JP5839134B2 - Transparent substrate with antifouling film - Google Patents

Description

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

  In recent years, various display devices such as a liquid crystal display have been frequently used particularly in portable devices and in-vehicle devices. In such a display device, a structure in which a transparent substrate is conventionally disposed as the cover member is employed. A substrate configuration in which a touch panel with a transparent electrode and a cover glass are integrated is also known.

  In such a display device, there are many occasions where a human finger or the like touches the surface of the transparent substrate, and when a human finger or the like touches, grease or the like tends to adhere to the surface of the transparent substrate. And when fat etc. adhere, it will affect visibility, and what the antifouling process was given to the surface of a transparent substrate is used.

  For example, Patent Document 1 discloses a water-repellent glass in which a water-repellent layer is provided on the surface of a glass substrate having a concavo-convex shape as a transparent substrate having a surface subjected to antifouling treatment.

  Furthermore, in a water-repellent glass provided with a water-repellent layer, it is difficult to maintain the water-repellent performance because the adhesive strength between the water-repellent agent and the glass is weak. A method of making the surface shape of the film into a predetermined shape has been studied (for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 07-122601 Japanese Patent Laid-Open No. 11-171594

  However, the water-repellent glass of Patent Document 2 was developed for the purpose of windshield glass, window glass plate, and the like, and is not planned to be used as a transparent substrate for a display device or the like.

  For this reason, when the water-repellent glass is used as a cover glass that is integrated with a cover member of a display device such as a liquid crystal display or a transparent electrode of a touch panel, ambient light is reflected because there is almost no anti-glare property, and the display part There was a problem that the visibility of was reduced.

  In addition, as described above, the water-repellent glass of Patent Document 2 is a water-repellent glass that is planned to be used for a portion such as a window glass that has little chance of being touched by human hands. Durability was not sufficient for use as a substrate integrated with a cover member or touch panel that may be touched.

  The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a transparent substrate with an antifouling film having antiglare properties and improved durability of the antifouling film.

The present invention for solving the above problems, a transparent substrate for organic and first major surface and a second major surface opposite the first major surface,
Has a antifouling film consisting off Tsu-containing organic silicon compound is provided on the first main surface side of the transparent substrate, a low reflection film, and
The proof surface roughness RMS of the fouling layer is not more 0.05μm or 0.25μm or less, Ri average length RSm of Der least 40μm or less 10μm elements of the roughness curve of the antifouling film,
Provided is a transparent substrate with an antifouling film in which the low reflection film and the antifouling film are laminated in this order on the surface of the first main surface of the transparent substrate.

  In the present invention, it is possible to provide a transparent substrate with an antifouling film that has antiglare properties and has improved durability of the antifouling film.

Explanatory drawing of a structure of the transparent base | substrate with an antifouling film concerning a 1st embodiment of the present invention. Explanatory drawing of a structure of the transparent base | substrate with an antifouling film concerning a 2nd embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not departed from the scope of the present invention. Various modifications and substitutions can be made.
[First Embodiment]
In the present embodiment, the transparent substrate with an antifouling film of the present invention will be described.

  The transparent substrate with an antifouling film of the present embodiment has a first main surface and a second main surface opposite to the first main surface, and an anti-glare process on the surface of the first main surface. And a fluorine-containing organosilicon compound film that is an antifouling film provided on the first main surface side of the transparent substrate. The antifouling film has a surface roughness RMS of 0.05 μm or more and 0.25 μm or less, and an average length RSm of elements of the roughness curve is 10 μm or more and 40 μm or less.

  The transparent substrate with an antifouling film of this embodiment will be described with reference to FIG. FIG. 1 schematically shows a cross-sectional view of a transparent substrate with an antifouling film of the present embodiment, and has a configuration in which an antifouling film 12 is disposed on the first main surface side of the transparent substrate 11. ing. Each member constituting the transparent substrate with the antifouling film will be described below.

  First, the material of the transparent substrate 11 is not particularly limited, and various transparent substrates that transmit at least visible light can be used. Examples thereof include various materials such as a plastic substrate and a glass substrate. Among them, the transparent substrate is preferably a glass substrate from the viewpoints of transparency and strength. In this case, the type of glass is not particularly limited, and various types of glass such as alkali-free glass, soda lime glass, and aluminosilicate glass can be used. Among these, soda lime glass is preferably used from the viewpoint of adhesion to a layer (film) provided on the upper surface.

  When the transparent substrate 11 is a glass substrate, it is preferable to use a tempered glass substrate (for example, “Dragon Trail (registered trademark)”) obtained by chemically strengthening aluminosilicate glass from the viewpoint of the strength of the transparent substrate itself.

  The chemical strengthening treatment refers to a treatment for replacing alkali ions (for example, sodium ions) having a small ionic radius on the surface of the glass with alkali ions (for example, potassium ions) having a large ionic radius. For example, the glass containing sodium ions can be chemically strengthened by treating with a molten salt containing potassium ions. The composition of the compressive stress layer on the surface of the glass substrate after such chemical strengthening treatment is slightly different from the composition before chemical strengthening treatment, but the composition of the substrate deep layer portion is almost the same as the composition before chemical strengthening treatment.

  The conditions for chemical strengthening are not particularly limited, and can be selected according to the type of glass used for chemical strengthening, the required degree of chemical strengthening, and the like.

  What is necessary is just to select as a molten salt for performing a chemical strengthening process according to the glass substrate used for a chemical strengthening. Examples thereof include alkali sulfates and alkali chlorides such as potassium nitrate, sodium sulfate, potassium sulfate, sodium chloride and potassium chloride. These molten salts may be used alone or in combination of two or more.

  The heating temperature of the molten salt is preferably 350 ° C. or higher, and more preferably 380 ° C. or higher. Moreover, 500 degrees C or less is preferable and 480 degrees C or less is more preferable.

  By setting the heating temperature of the molten salt to 350 ° C. or higher, it is possible to prevent chemical strengthening from becoming difficult due to a decrease in the ion exchange rate. Moreover, decomposition | disassembly and deterioration of molten salt can be suppressed by setting it as 500 degrees C or less.

  The time for bringing the glass substrate into contact with the molten salt is preferably 1 hour or longer, and more preferably 2 hours or longer, in order to impart sufficient compressive stress. Moreover, in long-time ion exchange, while productivity falls and a compressive stress value falls by relaxation, 24 hours or less are preferable and 20 hours or less are more preferable.

  The shape of the transparent substrate is not particularly limited, and various shapes of transparent substrates can be used.

  As described above, the transparent substrate 11 has the first main surface 11A and the second main surface 11B facing the first main surface 11A. The first main surface 11A is subjected to an antiglare process for forming a desired uneven shape. At this time, the RMS which is the surface roughness of the first main surface 11A is 0.05 μm or more and 0.25 μm or less, and the RSm which is the average length of the elements of the roughness curve of the first main surface 11A is 10 μm or more and 40 μm or less. It is preferable that By setting it as such a range, the surface roughness RMS of the antifouling film described later and the average length RSm of the elements of the roughness curve can be set as desired ranges.

  Here, the surface roughness RMS is the average depth of irregularities from the reference plane (here, the substrate surface before the surface treatment). In addition, it is also called a root mean square roughness and may be represented by Rq. The average length RSm of the elements of the roughness curve is a length obtained by averaging the lengths on the reference surface where irregularities for one period are generated in the roughness curve included in the reference length taken on the reference surface. is there. The surface roughness RMS (μm) and the average length RSm of the elements of the roughness curve can be measured by a method based on the method defined in JIS B 0601 (2001).

  This is because when the inventors of the present invention have studied in order to increase the durability of the antifouling film in the transparent substrate with the antifouling film, the surface characteristics of the first main surface 11A have the above characteristics. In addition to the antiglare property, it has been found that the durability of the antifouling film is particularly improved as compared with a conventional transparent substrate with an antifouling film.

  Since the antifouling film is formed on the first main surface side of the transparent substrate, and the antifouling film traces the surface shape of the transparent substrate, the antifouling film surface has the same surface roughness characteristics as the transparent substrate. Have.

  When the first main surface 11A of the transparent substrate satisfies the above-mentioned definition, it is compared with a conventionally used transparent substrate that has been subjected to an antiglare process in which RMS exceeds 0.25 μm or RSm exceeds 40 μm. In the fine unevenness of the first main surface of the transparent substrate, it means that the pitch between the concave portions is reduced and the area of the convex portions is increased. As described above, the surface of the antifouling film also has the same surface shape.

  The surface of the transparent substrate with the antifouling film, that is, when a finger or the like comes into contact with the antifouling film, the area of the convex portion of the antifouling film that comes into contact with the finger or the like is compared with the conventional transparent substrate with the antifouling film It is getting bigger. For this reason, it is estimated that the force applied to the surface (antifouling film) part of the transparent substrate with antifouling film is dispersed by fingers, etc., the pressure applied to the antifouling film can be reduced, and peeling and abrasion of the antifouling film can be suppressed Is done.

  It is presumed that the smaller the RSm that is the average length of the elements of the roughness curve, that is, the smaller the pitch of the recesses, the greater the contact area with the finger and the more the durability. However, in order to make RSm very small, for example, an etching process using a photomask or the like needs to be performed. From the viewpoint of cost, it can be preferably created if RSm is 10 μm or more. For this reason, it is preferable to use the transparent base | substrate which satisfy | fills the said RSm range about the surface which forms an antifouling film | membrane.

  Further, in the case of a transparent substrate in which RMS and RSm are in the above numerical ranges, since the pitch of the recesses is in an appropriate range, a transparent substrate having antiglare properties can be obtained.

  Furthermore, the RMS which is the surface roughness of the first main surface 11A is more preferably 0.08 μm or more and 0.20 μm or less, and the RSm which is the average length of the elements of the roughness curve is 15 μm or more and 35 μm or less. It is more preferable. By satisfying these parameters, it is possible to further improve the durability of the antifouling film.

  The anti-glare processing method for forming a transparent substrate having such surface characteristics is not particularly limited, and a method of performing surface treatment on the first main surface to form desired irregularities can be used.

  Specifically, a method of performing a frost treatment on the first main surface of the transparent substrate can be mentioned. The frost treatment can be performed, for example, by immersing a transparent substrate, which is an object to be processed, in a mixed solution of hydrogen fluoride and ammonium fluoride and chemically treating the immersion surface.

  In addition to such a chemical treatment method, for example, a so-called sand blast treatment in which crystalline silicon dioxide powder, silicon carbide powder or the like is sprayed onto the transparent substrate surface with pressurized air, crystalline silicon dioxide powder, silicon carbide, etc. It is also possible to use a method based on physical treatment such as polishing a brush to which powder or the like is adhered with water dampened with water.

  In particular, in the method of performing a frost treatment that chemically performs a surface treatment using a chemical solution such as hydrogen fluoride, microcracks on the surface of the object to be treated are unlikely to occur, and mechanical strength is unlikely to decrease. It can preferably be used as a method of applying.

  In general, the surface of the glass is chemically etched after the irregularities are formed in this manner in order to adjust the surface shape. By doing so, the haze can be adjusted to a desired value depending on the etching amount, cracks generated by sandblasting or the like can be removed, and glare can be suppressed.

  As the etching, a method of immersing a transparent substrate, which is an object to be processed, in a solution containing hydrogen fluoride as a main component is preferably used. Components other than hydrogen fluoride may include hydrochloric acid, nitric acid, citric acid, and the like. By containing these, it can suppress that the alkaline component and hydrogen fluoride which are contained in glass react, and local precipitation reaction arises, and can make etching progress uniformly in a surface.

  The characteristics of the second main surface 11B of the transparent substrate are not particularly limited, and have the same surface roughness RMS as the first main surface and RSm that is the average length of the elements of the roughness curve. Can also be processed.

  Moreover, the transparent electrode for touchscreens can also be created in the 2nd main surface 11B of a transparent base | substrate. In this way, by making the transparent electrode of the touch panel and the transparent substrate with the antifouling film integrated, a further reduction in thickness and weight can be achieved. In this case, it is preferable not to perform the same antiglare processing as the first main surface 11A described above with respect to the second main surface 11B.

  And the antifouling film | membrane 12 is formed in the 1st main surface 11A side of the transparent base | substrate 11 as shown in FIG. The antifouling film 12 can be composed of a fluorine-containing organosilicon compound.

  Here, the fluorine-containing organosilicon compound will be described. The fluorine-containing organosilicon compound used in this embodiment is not particularly limited as long as it imparts antifouling properties, water repellency, and oil repellency.

  Examples of such fluorine-containing organosilicon compounds include fluorine-containing organosilicon compounds having one or more groups selected from the group consisting of polyfluoropolyether groups, polyfluoroalkylene groups, and polyfluoroalkyl groups. The polyfluoropolyether group is a divalent group having a structure in which polyfluoroalkylene groups and etheric oxygen atoms are alternately bonded.

  Specific examples of the fluorine-containing organosilicon compound having one or more groups selected from the group consisting of this polyfluoropolyether group, polyfluoroalkylene group and polyfluoroalkyl group include the following general formulas (I) to (V): The compound etc. which are represented by these are mentioned.

式中、Ｒｆは炭素数１〜１６の直鎖状のポリフルオロアルキル基（アルキル基として、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｘは水素原子又は炭素数１〜５の低級アルキル基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｒ１は加水分解可能な基（例えば、アミノ基、アルコキシ基等）又はハロゲン原子（例えば、フッ素、塩素、臭素、ヨウ素等）、ｍは１〜５０、好ましくは１〜３０の整数、ｎは０〜２、好ましくは１〜２の整数、ｐは１〜１０、好ましくは１〜８の整数である。

In the formula, Rf is a linear polyfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X is hydrogen. An atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), R1 is a hydrolyzable group (for example, amino group, alkoxy group) Etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1 to 50, preferably 1 to 30, n is an integer of 0 to 2, preferably 1 to 2, and p is 1 to 2. It is an integer of 10, preferably 1-8.

_{C q F 2q + 1 CH 2} CH 2 Si (NH 2) 3 (II)
Here, q is 1 or more, preferably an integer of 2 to 20.

Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ), n-heptafluoro. Examples thereof include (1,1,2,2-tetrahydro) pentylsilazane (nC ₃ F ₇ CH ₂ CH ₂ Si (NH ₂ ) ₃ ).

C _{q ′} F _{2q ′ + 1} CH ₂ CH ₂ Si (OCH ₃ ) ₃ (III)
Here, q ′ is 1 or more, preferably an integer of 1-20.

Examples of the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane _{(n-C 8 F 17 CH} 2 CH 2 Si (OCH 3) 3) or the like can be mentioned.

式（ＩＶ）中、Ｒ^ｆ２は、−（ＯＣ_３Ｆ_６）_ｓ−（ＯＣ_２Ｆ_４）_ｔ−（ＯＣＦ_２）_ｕ−（ｓ、ｔ、ｕはそれぞれ独立に０〜２００の整数）で表わされる２価の直鎖状ポリフルオロポリエーテル基であり、Ｒ^２、Ｒ^３は、それぞれ独立に炭素原子数１〜８の一価炭化水素基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）である。Ｘ^２、Ｘ^３は独立に加水分解可能な基（例えば、アミノ基、アルコキシ基、アシロキシ基、アルケニルオキシ基、イソシアネート基等）またはハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等）であり、ｄ、ｅは独立に１〜２の整数であり、ｃ、ｆは独立に１〜５（好ましくは１〜２）の整数であり、ａおよびｂは独立に２または３である。

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

In R ^f2 of the compound (IV), s + t + u is preferably 20 to 300, more preferably 25 to 100. R ² and R ³ are more preferably a methyl group, an ethyl group, or a butyl group. As a hydrolysable group shown by X < ² >, X < ³ >, a C1-C6 alkoxy group is more preferable, and a methoxy group and an ethoxy group are especially preferable. Further, a and b are each preferably 3.

式（Ｖ）中、ｖは１〜３の整数であり、ｗ、ｙ、ｚはそれぞれ独立に０〜２００の整数であり、ｈは１または２であり、ｉは２〜２０の整数であり、Ｘ^４は加水分解性基であり、Ｒ^４は炭素数１〜２２の直鎖または分岐の炭化水素基であり、ｋは０〜２の整数である。ｗ＋ｙ＋ｚは、２０〜３００であることが好ましく、２５〜１００であることがより好ましい。また、ｉは２〜１０であることがより好ましい。Ｘ^４は、炭素数１〜６のアルコキシ基が好ましく、メトキシ基、エトキシ基がより好ましい。Ｒ^４としては、炭素数１〜１０のアルキル基がより好ましい。

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

  Further, as a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a commercially available polyfluoropolyether group, polyfluoroalkylene group and polyfluoroalkyl group, KP-801 (trade name, Shin-Etsu Chemical Co., Ltd.) KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL (registered trademark) DSX and OPTOOL AES (both trade names, manufactured by Daikin) and the like can be preferably used.

  In general, fluorine-containing organosilicon compounds are stored in a mixture with a solvent such as a fluorinated solvent in order to suppress deterioration due to reaction with moisture in the atmosphere. If it is subjected to the film forming process as it is, the durability of the obtained thin film may be adversely affected.

  For this reason, in the present embodiment, the fluorine-containing organosilicon compound that has been subjected to the solvent removal treatment before heating in the heating container, or the fluorine-containing organosilicon that has not been diluted with the solvent (no solvent added) It is preferable to use a compound. For example, the concentration of the solvent contained in the fluorine-containing organosilicon compound solution is preferably 1 mol% or less, more preferably 0.2 mol% or less. It is particularly preferable to use a fluorine-containing organosilicon compound that does not contain a solvent.

Examples of the solvent used for storing the fluorine-containing organosilicon compound include perfluorohexane, metaxylene hexafluoride (C ₆ H ₄ (CF ₃ ) ₂ ), hydrofluoropolyether, HFE7200 / 7100 (trade name, manufactured by Sumitomo 3M Ltd., HFE7200 is represented by C ₄ F ₉ C ₂ H ₅ , and HFE 7100 is represented by C ₄ F ₉ OCH ₃ ).

  The removal treatment of the solvent (solvent) from the fluorine-containing organosilicon compound solution containing the fluorine-based solvent can be performed, for example, by evacuating a container containing the fluorine-containing organosilicon compound solution.

  The time for performing vacuum evacuation is not limited because it varies depending on the exhaust capacity of the exhaust line, vacuum pump, etc., the amount of the solution, and the like, but may be, for example, about 10 hours or more.

  The method for forming the antifouling film of this embodiment is not particularly limited, but it is preferable to form the film by vacuum deposition using the above materials.

  In addition, the solvent removal treatment is performed by evacuating the heating container at room temperature after introducing the fluorine-containing organosilicon compound solution into the heating container of the film forming apparatus for forming the antifouling film and before raising the temperature. You can also. Further, the solvent can be removed beforehand by an evaporator or the like before being introduced into the heating container.

  However, as described above, the fluorine-containing organosilicon compound having a small or no solvent content is more likely to be deteriorated by contact with the atmosphere as compared with a compound containing a solvent.

  For this reason, storage containers for fluorine-containing organosilicon compounds with low (or no) solvent content should be replaced with an inert gas such as nitrogen and sealed, and exposed to the atmosphere when handled. It is preferable to shorten the contact time.

  Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into a heating container of a film forming apparatus for forming an antifouling film immediately after opening the storage container. And after introduction | transduction, it is preferable to remove the air | atmosphere (air) contained in a heating container by evacuating the inside of a heating container or substituting with inert gas, such as nitrogen and a noble gas. For example, the storage container and the heating container are more preferably connected by a pipe with a valve so that the storage container (storage container) can be introduced into the heating container of the present manufacturing apparatus without coming into contact with the atmosphere.

  Then, after introducing the fluorine-containing organosilicon compound into the heating container and replacing the inside of the container with a vacuum or an inert gas, it is preferable to immediately start heating for film formation.

  As an example of the method for forming the antifouling film, in the description of the present embodiment, an example using a fluorine-containing organosilicon compound as a solution or stock solution has been described, but the present invention is not limited thereto. As another method, for example, a so-called deposition pellet in which a certain amount of a fluorine-containing organosilicon compound is impregnated with a porous metal (for example, tin or copper) or a fibrous metal (for example, stainless steel) is commercially available. There is a method of using this (for example, Surf Clear manufactured by Canon Optron). In this case, the antifouling film can be easily formed using the amount of pellets corresponding to the capacity of the vapor deposition apparatus and the required film thickness as the vapor deposition source.

  As described above, since the antifouling film traces the surface shape of the transparent substrate as it is, its surface characteristics are equivalent to the surface roughness RMS of the transparent substrate and the average length RSm of the elements of the roughness curve. Therefore, the surface roughness RMS is 0.05 μm or more and 0.25 μm or less, and the average length RSm of the elements of the roughness curve is 10 μm or more and 40 μm or less. In particular, the surface roughness RMS is more preferably 0.08 μm or more and 0.20 μm or less, and the average length RSm of the elements of the roughness curve is more preferably 15 μm or more and 35 μm or less.

  Further, for the purpose of improving the adhesion between the transparent substrate and the antifouling film, an adhesion layer may be inserted between the transparent substrate and the antifouling film. When the adhesion layer is inserted, it may be formed in advance on the first main surface of the transparent substrate before forming the antifouling film. A silicon oxide film is preferably used as the adhesion layer. The film thickness is 2 nm to 50 nm, preferably 5 nm to 20 nm.

  Although each member of the transparent substrate with an antifouling film of the present embodiment has been described above, the haze of the transparent substrate with an antifouling film of the present embodiment is preferably 2% or more and 30% or less. If the haze is 2% or more, the reflection of light can be confirmed visually and compared with a substrate that has not been antiglare processed, but if it exceeds 30%, the light will be diffusely reflected. This is because, when used as a substrate integrated with a cover member or a touch panel of the display device, the display visibility of the display device is lowered. Further, the haze of the transparent substrate with an antifouling film of the present embodiment is more preferably 15% or more and 27% or less.

  The haze in the above range indicates that the transparent substrate with the antifouling film of this embodiment has sufficient antiglare properties, and can be more preferably used as a substrate integrated with a cover member or a touch panel of a display device or the like. .

According to the transparent substrate with an antifouling film of the present embodiment described above, it is possible to provide a transparent substrate with an antifouling film having antiglare properties and improved durability of the antifouling film.
[Second Embodiment]
In the present embodiment, a configuration in which a low reflection film is further provided in the first embodiment will be described. Since other configurations are the same as those described in the first embodiment, they are omitted here.

  Since the low reflection film can suppress light reflection on the surface of the transparent substrate with the antifouling film, the antiglare property can be further improved. For example, when used as a cover member of a display device, it is possible to suppress the reflection of ambient light and further improve the display visibility of the display device.

  The material of the low reflection film is not particularly limited, and various materials can be used as long as the material can suppress reflection. For example, the low reflective film can be configured by laminating a high refractive index layer and a low refractive index layer.

  The high refractive index layer and the low refractive index layer may each include one layer, but may include two or more layers. When two or more high refractive index layers and low refractive index layers are included, it is preferable that the high refractive index layers and the low refractive index layers are alternately laminated.

  In order to obtain sufficient antireflection performance, the low reflection film is preferably a laminate in which a plurality of films (layers) are laminated. For example, the laminate preferably has a total of 2 or more and 6 or less layers, more preferably 2 or more and 4 or less layers. The laminate here is preferably a laminate in which a high refractive index layer and a low refractive index layer are laminated as described above, and the total number of layers of the high refractive index layer and the low refractive index layer is the above. A range is preferable.

The materials of the high refractive index layer and the low refractive index layer are not particularly limited, and can be selected in consideration of the required degree of antireflection, 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 ), silicon nitride (SiN), and tantalum oxide (Ta ₂ O ₅ ). One or more selected can be preferably used. As a material constituting the low refractive index layer, silicon oxide (SiO ₂ ) can be preferably used.

  Niobium oxide can be particularly preferably used as the high refractive index layer from the viewpoint of productivity and the degree of refractive index. For this reason, the low reflection film is more preferably a laminate of a niobium oxide layer and a silicon oxide layer.

  In the transparent substrate with an antifouling film of the present embodiment, the place where the low reflection film is provided is not particularly limited, and can be disposed on the first main surface 11A and / or the second main surface 11B of the transparent substrate. . It is particularly preferable to provide the first main surface 11A of the transparent substrate. For example, as shown in FIG. 2, the low reflection film 13 and the fluorine-containing organosilicon compound coating 12 are laminated in this order on the surface of the first main surface 11A of the transparent substrate 11 (from the first main surface side). It is more preferable.

  In this way, the low reflection film 13 and the fluorine-containing organic silicon compound film (antifouling film) 12 are laminated on the first main surface 11A of the transparent substrate, whereby the low reflection film 13 is also peeled off. It is preferable because it can prevent and improve durability.

  Moreover, when inserting the contact | adherence layer which improves durability of an antifouling film | membrane, it is preferable to put between a low reflection film and an antifouling film | membrane. In this case as well, the silicon oxide film is preferably used. However, when the uppermost layer of the low reflection film is also silicon oxide as in the above example, the low reflectivity and the effect of the adhesion layer can be achieved at the same time. Therefore, this is a preferable configuration.

  In FIG. 2, the low reflection film 13 has a configuration in which two layers 131 and 132 are stacked. However, the present invention is not limited to such a configuration, and a configuration in which a plurality of layers are further stacked as described above. You can also.

  Further, for the transparent substrate with an antifouling film of the present embodiment, the haze is preferably 2% or more and 30% or less, and preferably 15% or more and 27% or less for the same reason described in the first embodiment. More preferred.

  As mentioned above, although this embodiment has demonstrated the transparent base | substrate with an antifouling film | membrane which has a low reflection film, having such a structure can improve an anti-glare characteristic more. For this reason, it can be more preferably used in applications that require anti-glare properties such as a cover device of a display device and a substrate integrated with a touch panel.

Specific examples will be described below, but the present invention is not limited to these examples. Examples 1 to 4 are examples, and examples 5 to 7 are comparative examples.
(1) Evaluation method The characteristic evaluation method of the transparent substrate with an antifouling film obtained in Examples 1 to 7 below will be described below.
(Surface shape measurement)
About the surface shape of the antifouling film of the sample after the antifouling film formation used in Examples 1 to 7, using a laser microscope (trade name: VK-9700, manufactured by Keyence Corporation), a planar profile at a magnification of 50 times Was measured. Then, from the obtained planar profile, values of the surface roughness RMS and the average length RSm of the roughness curve elements were obtained based on JIS B 0601 (2001).

Since the antifouling film and the low reflection film formed in each example are very thin with respect to the thickness of the transparent substrate, the surface uneven structure substantially traces the surface shape of the transparent substrate as it is. Therefore, the surface shape of the transparent substrate (on the surface on which the antifouling film is formed) is considered to be equivalent.
(Measure haze)
In Examples and Comparative Examples, permeation haze was measured for samples after the antifouling film was formed. The haze measurement was performed using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model: HZ-V3).
(Rubbing durability (wear resistance) test)
For the samples after the antifouling film was formed in Examples 1 to 7, a rubbing durability test was performed on the antifouling film of the sample according to the following procedure.

  First, a rubbing test was performed on the antifouling films of Examples 1 to 7 according to the following procedure.

  Steel wool # 0000 was attached to the surface of a flat metal indenter having a bottom surface of 10 mm × 10 mm to obtain a friction element for rubbing the sample.

  Next, a rubbing test was carried out using the above-mentioned friction piece with a plane wear tester triple type (manufactured by Daiei Kagaku Seiki Co., Ltd., model: PA-300A). Specifically, first, the indenter is attached to a wear tester so that the bottom surface of the indenter contacts the antifouling film surface of the sample, and a weight is placed so that the load on the friction element is 1000 g, the average speed is 6400 mm / min, one way Reciprocated at 40 mm. The test was performed so that one reciprocation was counted as one rubbing and the number of rubbing was 1000.

  Thereafter, the water contact angle of the antifouling film was measured according to the following procedure.

  The water contact angle of the antifouling film is measured by dropping 1 μL of pure water onto the antifouling film using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: DM-501) and measuring the contact angle. Was done. In the measurement, each sample was measured at 10 locations on the antifouling film surface, and the average value was taken as the water contact angle after the durability test of the sample.

In this case, the contact angle of water was evaluated as 90 ° or more as acceptable and 90 ° or less as unacceptable.
(2) Experimental procedure [Example 1]
A transparent substrate with an antifouling film was produced by the following procedure.

  In this example, a glass substrate (trade name: Dragon Trail (registered trademark) manufactured by Asahi Glass Co., Ltd.) subjected to chemical strengthening treatment is used as a transparent substrate, and a predetermined frost treatment is performed on the first main surface of the glass substrate. A glass substrate (hereinafter referred to as a transparent substrate A) was used.

  Then, an antifouling film was formed on the first main surface of the transparent substrate A by the following procedure.

  First, as a vapor deposition material, a fluorine-containing organosilicon compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KY-185) was introduced into a heating container. Thereafter, the inside of the heating vessel was degassed with a vacuum pump for 10 hours or more, and the solvent in the solution was removed to obtain a composition for forming a fluorine-containing organosilicon compound film.

Subsequently, the heating container containing the composition for forming the fluorine-containing organosilicon compound film was heated to 270 ° C. After reaching 270 ° C., that state was maintained for 10 minutes until the temperature stabilized.

And the nozzle connected with the heating container containing the said composition for fluorine-containing organosilicon compound film formation with respect to the 1st main surface (surface which carried out the frost process) of the transparent base | substrate A installed in the vacuum chamber Then, a composition for forming a fluorine-containing organosilicon compound film was supplied to form a film.

During film formation, the film thickness is measured with a quartz crystal monitor installed in a vacuum chamber, and film formation is performed until the film thickness of the fluorine-containing organosilicon compound film formed on the transparent substrate A reaches 10 nm. went.

When the fluorine-containing organosilicon compound film reached 10 nm, the supply of the raw material was stopped from the nozzle, and the transparent substrate A on which the fluorine-containing organosilicon compound film was formed was taken out from the vacuum chamber.

The extracted transparent substrate A on which the fluorine-containing organosilicon compound film was formed was placed on a hot plate with the film surface facing upward, and heat-treated in the atmosphere at 150 ° C. for 60 minutes.

The sample thus obtained was subjected to the surface shape measurement, haze measurement, and rubbing durability test. The results are shown in Table 1.
[Example 2]
Using a glass substrate (trade name: Dragon Trail (registered trademark) manufactured by Asahi Glass Co., Ltd.) subjected to chemical strengthening treatment as a transparent substrate, and using a transparent substrate B subjected to frost treatment on the first main surface of the glass substrate An antifouling film was formed on the first main surface of the transparent substrate B in the same manner as in Example 1 except that. The obtained transparent substrate with an antifouling film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 3]
Using a glass substrate (trade name: Dragon Trail (registered trademark) manufactured by Asahi Glass Co., Ltd.) subjected to chemical strengthening treatment as a transparent substrate, and using a transparent substrate C subjected to frost treatment on the first main surface of the glass substrate An antifouling film was formed on the first main surface of the transparent substrate C in the same manner as in Example 1 except that. The obtained transparent substrate with an antifouling film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 4]
On the transparent substrate A, a low reflection film was formed as follows.

First, a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3 using a niobium oxide target (manufactured by AGC Ceramics, trade name NBO target) while introducing a mixed gas obtained by mixing 10% by volume of oxygen gas with argon gas. Pulse sputtering was performed under the conditions of 0.8 W / cm ² and inversion pulse width of 5 μsec to form a high refractive index layer made of niobium oxide (niobium) having a thickness of 13 nm on the first main surface of the transparent substrate A.

Next, while introducing a mixed gas obtained by mixing 40% by volume of oxygen gas into argon gas, using a silicon target, conditions of pressure 0.3 Pa, frequency 20 kHz, power density 3.8 W / cm ² , and inversion pulse width 5 μsec Then, pulse sputtering was performed under the condition of a pulse width of 5 μsec, and a low refractive index layer made of silicon oxide (silica) having a thickness of 30 nm was formed on the high refractive index layer.

Next, while introducing a mixed gas obtained by mixing 10% by volume of oxygen gas into argon gas, using a niobium oxide target (manufactured by AGC Ceramics, trade name: NBO target), pressure 0.3 Pa, frequency 20 kHz, power density 3. Pulse sputtering was performed under the conditions of 8 W / cm ² and inversion pulse width of 5 μsec, and a high refractive index layer made of niobium oxide (niobium) having a thickness of 110 nm was formed on the low refractive index layer.

Next, while introducing a mixed gas obtained by mixing 40% by volume of oxygen gas into argon gas, using a silicon target, conditions of pressure 0.3 Pa, frequency 20 kHz, power density 3.8 W / cm ² , and inversion pulse width 5 μsec Then, pulse sputtering was performed under the condition of a pulse width of 5 μsec to form a low refractive index layer made of silicon oxide (silica) having a thickness of 90 nm.

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

  Next, in the same manner as in Example 1, an antifouling film was formed on the low reflection film.

The obtained transparent substrate with an antifouling film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 5]
Using a glass substrate (trade name: Dragon Trail (registered trademark) manufactured by Asahi Glass Co., Ltd.) subjected to chemical strengthening treatment as a transparent substrate, and using a transparent substrate D subjected to frost treatment on the first main surface of the glass substrate An antifouling film was formed on the first main surface of the transparent substrate D in the same manner as in Example 1 except that. The obtained transparent substrate with an antifouling film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 6]
Using a glass substrate (trade name: Dragon Trail (registered trademark) manufactured by Asahi Glass Co., Ltd.) that has been chemically strengthened as a transparent substrate, and using a transparent substrate E that is frosted on the first main surface of the glass substrate An antifouling film was formed on the first main surface of the transparent substrate E in the same manner as in Example 1 except that. The obtained transparent substrate with an antifouling film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 7]
A low reflection film and an antifouling film were formed in the same manner as in Example 4 except that the same transparent substrate D as in Example 5 was used as the transparent substrate, and the obtained transparent substrate with an antifouling film was the same as in Example 1. Evaluation was performed. The results are shown in Table 1.

表１に示した結果によると、本発明の規定を充足する例１〜４についてはいずれも擦り耐久性試験において水接触角が９０°以上となっているのに対して、例５〜７については、８０°以下であった。

According to the results shown in Table 1, with respect to Examples 1 to 4 that satisfy the provisions of the present invention, the water contact angle is 90 ° or more in the rubbing durability test, whereas Examples 5 to 7 Was 80 ° or less.

  The antifouling film has water repellency, and when the water contact angle is small as described above, it indicates that the antifouling film is peeled off and worn. For this reason, about Examples 5-7, it turns out that the antifouling film peels and wears.

  From these results, it was confirmed that the durability of the antifouling film was very high in Examples 1 to 4 satisfying the provisions of the present invention as compared with Examples 5 to 7 as comparative examples.

  Moreover, about Examples 1-4, it has also confirmed that it has an appropriate glare-proof characteristic from the value of the haze.

  Although the transparent substrate with an antifouling film has been described in the embodiment and examples, the present invention is not limited to the above embodiment and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

  This application claims priority based on Japanese Patent Application No. 2013-015968 filed with the Japan Patent Office on January 30, 2013. The entire contents of Japanese Patent Application No. 2013-015968 are incorporated herein by reference. Incorporate.

11 Transparent substrate 12 Antifouling film 13 Low reflection film

Claims (6)

A first major surface, and a transparent substrate which have a second major surface opposite the first major surface,
Has a antifouling film consisting off Tsu-containing organic silicon compound is provided on the first main surface side of the transparent substrate, a low reflection film, and
The proof surface roughness RMS of the fouling layer is not more 0.05μm or 0.25μm or less, Ri average length RSm of Der least 40μm or less 10μm elements of the roughness curve of the antifouling film,
A transparent substrate with an antifouling film, wherein the low reflection film and the antifouling film are laminated in this order on the surface of the first main surface of the transparent substrate.   2. The transparent substrate with an antifouling film according to claim 1, wherein the haze of the transparent substrate with an antifouling film is 2% or more and 30% or less.   The transparent substrate with an antifouling film according to claim 1 or 2, wherein the transparent substrate is a glass substrate. An uneven shape is formed on the first main surface of the transparent substrate,
The surface roughness RMS of the first main surface of the transparent substrate is 0.05 μm or more and 0.25 μm or less, and the average length RSm of the elements of the roughness curve of the first main surface of the transparent substrate is The transparent substrate with an antifouling film according to claim 3, wherein the transparent substrate has a thickness of 10 µm or more and 40 µm or less. The low reflection film, niobium oxide, titanium oxide, zirconium oxide, silicon nitride, a layer containing one or more selected from tantalum oxide, any one of claims 1 to 4, a laminate of a silicon oxide layer 1 A transparent substrate with an antifouling film as described in the paragraph Wherein a laminate a low reflective film is more layers are laminated, according to claim 1 wherein the laminate of the entire two or more layers 6 layers or less layers are laminated Transparent substrate with antifouling film.

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