JP2016153221A - Composition, member prepared with composition, and method for producing the same, and touch panel comprising member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member having excellent antifouling property, a composition that forms an antifouling layer of the member, and a touch panel comprising the member.SOLUTION: A member has an antifouling layer formed on a base material, where the antifouling layer has a condensation polymer of alkoxysilane having a perfluoro polyether structure and at least one selected from alkoxysilane represented by formulas (1) and (2). (In the formula (1), Ris an alkyl group; Ris an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group; x is an integer of 2-4) (In the formula (2), Ris an alkyl group; Y is a divalent organic group).SELECTED DRAWING: None

Description

  The present invention relates to a member having an antifouling layer formed on a substrate, a method for producing the same, a touch panel provided with the member, and a composition for forming the antifouling layer.

Liquid crystal display, plasma display, organic / inorganic EL display, electronic paper, VFD (Vacuum Fluorescent Display), image display device such as EPD (Electrophoretic Display), touch panel, mobile phone, music player and other portable electronic devices, CD (Compact An optical recording medium such as a disk (Disc), DVD (Digital Versatile Disk), or Blu-ray disc may have dirt such as fingerprints, sebum, and sweat on its surface during handling. Such dirt deteriorates the visibility in the case of an image display device, a touch panel, or a display of various electronic devices, and may adversely affect the operability when operated on the display. Further, in the optical recording medium, there may be a failure in signal recording and reproduction.
Therefore, it is necessary to impart characteristics (antifouling properties) such as dirt adhesion prevention and dirt wiping ease to the surface of the article.
Therefore, various investigations have been made to form an antifouling or water-repellent thin film on the surface of an article.

For example, Patent Document 1 discloses an antifouling thin film formed using a fluoroalkylsilane having antifouling property or water repellency on a substrate surface by a vacuum deposition method.
Patent Document 2 discloses an organic-inorganic hybrid film formed by hydrolyzing and polycondensing an organic silane and a metal alkoxide on a solid surface.

JP 2006-336109 A JP 2013-2131181 A

However, the thin film described in Patent Document 1 can reduce the surface free energy, but there is no mention of sliding property. Here, in the present invention, the “sliding property” is an index representing the difficulty of attaching dirt and the ease of wiping off the dirt. In general, a surface modified with a perfluoroalkyl group does not have slipperiness due to the rigidity of the perfluoroalkyl group, and the antifouling properties such as fingerprint attachment and wiping are not sufficient. Therefore, Patent Document 1 is considered to be the same.
Moreover, although the film | membrane of patent document 2 uses the metal alkoxide with organic silane, compared with the thin film formed only by the conventional organic silane, it has improved the sliding property of the droplet of this film | membrane surface. When alkylsilane is used, the surface free energy does not decrease sufficiently, and when perfluoroalkylsilane is used, the perfluoroalkyl group is rigid. It was not enough.

For operation of a terminal having a touch panel display such as a smartphone or a tablet terminal, an operation of touching the screen with a finger (tap) and moving the finger while touching (slide, pinch) is essential. Therefore, compared to conventional antifouling members used in displays such as televisions, the frequency of contamination due to fingerprint adhesion is high, and there is a greater demand for contamination prevention due to fingerprint adhesion, which is higher than the conventionally required antifouling property. Performance is required.
However, the conventional antifouling member as described above is insufficient to solve the fingerprint adhesion problem peculiar to the touch panel, in which the fingerprint is adhered while actually touching with a finger.

  The present invention has been made in view of such a situation, and is a member excellent in antifouling properties such as adhesion prevention of dirt and ease of wiping off dirt, a method for producing the member, and an antifouling layer of the member It aims at providing the composition which forms, and a touch panel provided with this member.

As a result of intensive studies to solve the above problems, the present inventors have found that an alkoxysilane having a perfluoropolyether structure and an alkoxysilane having a specific structure represented by the general formula (1) or (2) It was found that the antifouling property of the member surface can be improved by using in combination.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [8].
[1] A member formed by forming an antifouling layer on a substrate,
The antifouling layer contains a polycondensation product of an alkoxysilane having a perfluoropolyether structure and at least one selected from alkoxysilanes represented by the following general formulas (1) and (2): A member.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)
[2] The member according to [1] above, wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.
[3] The member according to [1] or [2], wherein the alkoxysilane represented by the general formula (1) is tetraalkoxysilane.
[4] The member according to any one of [1] to [3], wherein the tetraalkoxysilane is at least one selected from tetramethoxysilane and tetraethoxysilane.
[5] The contact angle of pure water on the surface of the antifouling layer is 95 ° or more and the sliding angle is 30 ° or less, according to any one of the above [1] to [4]. Members.
[6] A method for producing a member formed by forming an antifouling layer on a substrate, comprising an alkoxysilane having a perfluoropolyether structure and an alkoxysilane represented by the following general formulas (1) and (2) (1) preparing a composition containing a polycondensation product obtained by hydrolysis and polycondensation of at least one selected from the above in a mixed solvent of an organic solvent, water and an acid, and the composition And (2) forming an antifouling layer by applying an object to the substrate.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)
[7] A touch panel including the member according to any one of [1] to [5].
[8] A composition comprising a polycondensation product of an alkoxysilane having a perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the following general formulas (1) and (2).

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)

  According to the present invention, a member having excellent antifouling properties while maintaining the optical properties and physical properties inherently provided, a method for producing the member, a composition for forming an antifouling layer of the member, and the member are provided. A touch panel can be provided.

First, the member of this invention is demonstrated.
[Element]
The member of the present invention comprises a polycondensation product of an alkoxysilane having a perfluoropolyether structure on a substrate and at least one selected from the alkoxysilanes represented by the following general formulas (1) and (2). An antifouling layer is formed.
Here, in the present invention, “having a perfluoropolyether structure” means having a group containing a perfluoropolyether bond.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)

<Base material>
Examples of the substrate used for the member of the present invention include various inorganic materials such as glass plates, aluminum oxide plates, and spin-on-glass (SOG) materials, thermoplastic resins, thermosetting resins, and ionizing radiation curable resins. And various organic resin materials, organic-inorganic composite materials, and the like. Among them, from the viewpoint of reactivity with silane, those having a hydroxyl group on the surface are preferable, and from the viewpoints of workability of the material, mechanical strength of the resulting member, and ease of forming an antifouling layer, A glass plate or an organic-inorganic composite material is preferable, and a glass plate is more preferable. The glass plate may be chemically strengthened for the purpose of improving the strength. Examples of SOG materials include alkylsiloxane materials such as methylsiloxane, hydroxysilsesquioxane materials, silazane materials, silsesquioxane materials, and silsesquioxane materials in terms of durability. Is preferred.
Examples of commercially available SOG materials include an interlayer insulating film coating material “HSG” (trade name, manufactured by Hitachi Chemical Co., Ltd.) and an OCN series manufactured by Tokyo Ohka Kogyo Co., Ltd. Moreover, as a commercially available organic-inorganic composite material, an organic-inorganic composite material (trade name “NH-1000G”, manufactured by Nippon Soda Co., Ltd.) whose outermost surface is spontaneously mineralized by UV irradiation can be used.
In addition, the shape of the base material may be a planar structure or a three-dimensional structure.

Although the thickness of the glass plate used as a base material does not have a restriction | limiting in particular, From a viewpoint of an optical characteristic or durability, Preferably it is 0.01-100 mm, More preferably, it is 0.02-10 mm. The thickness of the resin film used as the substrate is preferably 1 to 500 μm, more preferably 3 to 300 μm, from the viewpoint of strength and optical properties.
A low reflection layer may be formed on the surface of the substrate in order to improve optical characteristics. The low reflection layer can be formed by laminating a plurality of inorganic compounds by sputtering or the like. In addition, on the surface of the base material and the low reflection layer, in order to improve adhesion and improve long-term reliability in the use environment, application of a coating called an anchor agent or primer, or as an adhesive layer The inorganic layer may be formed in advance. As the inorganic layer, a silicon-based compound is preferable, and SiO ₂ and SiOx are more preferable from the viewpoints of adhesiveness and durability. The adhesive layer can be formed using a method such as a vapor deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method. Moreover, in order to improve adhesiveness irrespective of the presence or absence of formation of these layers, you may perform physical processes, such as a corona discharge process, an oxidation process, and a plasma process.
Further, from the viewpoint of use as a display or the like, the total light transmittance of the substrate is preferably 85% or more, and more preferably 90% or more. The transmittance | permeability of a base material can be measured by the method based on JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

<Anti-fouling layer>
The antifouling layer used in the member of the present invention is an antifouling layer, and is selected from alkoxysilanes having a perfluoropolyether structure and alkoxysilanes represented by the general formulas (1) and (2). And at least one condensation polymer (hereinafter, also simply referred to as “condensation polymer”). When the polycondensation product has a perfluoropolyether structure, it is possible to reduce the surface free energy of the antifouling layer and make it difficult to be soiled. The polycondensation product is a polycondensation structure of an alkoxysilane having a perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the general formulas (1) and (2). Therefore, the spacing between adjacent perfluoropolyether structure sites is wide and sparse, and the perfluoropolyether structure sites are easy to move and have flexibility, thereby improving sliding properties, making it more difficult to get dirty, and The attached dirt can be easily wiped off.
The ratio of the condensation polymer occupying the antifouling layer is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass.

(Alkoxysilane having perfluoropolyether structure)
The alkoxysilane having a perfluoropolyether structure used as a raw material for the polycondensation product has a perfluoropolyether structure, thereby reducing the surface free energy of the antifouling layer and making it difficult to be stained. Furthermore, the interval between adjacent perfluoropolyether structure parts is wide and sparse, and the perfluoropolyether structure parts are easy to move and have flexibility, so that it is more difficult to get dirt and wipes off the attached dirt. make it easier.
Examples of the alkoxysilane having the perfluoropolyether structure include compounds represented by the following general formulas (3) to (6). From the viewpoint of antifouling properties, the alkoxysilane is represented by the following general formula (3). Are preferred.

(In the formula, R ⁴ is an alkyl group having 1 to 6 carbon atoms. However, a plurality of R ⁴ may be the same or different. R ^{5 to} R ¹² are each independently 1 to 12 carbon atoms. Z ¹ is a 1 to 10 valent organopolysiloxane group having a siloxane bond, Z ² is a 2 to 10 valent organopolysiloxane group having a siloxane bond, Q is A group containing a fluoropolyether bond, Rf is a linear or branched fluorinated alkyl group, n is an integer from 1 to 200, and m is an integer from 1 to 10.)

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, n-hexyl group, isohexyl group and the like. From the viewpoint of antifouling properties and reactivity, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
R ^{5 to} R ¹² are each independently a divalent organic group having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms. Specifically, methylene group, ethylene group, propylene group (trimethylene group) , Methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group and octamethylene group, arylene group such as phenylene group, or a combination of two or more of these groups. It is done. In addition, these groups may contain an ether bond, an amide bond, an ester bond, and a vinyl bond, and may further contain an oxygen atom, a nitrogen atom, and a fluorine atom.

Examples of the ² to 10 valent organopolysiloxane group having a siloxane bond of Z ² include groups represented by the following general formulas (7-1) to (7-12).

  Among the groups represented by the general formulas (7-1) to (7-12), from the viewpoint of obtaining the antifouling property that is the effect of the present invention, the general formulas (7-1), (7-2), Groups represented by (7-3), (7-4) and (7-7) are preferred.

The group containing a perfluoropolyether bond of the Q, for _{example, -CF 2 O -, - CF} 2 CF 2 O -, - CF 2 CF 2 CF 2 O -, - CF (CF 3) CF 2 O- _{, -OCF 2 OCF 2 CF 2 -} , - CF 2 CF 2 CF 2 CF 2 O -, - CF 2 CF (CF 3) CF 2 O -, - CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O- , -C _{(CF 3)} 2 O- and the like.
Among them, from the viewpoint of antifouling _{property, -CF 2 CF 2 O -,} - CF 2 CF 2 CF 2 O -, - CF (CF 3) CF 2 O -, - OCF 2 OCF 2 CF 2 -, - CF 2 CF (CF ₃ ) CF ₂ O— is preferred. These may include only one type or two or more types.

Rf is a linear or branched fluorinated alkyl group, and a linear fluorinated alkyl group is preferred from the viewpoint of obtaining the effects of the present invention.
Examples of the linear fluorinated alkyl group include a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, and a tridecafluorohexyl group. Examples of the fluorinated alkyl group having a branched chain structure include 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, 1,1-di (trifluoromethyl) -2,2,2 -Trifluoroethyl group, 2- (trifluoromethyl) -1,1,3,3,3-pentafluoropropyl group and the like can be mentioned.

The n is an integer of 1 to 200, and preferably 2 to 100, more preferably 3 to 60, from the viewpoint of antifouling properties. By setting n to 1 or more, the substrate surface can be sufficiently covered, the surface free energy of the antifouling layer surface can be reduced, and the antifouling property can be improved. By setting n to 200 or less, the reactivity of the alkoxysilyl group (—Si (OR ⁴ ) ₃ ) can be increased.

  M is an integer of 1 to 10, and preferably 1 to 7, more preferably 1 to 5, from the viewpoint of antifouling properties. When m is 1 or more, slipperiness is improved, and higher antifouling properties are obtained. By setting m to 10 or less, an increase in surface free energy can be suppressed and a decrease in antifouling property can be suppressed.

The alkoxysilane having a perfluoropolyether structure is preferably trimethoxysilane having a perfluoropolyether structure from the viewpoint of antifouling properties and reactivity.
In addition, as the alkoxysilane having the perfluoropolyether structure, “X-71-195”, “KY-178”, “KY-164”, “KY-108”, “KP-” manufactured by Shin-Etsu Chemical Co., Ltd. "911", "Optool DSX", "Optool DSX-E" manufactured by Daikin Industries, Ltd. are commercially available, and "X-71-195" is preferable from the viewpoint of productivity and antifouling property.

(Alkoxysilane represented by the general formulas (1) and (2))
The alkoxysilane represented by the following general formulas (1) and (2) is used as a raw material for the condensation polymer.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)

Examples of the alkyl group having 1 to 6 carbon atoms of R ^{1 in} the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. N-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group and the like. Among these, from the viewpoint of antifouling properties and reactivity, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

R ² is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 ring atoms, or an aryl group having 6 to 20 ring atoms. Among these, from the viewpoint of antifouling properties and reactivity, an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are preferable.

Examples of the alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms of R ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, Examples include n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Among these, from the viewpoint of antifouling properties and reactivity, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable, and a methyl group is more preferable.

Examples of the alkenyl group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms of R ² include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and the like. From the viewpoint of antifouling properties and reactivity, a vinyl group is preferable.

Examples of the cycloalkyl group having 3 to 10 ring atoms of R ² include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the aryl group having 6 to 20, preferably 6 to 12 ring-forming atoms of R ² include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group. Among them, a phenyl group is preferable.

  The alkyl group, alkenyl group, cycloalkyl group, and aryl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy group, acryloyloxy group, methacryloyloxy group and the like. Of these, a methacryloyloxy group is preferable.

  x is an integer of 2 to 4, and is preferably 3 or 4 from the viewpoint of antifouling properties and reactivity, and more preferably 4.

Examples of the alkyl group having 1 to 6 carbon atoms of R ^{3 in} the general formula (2) include the same ones as R ¹ above. From the viewpoint of antifouling property and reactivity, a methyl group and an ethyl group are particularly preferable. preferable.
Examples of the divalent organic group of Y include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like, an alkylene group having 1 to 12 carbon atoms, a phenylene group, and the like. Examples include an arylene group having 6 to 14 carbon atoms. Among these, a methylene group and an ethylene group are preferable from the viewpoint of durability.

The alkoxysilane represented by the general formulas (1) and (2) is preferably an alkoxysilane represented by the general formula (1) from the viewpoint of antifouling properties and reactivity. Alkoxysilane is preferable, and tetraalkoxysilane is more preferable.
Specific examples of trialkoxysilane include trimethoxy (methyl) silane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. Of these, trimethoxy (methyl) silane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane are preferable. Trimethoxy (methyl) silane, vinyltrimethoxysilane, and 3-methacryloxypropyltri Methoxysilane is more preferable, and trimethoxy (methyl) silane and vinyltrimethoxysilane are more preferable.

  Since tetraalkoxysilane has four alkoxy groups, it has high reactivity with the alkoxysilane having the perfluoropolyether structure. The tetraalkoxysilane is preferably at least one selected from tetramethoxysilane and tetraethoxysilane.

The alkoxysilane represented by the general formulas (1) and (2) may be used alone or in combination of two or more.
When using 2 or more types together, the combination is not particularly limited, but a combination of tetraalkoxysilane and trialkoxysilane is preferable from the viewpoint of antifouling property and reactivity. The weight ratio of tetraalkoxysilane and trialkoxysilane can obtain the effect of the present invention by any value, but in addition to antifouling properties, mechanical strength, chemical resistance, from the viewpoint of imparting, Preferably it is 1: 0-100, More preferably, it is 1: 0.01-99, More preferably, it is 1: 0.03-98.

(Composition)
The composition forming the antifouling layer contains the above condensation polymer. The polycondensation product is selected from an alkoxysilane having the perfluoropolyether structure and an alkoxysilane represented by the general formulas (1) and (2) in a mixed solvent of an organic solvent, water and an acid. An embodiment obtained by hydrolysis and polycondensation of at least one kind is preferred.
Specifically, the polycondensate is at least one selected from the alkoxy group of the alkoxysilane having the perfluoropolyether structure and the alkoxysilane represented by the general formulas (1) and (2). Each of the alkoxy groups possessed by is hydrolyzed to form silanol groups, and then each silanol group is obtained by condensation polymerization.

As the organic solvent, a fluorine-based solvent is preferably used from the viewpoint of dissolving the alkoxysilane having the perfluoropolyether structure. Further, from the viewpoint of solubility in water, a mixed organic solvent of a fluorinated solvent and an amphiphilic solvent is preferable.
As the amphiphilic solvent, for example, water-soluble organic solvents such as alcohols and ketones are preferably used. Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and tertiary butyl alcohol. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. As other water-soluble organic solvents, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate and the like are used. These can be used alone or in admixture of two or more.

  The compounding amount of the organic solvent in the composition is preferably 90.000 to 99.999% by mass, more preferably 92.00 to 99.99% by mass, and further preferably 95.0 to 99.9% by mass. . By making it 90.000% by mass or more, the reaction in the mixed solvent can be promoted uniformly, and the antifouling layer formed from the composition can be made uniform and transparent, and 99.999% by mass or less. By doing so, a sufficient antifouling layer can be formed on the substrate surface.

  Examples of water include ion exchange water and distilled water. The amount of water contained in the mixed solvent is not particularly limited as long as it is 0.001% by mass or more, but is preferably 0.001-1.000% by mass, more preferably 0.005- It mix | blends in the ratio of 0.500 mass%. By setting it as 0.001 mass% or more, the said hydrolysis is accelerated | stimulated, and precipitation of the alkoxysilane which has a perfluoro polyether structure can be suppressed by setting it as 1.000 mass% or less.

  The acid is not particularly limited as long as it has an action of promoting the hydrolysis, and includes hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, succinic acid, acetic acid, formic acid, oxalic acid, citric acid, benzoic acid, etc. From the viewpoint of reactivity and removal from the antifouling layer during drying, hydrochloric acid is preferred. Moreover, the compounding quantity of the acid contained in the mixed solvent is preferably 0.000001 to 10.000000 mass%, more preferably 0.00001 to 5.00000 mass%, from the viewpoint of promoting the hydrolysis. More preferably, it is 0.0001-1.0000 mass%.

In the composition of the present invention, in addition to the above-mentioned components, a photoacid generator or a photobase generator generally blended in this type of composition is added as necessary as long as the effects of the present invention are not impaired. Can be blended. By blending the photoacid generator or photobase generator, a stronger antifouling layer can be formed.
The solid content concentration of the composition is preferably 0.01 to 15.00% by mass, more preferably 0.05 to 10.00% by mass, and still more preferably 0.1 to 5.0%. % By mass. By setting the content to 0.01% by mass or more, the curing of the antifouling layer can be promoted, and by setting the content to 15.00% by mass or less, coloring of the antifouling layer and deterioration of the antifouling property can be suppressed. it can.

  Although the thickness of an antifouling layer is not specifically limited, From a viewpoint of antifouling property and durability, Preferably it is 1-30 nm (estimated value), More preferably, it is 1-10 nm (estimated value).

Conventionally, the antifouling layer has been studied to increase the contact angle between water and fat in order to make it difficult to get dirt. On the other hand, in the present invention, by increasing the contact angle between water and oil and fat, and reducing the sliding angle between the two, high sliding property is obtained, so that the dirt is difficult to be attached. It is easy to wipe off.
The sliding property can be evaluated by measuring the sliding angle of pure water and n-hexadecane. The smaller the sliding angle, the better the sliding property. The sliding angle is a tilt angle at which 10 μL of pure water and 3 μL of n-hexadecane are dropped in a horizontal state on the surface of the antifouling layer of the member to be measured, the member is gradually tilted, and the droplet starts to slide. It is obtained by measuring (sliding angle). As the measuring device, for example, a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd. can be used. Specifically, the sliding angle can be measured by the method described in Examples.

In the member of the present invention, the contact angle of pure water on the surface of the antifouling layer is preferably 95 ° or more, more preferably 112 ° or more, and further preferably 114 ° or more. Further, the sliding angle of pure water on the surface of the antifouling layer is preferably 30 ° or less, more preferably 15 ° or less, and further preferably less than 8 °.
When the contact angle is 95 ° or more, it indicates that the antifouling layer has low surface free energy, and it is possible to make the antifouling difficult. Further, when the sliding angle is 30 ° or less, the sliding property of the surface of the antifouling layer is improved, the dirt is hardly attached, and the attached dirt can be easily wiped off.
In the present invention, the reason why the contact angle can be 95 ° or more is considered to be that the condensation polymer has a perfluoropolyether structure site. The sliding angle can be set to 30 ° or less because the polycondensation product is an alkoxysilane having a perfluoropolyether structure and an alkoxysilane represented by the general formulas (1) and (2). Due to the polycondensation structure of at least one selected from among them, the spacing between adjacent perfluoropolyether structure sites is wide and sparse, and the perfluoropolyether structure sites are easy to move and have flexibility. It is thought that.
The contact angle is measured by the θ / 2 method with respect to pure water and n-hexadecane using a contact angle measuring device (for example, a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd.). Is required. Specifically, the contact angle can be measured by the method described in Examples.

  In the member of the present invention, the contact angle of n-hexadecane on the antifouling layer surface is preferably 50 ° or more, more preferably 55 ° or more, and further preferably 60 ° or more. Further, the sliding angle of n-hexadecane on the surface of the antifouling layer is preferably 15 ° or less, more preferably 10 ° or less, and further preferably 6 ° or less.

The present inventors provide a polycondensation product of an alkoxysilane having a perfluoropolyether structure in an antifouling layer and at least one selected from the alkoxysilanes represented by the general formulas (1) and (2). It has been found that the inclusion reduces the friction coefficient between the surface of the antifouling layer and the finger or cloth used for wiping, thereby improving the slipperiness. The member of the present invention reduces the surface free energy of the antifouling layer by increasing the contact angle between water and oil and fat, and high sliding properties can be obtained by reducing the sliding angle between water and oil and fat. In addition, high slipperiness makes it difficult to get dirt on the surface of the antifouling layer (less fingerprint adhesion) and makes it easy to wipe off the attached dirt (good fingerprint wiping performance). Can do.
As described above, the member of the present invention has an extremely excellent antifouling property that could not be obtained with the conventional antifouling member, because the interval between adjacent perfluoropolyether structural parts of the above-mentioned polycondensation product is wide. It is considered that this is because the perfluoropolyether structure site is easy to move and has flexibility.
In particular, in order to obtain the antifouling property of the surface used by sliding with a finger such as a touch panel, the improvement of the slip property is important.
In the present invention, “slipperiness” is an index representing the smoothness of the surface of the antifouling layer of the member. Specifically, the slip property can be evaluated by the method described in Examples.

[Manufacturing method of member]
Next, the manufacturing method of the member mentioned above is demonstrated.
In the method for producing a member of the present invention, an alkoxysilane having a perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the general formulas (1) and (2) are mixed with an organic solvent and water. (1) for preparing a composition containing a condensation polymer obtained by hydrolysis and condensation polymerization in a mixed solvent of acid and acid, and applying the composition to the substrate to form an antifouling layer Step (2).
Hereafter, the manufacturing method of the member of this invention is demonstrated in detail.

(Process (1))
In this step, for example, an alkoxysilane having a perfluoropolyether structure and an alkoxysilane represented by the general formulas (1) and (2) are selected from a mixed solvent of an organic solvent, water and an acid. At least one selected from the group consisting of the alkoxysilane having the perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the general formulas (1) and (2). By decomposing and then condensation polymerization, a condensation polymerization product is obtained.
As the alkoxysilane having the perfluoropolyether structure, the alkoxysilane represented by the general formulas (1) and (2), the organic solvent, water, and the acid, those described in the section of the above member may be used. The blending amounts of the organic solvent, water, and acid are appropriately adjusted within the ranges described in the above-mentioned members.
The weight average molecular weight of the alkoxysilane having the perfluoropolyether structure can be determined by GPC measurement.

  The weight ratio between the alkoxysilane having the perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the general formulas (1) and (2) is preferably 1: 0.1 to 0.1. It is 10.0, More preferably, it is 1: 0.15-8.0, More preferably, it is 1: 0.2-6.0. By setting it within the above range, the antifouling property can be improved.

The hydrolysis and polycondensation reactions are preferably performed under a certain atmosphere in which these reactions occur appropriately. Specifically, it is preferably performed for about 0.1 to 200 hours in the range of −25 to 120 ° C., more preferably for about 0.5 to 150 hours at −10 to 100 ° C., and 0 to 70 ° C. And more preferably for about 1 to 120 hours.
In addition to the above components, other components described in the above section can be added as necessary.

(Process (2))
An antifouling layer is formed by applying the composition prepared in the step (1) onto a substrate, drying and curing the composition.
The method for applying the composition may be any method that can be applied uniformly to a desired thickness, and may be appropriately selected from conventionally known methods. For example, gravure coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, curtain coating method, die coating method, casting method, bar coating method, extrusion coating method, etc. Is mentioned.

  The setting conditions for the drying treatment of the film formed by applying the above composition vary depending on the raw material, the solvent, the temperature and humidity of the atmosphere, but are controlled in a certain atmosphere suitable for obtaining the effects of the present invention. It is preferable to do in the situation. For example, it is usually performed at room temperature (25 ° C.) to 300 ° C. for about 0.1 to 48 hours, more preferably at 25 to 250 ° C. for about 0.2 to 24 hours. These treatments may be completed under one kind of atmosphere, or may be carried out stepwise under two or more kinds of atmospheres.

  The member of the present invention is excellent in antifouling property, so that when touched by hand, dirt such as fingerprints, sebum, sweat, etc. is likely to adhere to the surface. Image display devices such as paper, VFD, EPD, portable electronic devices such as touch panels, mobile phones, music players, optical recording media such as CDs, DVDs, Blu-ray discs, window glass for automobiles, trains, aircraft, etc., building materials for outer walls It is suitably used as a surface material for interior walls such as wallpaper, home appliances, and in-vehicle panels.

[Touch panel]
The touch panel of this invention is provided with the said member.
Examples of the touch panel include a capacitive touch panel, a resistive touch panel, an optical touch panel, an ultrasonic touch panel, and an electromagnetic induction touch panel. The touch panel may be on-cell type or in-cell type.
The touch panel of the present invention can be used, for example, in various image display devices including the member of the present invention as a surface material. In addition, the said member can be used suitably as an antifouling film used for the image display part surface of various image display apparatuses.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.
Evaluation of the members of Examples and Comparative Examples was performed as follows.

(1) Measurement of contact angle The contact angle of pure water and n-hexadecane was measured using a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd. 1.5 μL of pure water is dropped on the surface of the antifouling layer of the member, and after 1 second of landing, the contact angle from the angle of the straight line connecting the left and right end points and the apex of the dropped droplet to the solid surface according to the θ / 2 method Was calculated. The average value measured five times was taken as the value of the contact angle.
(2) Surface free energy From the measurement result of the contact angle, the surface free energy was evaluated according to the following criteria. The larger the contact angle, the lower the surface free energy and the better.
◎: Pure water 110 ° or more and n-hexadecane 60 ° or more ○: Pure water less than 110 ° 95 ° or more and n-hexadecane less than 60 ° 50 ° or more ×: Pure water less than 95 ° or n-hexadecane less than 50 ° (3) Measurement of sliding angle Using a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd., sliding angles of pure water and n-hexadecane were measured. The member is placed horizontally, 10 μL of pure water and 3 μL of n-hexadecane are dropped onto the surface of the antifouling layer of the member, the member is gradually inclined, and the inclination angle (sliding angle) at which the liquid droplet starts to slide. Was measured. The average value measured five times was taken as the sliding angle value.
(4) Sliding property The sliding property was evaluated according to the following criteria from the measurement result of the sliding angle. The smaller the sliding angle, the better the sliding property.
◎: Pure water less than 15 ° and n-hexadecane less than 10 ° ○: Pure water 15 ° or more and 30 ° or less, or n-hexadecane 10 ° or more and 15 ° or less ×: Pure water more than 30 ° or n-hexadecane more than 15 ° (5) Evaluation of slipperiness Ten test subjects made fingers contact the antifouling layer surface of each member produced in Examples 1 to 15 and Comparative Examples 1 to 6, and the fingers were parallel to the antifouling layer surface. Moved back and forth in the horizontal direction (slide operation with a smartphone). Tactile sensation due to friction between the finger and the antifouling layer surface at that time was determined according to the following evaluation criteria, and an average value of 10 subjects was obtained. This average value was determined according to the following criteria.
<Evaluation criteria>
5 points: always smooth 3 points: smooth 0 point: bad <Criteria>
○: 4.4 points or more Δ: 2.1 points or more and less than 4.4 points ×: less than 2.1 points (6) Fingerprint adhesion Artificial fingerprint liquid (Isehisa Co., Ltd.) on a silicone resin plate (10 mmφ × 30 mm cylindrical shape) ) Manufactured and conforming to JIS C 9606 appendix 4) was pressed against the surface of the antifouling layer of the member to attach a fingerprint. The state of fingerprint attachment was visually observed and evaluated according to the following criteria.
◎: The fingerprint is strongly played and the amount of adhesion is very small. ○: The fingerprint is played and the amount of adhesion is small. △: The fingerprint is flipped but adheres. ×: The fingerprint adheres widely (7) Fingerprint wiping property A silicone resin plate (10 mmφ × 30 mm cylindrical shape) with an artificial fingerprint liquid (Isehisa Co., Ltd., compliant with JIS C9606 appendix 4) attached is pressed against the surface of the antifouling layer of the member to attach the fingerprint. It was. The attached fingerprint was wiped with Ben Cotton manufactured by Asahi Kasei Co., Ltd., and the remaining fingerprint was visually observed and evaluated according to the following criteria.
◎: The fingerprint trace is completely invisible after wiping up to 3 times. ○: The fingerprint trace is completely invisible after wiping 4-7 times. △: With 8 to 10 wipes. ： Fingerprint adhesion traces are not completely visible ×: Fingerprint wipe traces are clearly visible after 10 wipes

Example 1
(Preparation of composition)
Fluorine-based organic solvent (made by 3M, trade name: Novec 7300) 28.1 g, amphiphilic solvent (made by Kanto Chemical Co., Inc., trade name: 2-propanol), and perfluoropolyether structure 0.15 g of alkoxysilane solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) and tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: orthosilicic acid) Tetramethyl) In a mixed solution in which 0.076 g was mixed, 5.9 mg of water and 31.1 mg of 1M hydrochloric acid were added, and the mixture was stirred at 25 ° C. for 3 hours. The alkoxysilane having a perfluoropolyether structure and tetra Composition 1 containing a polycondensation product with alkoxysilane was obtained.
(Manufacture of parts)
The composition 1 was applied on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 700 μm) using a spin coater at a rotational speed of 3000 rpm, and the coating film was applied. Formed. The coating film was dried at room temperature (25 ° C.) for 12 hours, and the solvent was removed and cured to obtain a member having a film thickness of 10 nm (estimated value).

Example 2
(Preparation of base material)
Using a bar coater on a polyester film (Toyobo Co., Ltd., trade name: Cosmo Shine A4100, thickness 100 μm), an organic-inorganic composite material (Nippon Soda Co., Ltd., trade name “NH-1000G”) A 53 mass% methyl isobutyl ketone (MIBK) solution was applied to form a coating film. The coating film was dried at 70 ° C. for 60 seconds to remove the solvent.
Subsequently, the coating film was irradiated with a high-pressure mercury lamp at an irradiation amount of 100 mJ / cm ² to cure the coating film, thereby obtaining a base material with a surface having a thickness of 10 μm after curing.
(Preparation of composition)
18.7 g of fluorine-based organic solvent (product name: Novec 7300) manufactured by 3M, 3.2 g of amphiphilic solvent (product name: 2-propanol manufactured by Kanto Chemical Co., Ltd.), and a perfluoropolyether structure 0.1 g of alkoxysilane solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) and tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: orthosilicic acid) Tetramethyl) In a mixed solution in which 0.051 g is mixed, 4.0 mg of water and 20.7 mg of 1M hydrochloric acid are added and stirred at room temperature (25 ° C.) for 3 hours to obtain an alkoxy having a perfluoropolyether structure. A composition 2 containing a condensation polymerization product of silane and tetraalkoxysilane was obtained.
(Manufacture of parts)
The composition 2 was applied onto the substrate using a spin coater at a rotation speed of 3000 rotations / min to form a coating film. The coating film was dried at 25 ° C. for 12 hours, and the solvent was removed and cured to obtain a member having a film thickness of 10 nm (estimated value).

Example 3
0.165 g of alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-178”, solid content 20%), tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., product) A member was obtained in the same manner as in Example 1 except that 0.076 g of tetramethyl orthosilicate) was used.

Example 4
0.11 g of an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-178”, solid content 20%), tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., product) A member was obtained in the same manner as in Example 2 except that 0.051 g of tetramethyl orthosilicate) was used.

Example 5
1.0 g of an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%), tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) A product was obtained in the same manner as in Example 1 except that 50.7 mg of (trade name: tetramethyl orthosilicate) was used.

Example 6
(Preparation of composition)
Fluorine-based organic solvent (made by 3M, trade name: Novec 7300) 28.1 g, amphiphilic solvent (made by Kanto Chemical Co., Inc., trade name: 2-propanol), and perfluoropolyether structure Alkoxysilane solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) 0.15 g and trialkoxysilane (trimethoxy (methyl) silane) (manufactured by Tokyo Chemical Industry Co., Ltd.) In this case, 11.9 mg of water and 60.6 mg of 1M hydrochloric acid were added to a mixed solution in which 0.14 g of solid content was mixed, and the mixture was stirred at 25 ° C. for 3 hours to obtain an alkoxy having a perfluoropolyether structure. A composition 6 containing a condensation polymer of silane and trialkoxysilane was obtained.
(Manufacture of parts)
The composition 6 was applied on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 700 μm) using a spin coater at a rotation speed of 3000 rpm, and the coating film was applied. Formed. The coating film was dried at room temperature (25 ° C.) for 12 hours, and the solvent was removed and cured to obtain a member having a film thickness of 10 nm (estimated value).

Example 7
A member was obtained in the same manner as in Example 6 except that 0.15 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., solid content: 100%) was used instead of trimethoxy (methyl) silane as trialkoxysilane. It was.

Example 8
A member was obtained in the same manner as in Example 6 except that 0.20 g of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., solid content: 100%) was used instead of trimethoxy (methyl) silane as trialkoxysilane. It was.

Example 9
As a trialkoxysilane, 0.25 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503, solid content 100%) was used instead of trimethoxy (methyl) silane. In the same manner as in Example 6, a member was obtained.

Example 10
As a trialkoxysilane, instead of trimethoxy (methyl) silane, 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-5103, solid content 100%) was used except 0.23 g. In the same manner as in Example 6, a member was obtained.

Example 11
The same procedure as in Example 6 was conducted except that 0.17 g of alkoxysilane (bis (triethoxysilyl) methane) (manufactured by Gelest, solid content: 100%) represented by the following formula (8) was used instead of trialkoxysilane. The member was obtained.

Example 12
0.076 g of tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: tetramethyl orthosilicate), trialkoxysilane (trimethoxy (methyl) silane) (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100%) Was used in the same manner as in Example 6 except that 0.068 g was used together.

Example 13
0.15 g of an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) and tetraalkoxysilane (Tokyo Chemical Industry Co., Ltd.) Manufactured and trade name: 0.038 g of tetramethyl orthosilicate) and a mixed solution of 0.11 g of trialkoxysilane (vinyltrimethoxysilane) (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100%) A member was obtained in the same manner as in Example 6 except that 60.6 mg of 1M hydrochloric acid was added.

Example 14
0.15 g of an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) and tetraalkoxysilane (Tokyo Chemical Industry Co., Ltd.) Manufactured and trade name: 0.076 g of tetramethyl orthosilicate) and a mixed solution of trialkoxysilane (vinyltrimethoxysilane) (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100%) 0.074 g. A member was obtained in the same manner as in Example 13 except that 2.94 mg of water and 60.6 mg of 1M hydrochloric acid were added.

Example 15
0.11 g of tetraalkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: tetramethyl orthosilicate), trialkoxysilane (vinyltrimethoxysilane) (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100%) A member was obtained in the same manner as in Example 14 except for changing to 0.037 g and water 7.44 mg.

Comparative Example 1
A perfluoropolyether structure obtained by removing a solvent in an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-71-195”, solid content 20%) An alkoxysilane having a thickness of 10 nm (estimated value) is deposited on the entire surface of the glass substrate by vapor deposition on a glass substrate by an electron beam vapor deposition method (degree of vacuum = 1.0 × 10 ⁻³ Pa, current value = 9 mA). Thus, a member was obtained.

Comparative Example 2
A member was obtained in the same manner as in Comparative Example 1 except that an alkoxysilane solution having a perfluoropolyether structure (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KY-178”, solid content 20%) was used.

Comparative Example 3
4.6 g of ethanol, 0.22 g of alkylsilane (manufactured by Gelest, trade name: decyltriethoxysilane), and 1.6 g of metal alkoxide (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: tetramethyl orthosilicate) To the mixed solvent (decyltriethoxysilane / tetramethyl orthosilicate = 1/14), 0.78 g of 0.01M hydrochloric acid was added and stirred at room temperature (25 ° C.) for 24 hours. The obtained solution was spin-coated on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 700 μm), and allowed to stand at room temperature (25 ° C.) for one day. An estimated value member was obtained.

Comparative Example 4
2.4 g of ethanol, 0.37 g of fluorinated alkylsilane (manufactured by Gelest, trade name: triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane), and metal alkoxide (Tokyo Chemical Industry Co., Ltd.) Product, trade name: tetramethyl orthosilicate) in a mixed solvent (triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane / tetramethyl orthosilicate = 1/7) ) Was added 0.4M g of 0.01M hydrochloric acid and stirred at room temperature (25 ° C.) for 24 hours. The obtained solution was spin-coated on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 700 μm), and allowed to stand at room temperature (25 ° C.) for one day. An estimated value member was obtained.

Comparative Example 5
28.1 g of fluorine-based organic solvent (trade name: Novec 7300, manufactured by 3M) and an alkoxysilane solution having a perfluoropolyether structure (trade name “X-71-195”, manufactured by Shin-Etsu Chemical Co., Ltd.), solid content 20%) The mixed solution mixed with 0.15 g was rotated on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 700 μm) using a spin coater at a rotation speed of 3000 rpm. And coated to form a coating film. The coating film was dried at 25 ° C. for 12 hours, and the solvent was removed and cured to obtain a member having a film thickness of 10 nm (estimated value).

Comparative Example 6
18.7 g of fluorine-based organic solvent (manufactured by 3M, trade name: Novec 7300) and alkoxysilane solution having a perfluoropolyether structure (trade name “X-71-195”, manufactured by Shin-Etsu Chemical Co., Ltd.), solid content 20%) A mixed solution mixed with 0.05 g was applied on the base material prepared in Example 2 using a spin coater at a rotation speed of 3000 rotations / min to form a coating film. The coating film was dried at 25 ° C. for 12 hours, and the solvent was removed and cured to obtain a member having a film thickness of 10 nm (estimated value).

(Summary of results)
As shown in Table 1, in Examples 1 to 15 in which an alkoxysilane having a perfluoropolyether structure and an alkoxysilane having a specific structure were used in combination, the contact angle of pure water was 112 to 117 °, n− The contact angle of hexadecane was 65 to 68 °, and all of them were excellent in low surface free energy. Moreover, the sliding angle of pure water was 3 to 14 °, and the sliding angle of n-hexadecane was 2 to 6 °, both of which were excellent in sliding property and the evaluation of sliding property was also high. From these results, it can be seen that the members of Examples 1 to 15 are difficult to attach fingerprints and have excellent fingerprint wiping properties, and these effects are the same as that of alkoxysilane having a perfluoropolyether structure. It is considered that the interval between adjacent perfluoropolyether structure sites in the polycondensation product with an alkoxysilane having a specific structure is wide and sparse, and the perfluoropolyether structure sites are easy to move and have flexibility. .
On the other hand, in Comparative Examples 1 and 2 in which alkoxysilane having a perfluoropolyether structure was deposited by the deposition method, the surface free energy is low and the sliding property is good, but the evaluation of the sliding property is inferior to the examples. In both cases, the evaluation of fingerprint adhesion and fingerprint wiping property was inferior to those of the Examples. Further, in Comparative Example 3 using alkylsilane, although it has excellent sliding property, the surface free energy is high and the evaluation of slipping property is poor. As a result, fingerprints are widely attached, and fingerprints are wiped off even after 10 times of wiping. The trace was clearly visible. In Comparative Example 4 using fluorinated alkylsilane, although the surface free energy is low and the sliding property is excellent, the evaluation of the sliding property is poor. As a result, the fingerprint adheres widely and the fingerprint is wiped off even after 10 times of wiping. The trace was clearly visible. In Comparative Examples 5 and 6, since alkoxysilane having a specific structure was not used, both the fingerprint adhesion and the fingerprint wiping evaluation were inferior to those in Examples.

  Since the member of this invention is excellent in antifouling property, it can be used suitably especially for the portable electronic device which has a touchscreen display.

Claims (8)

A member formed by forming an antifouling layer on a substrate,
The antifouling layer contains a polycondensation product of an alkoxysilane having a perfluoropolyether structure and at least one selected from alkoxysilanes represented by the following general formulas (1) and (2): A member.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)   The member according to claim 1, wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.   The member according to claim 1 or 2, wherein the alkoxysilane represented by the general formula (1) is a tetraalkoxysilane.   The member according to claim 1, wherein the tetraalkoxysilane is at least one selected from tetramethoxysilane and tetraethoxysilane.   5. The member according to claim 1, wherein a contact angle of pure water on the surface of the antifouling layer is 95 ° or more and a sliding angle is 30 ° or less. A method for producing a member formed by forming an antifouling layer on a substrate,
Hydrolysis of an alkoxysilane having a perfluoropolyether structure and at least one selected from the alkoxysilanes represented by the following general formulas (1) and (2) in a mixed solvent of an organic solvent, water and an acid. A step (1) of preparing a composition containing a condensation polymer obtained by decomposition and condensation polymerization;
And (2) forming an antifouling layer by applying the composition to the substrate.

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)   The touch panel provided with the member as described in any one of Claims 1-5. A composition comprising a polycondensation product of an alkoxysilane having a perfluoropolyether structure and at least one selected from alkoxysilanes represented by the following general formulas (1) and (2).

(In the formula, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms, and each R ² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a ring-forming atom. If a C 3-10 cycloalkyl group, or .R ¹ and ^{R 2} is an aryl group ring atoms 6 to 20 are a plurality, the plurality of ^{R 1} and ^{R 2} may each be the same or different X is an integer from 2 to 4.)

(In the formula, each R ³ is independently an alkyl group having 1 to 6 carbon atoms, and Y is a divalent organic group. The plurality of R ³ may be the same or different.)