylic adhesive, the 180 degree peel adhesive force of the adhesive layer to the acrylic substrate (based on JIS Z 0237) is 0.3 N/25 mm, The thickness is 25 μm. It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Example 6]

As a raw material for the antifouling film, a fluorine-containing hydrolyzable silicon compound (Offtool DSX, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and an anti-glare treatment was not performed and an anti-reflection film was not formed. An antifouling film with an optical film thickness of 30 nm was formed thereon. Further, on both surfaces of the transparent substrate on which the antifouling film was formed, a protective film with an adhesive layer (RP-207, manufactured by Nitto Denko Co., Ltd.) was installed using the same laminating machine as in Example 1 to prepare the antifouling film forming substrate 6 . did. It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Example 7]

Except not having formed the antireflection film, it carried out similarly to Example 1, and formed the antifouling|stain-resistant film with an optical film thickness of 20 nm on the transparent substrate. Further, in the same manner as in Example 1, protective films with adhesive layers (EC-9000AS, manufactured by Sumiron Corporation) were provided on both surfaces of the transparent substrate on which the antifouling film was formed, to prepare an antifouling film-forming substrate (7). . It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Comparative Example 1]

An anti-fouling film with an optical film thickness of 10 nm was formed on the transparent substrate in the same manner as in Example 1 except that the anti-glare treatment was not performed and the anti-reflection film was not formed. Further, on both surfaces of the transparent substrate on which the antifouling film was formed, a protective film with an adhesive layer (TG-3030, manufactured by Sumiron Co., Ltd.) was installed using the same laminating machine as in Example 1, and the antifouling film forming substrate 1C was applied prepared. Adhesive layer installation The material of the adhesive layer constituting the protective film is an acrylic adhesive, the 180-degree peel adhesive force of the adhesive layer to the acrylic substrate (based on JIS Z 0237) is 3.0 N/25 mm, and the protective film is a PET film and a protective film. The thickness is 25 μm. It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

[Comparative Example 2]

An antifouling film with an optical film thickness of 60 nm was formed on the transparent substrate in the same manner as in Example 1 except that the anti-glare treatment was not performed and the anti-reflection film was not formed. Further, in the same manner as in Example 1, protective films with adhesive layers (EC-9000AS, manufactured by Sumiron Corporation) were provided on both sides of the transparent substrate on which the antifouling film was formed, to prepare an antifouling film forming substrate (2C). . It carried out similarly to Example 1, and the friction durability of an antifouling|stain-resistant film, optical film thickness, and optical nonuniformity were measured.

Manufacturing conditions of the antifouling film-forming substrates (1 to 7) prepared in Examples 1 to 7 and the antifouling film-forming substrates (1C to 2C) prepared in Comparative Examples 1 to 2, friction durability of the antifouling film, optical film thickness, and The measurement result of optical nonuniformity is shown in Table 1. Moreover, the change rate of the optical film thickness of the antifouling|stain-resistant film computed by Formula (1) mentioned above is shown in Table 1.

As shown in Table 1, the optical film thickness of the antifouling film in the state provided with an adhesion layer and a protective film shall be 10 nm - 50 nm, and the optical film thickness of the antifouling film after removing an adhesion layer and a protective film is 3 nm - 30 It turns out that the abrasion resistance fall of the antifouling|stain-resistant film by removing the adhesion layer and a protective film is suppressed in the antifouling|stain-resistant film-forming base|substrates 1-7 set to nm. Moreover, it turns out that the antifouling|stain-resistant film-forming base|substrates 1-7 do not have optical nonuniformity and are provided with the outstanding transparency.

1: antifouling film-forming gas;
2: transparent gas,
3, 3a: antifouling film,
4: adhesive layer,
5: Protective film.

Claims (7)

delete An antifouling film-forming substrate comprising an antifouling film, an adhesive layer, and a protective film sequentially provided on a main surface of a transparent substrate, and used by removing the adhesive layer and the protective film,
The optical film thickness of the antifouling film after removing the adhesive layer and the protective film is 3 nm to 30 nm,
{(optical film thickness of the antifouling film in a state including the adhesive layer and the protective film) - (the optical film thickness of the antifouling film after removing the adhesive layer and the protective film)} × 100/(the adhesive layer and The antifouling film-forming substrate, wherein the rate of change given in (%) of the optical film thickness of the antifouling film in the state in which the protective film is provided is 10 to 60%. 3. The method of claim 2,
The antifouling film-forming substrate, wherein the adhesive layer has a peel adhesive force at 180 degrees to the acrylic substrate (according to JIS Z 0237) of 0.02 N/25 mm to 0.4 N/25 mm. 4. The method according to claim 2 or 3,
The antifouling film-forming gas, wherein the transparent gas is a glass gas. 4. The method according to claim 2 or 3,
An antifouling film-forming substrate further comprising an antireflection film between the transparent substrate and the antifouling film. 4. The method according to claim 2 or 3,
An antifouling film-forming substrate, wherein a main surface of the transparent substrate has an uneven shape. 4. The method according to claim 2 or 3,
The antifouling film-forming substrate, wherein the antifouling film is formed from a film formation composition containing a fluorine-containing hydrolyzable silicon compound.

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