WO2019230571A1 - Vapor deposition material containing silicon oxide, and method for producing base material provided with silicon oxide layer using same - Google Patents

Abstract

Provided are: a vapor deposition material from which a silicon oxide layer capable of imparting a sufficient durability to a surface layer can be formed; and a method for producing a base material provided with a silicon oxide layer which is capable of imparting a sufficient durability to a surface layer, said surface layer being formed on the silicon oxide layer serving as an underlayer. The vapor deposition material contains silicon oxide as a major component together with 0.03-800 ppm by mass, relative to the silicon oxide, of a platinum-group metal. The method for producing a base material provided with a silicon oxide layer comprises forming a silicon oxide layer on a base material by vacuum deposition using a vapor deposition material which contains silicon oxide as a major component together with 0.03-800 ppm by mass, relative to the silicon oxide, of a platinum-group metal.

Description

Silicon oxide-containing vapor deposition material and method for producing a substrate with a silicon oxide layer using the same

The present invention relates to a silicon oxide-containing vapor deposition material, a method for producing a substrate with a silicon oxide layer using the same, and a method for producing a substrate with a surface layer.

Conventionally, a technique for providing a surface layer having a target performance on a base material in order to modify the surface of various base materials is known. In order to maintain the target performance, the surface layer is required to have durability such as wear resistance, and a technique for imparting durability to the surface layer is also known.

For example, Patent Document 1 uses a perfluoro (poly) ether group-containing silane compound having a specific structure as a surface treatment layer having water repellency, oil repellency, antifouling properties and excellent friction durability. The technology to form is described. Patent Document 2 discloses a surface treatment layer having an outermost layer and a lower layer, wherein the outermost layer is formed of a surface treatment agent containing an isocyanate silane compound as an essential component, and is a lower layer provided between the outermost layer and the substrate. Describes a technique for improving the long-term durability of water repellency and antifouling properties by forming a surface treatment agent containing a silane compound such as Si (NCO) ₄ .

Japanese Unexamined Patent Publication No. 2014-218639 Japanese Unexamined Patent Publication No. 10-180937

The inventors of the present invention obtained an article obtained using a known technique has good surface layer film formability and sufficient performance in the initial state. As a result, it was found that the performance disappeared.

The present invention has been made from the above viewpoint, and relates to an underlayer provided between the substrate and the surface layer, particularly a silicon oxide layer, in order to improve the durability of the surface layer provided on the substrate. An object of the present invention is to provide a vapor deposition material capable of forming an underlayer capable of imparting sufficient durability to the surface layer, particularly a silicon oxide layer. The present invention relates to a method for producing a substrate with a silicon oxide layer capable of imparting sufficient durability to a surface layer formed on a silicon oxide layer as an underlayer, and a surface layer with a surface layer having sufficient durability. It is an object to provide a method for manufacturing a base material.

The present invention can achieve the above-described problems and has the following aspects.
[1] A vapor deposition material containing silicon oxide as a main component and containing 0.03 to 800 ppm by mass of a platinum group metal in a ratio to the silicon oxide.
[2] The vapor deposition material according to [1], wherein a ratio of the silicon oxide to the total amount of the vapor deposition material is 65 to 99% by mass.
[3] The vapor deposition material according to [1] or [2], wherein a ratio of the platinum group metal to the total amount of the vapor deposition material is 0.02 to 800 ppm by mass.
[4] The vapor deposition material according to any one of [1] to [3], further comprising at least one of sodium oxide and calcium oxide.
[5] The vapor deposition material according to [4], wherein the total amount of the sodium oxide and calcium oxide relative to the silicon oxide is 0.1 to 13% by mass.
[6] The component obtained by removing the platinum group metal from the vapor deposition material is expressed by mass% in terms of oxide, SiO ₂ is 65 to 95%, Na ₂ O is 0 to 20%, CaO is 0 to 32%, The vapor deposition material of any one of [1] to [5], containing 0 to 15% Al ₂ O ₃ and 0 to 4% MgO.
[7] The component obtained by removing the platinum group metal from the vapor deposition material is expressed in terms of mass% in terms of oxide, SiO ₂ is 65 to 75%, Na ₂ O is 1 to 20%, CaO is 5 to 32%, The vapor deposition material according to any one of [1] to [6], which is soda-lime glass containing 0 to 2% Al ₂ O ₃ and 0 to 4% MgO.
[8] The vapor deposition material according to any one of [1] to [7], wherein the platinum group metal is at least one selected from platinum and rhodium.
[9] A silicon oxide layer is formed on a substrate by vacuum deposition using a vapor deposition material containing silicon oxide as a main component and containing 0.03 to 800 ppm by mass of a platinum group metal in a ratio to the silicon oxide. The manufacturing method of the base material with a silicon oxide layer including this.
[10] A surface comprising forming a surface layer using an organic compound having a group capable of reacting with silicon oxide on the silicon oxide layer of the substrate with a silicon oxide layer obtained by the production method according to claim 9 The manufacturing method of a base material with a layer.
[11] The method for producing a substrate with a surface layer according to [10], wherein the organic compound contains a fluorine-containing compound.
[12] The method for producing a substrate with a surface layer according to [11], wherein the fluorine-containing compound has a poly (oxyperfluoroalkylene) chain.
[13] The method for producing a substrate with a surface layer according to any one of [9] to [12], wherein the fluorine-containing compound is a fluorine-containing ether compound represented by the following formula 1.
[AO—Z ¹ — (R ^f O) _m —] _j Z ² [—SiR _n L _3-n ] _q Formula 1
However, A is a perfluoroalkyl group or a _{-Q [-SiR n L 3-n} ] k. Q is a (k + 1) -valent linking group, and k is an integer of 1 to 10. R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer of 0-2.
Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms or a poly (oxyfluoroalkylene) group in which one or more hydrogen atoms are substituted with fluorine atoms. R ^f is a perfluoroalkylene group. m is an integer of 2 to 200. Z ² is a (j + q) -valent linking group, j is an integer of 1 or more, and q is an integer of 1 or more.
[14] Production of a substrate with a surface layer according to any one of [9] to [13], wherein a surface layer is formed by a vacuum deposition method using an organic compound having a group capable of reacting with silicon oxide on the silicon oxide layer Method.
[15] The method for producing a substrate with a surface layer according to any one of [9] to [14], wherein the thickness of the surface layer is 0.1 to 100 nm.

According to the present invention, in order to improve the durability of the surface layer provided on the base material, the underlying layer provided between the base material and the surface layer, in particular, oxidation that can impart sufficient durability to the surface layer. An evaporation material capable of forming a silicon layer can be provided. In addition, the present invention provides a method for producing a substrate with a silicon oxide layer capable of imparting sufficient durability to a surface layer formed on a silicon oxide layer as an underlayer, and a surface on which the surface layer has sufficient durability Provision of the manufacturing method of a base material with a layer can be provided.

Definitions of terms and how to describe them in this specification are as follows.
The compound represented by Formula 1 is referred to as Compound 1. The same applies to compounds represented by other formulas. A group represented by Formula 1 is referred to as Group 1. Groups represented by other formulas are also described in the same manner.
When "an alkylene group may have an A group" is mentioned, the alkylene group may have an A group between carbon atoms in the alkylene group-carbon atom, or an alkylene group-A group- As such, the terminal may have an A group.

“˜” representing a numerical range is a range including the lower limit and the upper limit. In addition, when the lower limit value and the upper limit value of the numerical range are in the same unit, the description of the unit of the lower limit value may be omitted for the sake of brevity.
"Mean particle diameter" _is the _{D 50.} D ₅₀ represents the particle size when the cumulative amount occupies 50% on a volume basis in the cumulative particle size curve of the particle size distribution measured using a laser diffraction / scattering type particle size distribution measuring apparatus.

The “reactive silyl group” means a group (hydrolyzable silyl group) and a silanol group that can form a silanol group (Si—OH) by a hydrolysis reaction. For example, —SiR _n L _3-n in Formula 1.
The “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms. In the chemical formula of the oxyperfluoroalkylene group, the oxygen atom is described on the right side of the perfluoroalkylene group.

The “divalent organopolysiloxane residue” is a group represented by the following formula. R ^a in the following formula is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. G1 is an integer of 1 or more, preferably 1 to 9, and particularly preferably 1 to 4.

The “silphenylene skeleton group” is a group represented by —Si (R ^b ) ₂ PhSi (R ^b ) ₂ — (where Ph is a phenylene group and R ^b is a monovalent organic group). It is. R ^b is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
The “dialkylsilylene group” is a group represented by —Si (R ^c ) ₂ — (wherein R ^c is an alkyl group (preferably having 1 to 10 carbon atoms)).
The “number average molecular weight” of the fluorinated ether compound is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the end groups by ¹ H-NMR and ¹⁹ F-NMR using NMR analysis. Is done.

[Vapor deposition material]
The vapor deposition material of the present invention is typically used for vacuum vapor deposition. Vacuum deposition is one of the film formation techniques, and is a technique for forming a vapor deposition layer by heating and vaporizing a vapor deposition material in a high vacuum and attaching the vapor deposition material that has become a gas to the substrate surface. . The vapor deposition material of the present invention contains a silicon oxide as a main component, so that the vapor deposition layer obtained is a silicon oxide layer containing silicon oxide as a main component.

In this specification, that the vapor deposition material contains silicon oxide as a main component means that the silicon oxide contains 65% by mass or more of silicon oxide with respect to the total amount of the vapor deposition material. This also applies to the silicon oxide layer, and the silicon oxide layer in the present invention is a layer containing 65% by mass or more of silicon oxide.

When vacuum deposition is performed using the vapor deposition material of the present invention, the platinum group metal contained in the vapor deposition material precipitates as fine particles on the substrate surface at an appropriate interval, and the platinum group metal particles are used as seeds. It is considered that a dense silicon oxide layer is formed on the material surface. Thus, the silicon oxide layer obtained by using the vapor deposition material of the present invention has high substrate adhesion and excellent wear resistance. Furthermore, if the surface layer is formed on the silicon oxide layer using an organic compound having a group capable of reacting with silicon oxide, a substrate with a surface layer having excellent surface layer durability can be obtained.
The vapor deposition material of the present invention may contain optional components in addition to the predetermined amounts of silicon oxide and platinum group metal. Hereinafter, each component contained in the vapor deposition material of the present invention will be described.

Examples of the platinum group metal contained in the vapor deposition material of the present invention include platinum, rhodium, ruthenium, palladium, osmium, and iridium. These may be used individually by 1 type and may be used in combination of 2 or more type. The platinum group metal is preferably at least one selected from platinum and rhodium.

The platinum group metal content in the vapor deposition material is 0.03 to 800 ppm by mass in terms of the silicon oxide contained in the vapor deposition material. When the content is within the above range, sufficient substrate adhesion can be obtained in the obtained silicon oxide layer. The content is preferably 0.05 mass ppm or more, more preferably 1 mass ppm or more, in terms of the ratio to the silicon oxide. The content is preferably 600 mass ppm or less, more preferably 200 mass ppm or less in terms of the ratio to the silicon oxide.

The content of the platinum group metal with respect to the total amount of the vapor deposition material is preferably 0.02 to 800 ppm by mass, more preferably 0.04 to 600 ppm by mass, and 0.7 to 200 ppm by mass from the same viewpoint as described above. Further preferred.

The lower limit of the ratio of silicon oxide contained in the vapor deposition material is 65% by mass with respect to the total amount of the vapor deposition material, and the upper limit is a value obtained by excluding the platinum group metal content from the total amount of the vapor deposition material. When the ratio of silicon oxide is within the above range, the resulting silicon oxide layer has high substrate adhesion.

In the vapor deposition material, when the content of silicon oxide is less than the above upper limit value, the vapor deposition material contains an optional component other than silicon oxide and a platinum group metal. In that case, content of silicon oxide is 65 mass% or more from a viewpoint of base-material adhesiveness, 70 mass% or more is preferable and 75 mass% or more is further more preferable. The content of silicon oxide is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less, from the viewpoint of ease of manufacture of the vapor deposition material.

As an optional component that may be contained in the vapor deposition material, a metal oxide is preferable. Examples of the metal oxide include alkali metals such as Li, Na, and K, alkaline earth metals such as Ca, Sr, Mg, and Ba, Mo, W, B, Fe, Sc, Y, La, Ce, Gd, Ti, Zr, V, Nb, Ta, Cr, Mn, Co, Ni, Cu, Zn, Al, Ga, Ge, Sn, Sb, Bi, P, etc. are mentioned.

The vapor deposition material of the present invention is usually constituted by using a component obtained by removing the platinum group metal from the vapor deposition material as a base material and containing the platinum group metal in a predetermined ratio in the base material. The base material contains an amount of silicon oxide as a main component when used as a vapor deposition material. The base material may be composed only of silicon oxide, or may be composed of silicon oxide and the optional components described above. Furthermore, when a platinum group metal is introduced as a salt into the vapor deposition material, the base material contains a counter anion of the platinum group metal.

The base material in the vapor deposition material of the present invention is not particularly limited as long as it is silicon oxide or a composition containing silicon oxide in the above amount. Specific examples include silicon oxide, hydrolyzed condensate of silicic acid, hydrolyzed condensate of alkoxysilane, silicate glass such as soda lime glass, etc., and hydrolyzed condensate of silicic acid or soda lime glass is preferred. When the base material is a composition, the composition is appropriately adjusted according to the type of the base material. When the base material is a composition, the base material preferably contains at least one of sodium oxide and calcium oxide in addition to silicon oxide.

When the base material is silicon oxide, a method for producing a vapor deposition material is to mix silicon oxide powder and platinum group metal powder so that the ratio of silicon oxide and platinum group metal is in the above range in the obtained vapor deposition material. Examples thereof include a method of adding silicon to a platinum group metal-containing aqueous solution and removing water after stirring. When the silicon oxide powder and the platinum group metal powder are mixed, the average particle diameter of the powder is preferably 0.1 to 100 μm, and more preferably 1 to 10 μm. In this case, after mixing the powder, it is preferable to pelletize and use as described later. Examples of the platinum group metal-containing aqueous solution include aqueous solutions of platinum group metal salts such as hydroxides, chlorides, and carbonates. Note that when an aqueous solution of a platinum group metal salt is used, the platinum group metal is contained in the vapor deposition material as a salt.

When the base material is a hydrolyzed condensate of silicic acid, a method of drying a solution containing at least one selected from the group consisting of silicic acid and a partially hydrolyzed condensate thereof, a platinum group metal, and water can be mentioned. The platinum group metal is usually contained in the solution as a salt. Examples of the platinum group metal salt include the same salts as described above. As the silicic acid, desalted sodium silicate or potassium silicate can be used. In addition, you may make the solution contain an organic solvent as needed.

Examples of sodium silicate include Na ₂ O · nSiO ₂ defined in JIS K1408-1966. Specifically, sodium metasilicate (Na ₂ SiO ₃ ), sodium orthosilicate (Na ₄ SiO ₄ ), sodium disilicate (Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ Si ₄ O ₉ ) Etc. Examples of potassium silicate include K ₂ O · nSiO ₂ , and specifically, potassium metasilicate (K ₂ SiO ₃ ), potassium orthosilicate (K ₄ SiO ₄ ), potassium disilicate (K ₂ Si _2). O ₅ ), potassium tetrasilicate (K ₂ Si ₄ O ₉ ) and the like.

Examples of the desalting treatment include a method in which a sodium silicate aqueous solution or a potassium silicate aqueous solution and a cation exchange resin are mixed and stirred, and then the cation exchange resin is removed. The temperature at which the solution containing silicic acid and / or the partial hydrolysis-condensation product, the platinum group metal, and water is dried is preferably 5 to 50 ° C., more preferably 15 to 30 ° C.

In addition, in the above, using sodium silicate or potassium silicate as it is, or using sodium silicate or potassium silicate in which the amount of sodium or potassium is appropriately adjusted by appropriately selecting conditions in the desalting treatment, The base material may include sodium oxide or potassium oxide. In that case, the total ratio of sodium oxide and potassium oxide to silicon oxide is preferably 0.1 to 13% by mass, and more preferably 1.0 to 10% by mass.

When the base material is a composition containing silicon oxide in the above amount, the composition is appropriately adjusted according to the type of base material. When the base material is soda lime glass, the base material usually contains silicon oxide, sodium oxide and calcium oxide. In addition, content of the silicon oxide in soda-lime glass is the quantity used as a main component, when it is set as a vapor deposition material. In the case of soda lime glass, an appropriate amount of the above metal oxide can be appropriately contained as other components other than these three components. Among the above metal oxides, it is preferable to contain at least one selected from aluminum oxide and magnesium oxide from the viewpoint of adjusting dissolution characteristics.

Specifically, in a silicate glass used for a base material, SiO ₂ is 65 to 95%, Na ₂ O is 0 to 20%, CaO is 0 to 32%, and Al ₂ O is expressed in terms of mass% in terms of oxide. A composition containing ₃ to 0 to 15% and MgO to 0 to 4% is preferable. Among silicate glasses, particularly soda lime glass, SiO ₂ is 65 to 75%, Na ₂ O is 1 to 20%, CaO is 5 to 32%, Al ₂ O ₃ is 0 to 2%, and MgO is 0%. A composition containing ˜4% is preferred.
The content of each component in the soda lime glass is determined from the result of inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis of the obtained glass.

By containing 65 to 75% of SiO _{2 in} soda lime glass, the melting temperature is lowered and the productivity is improved. The content of SiO ₂ is more preferably 67 to 73%, further preferably 69 to 71%. When soda lime glass contains 1 to 20% of Na ₂ O, the melting temperature is lowered. The content of Na ₂ O is more preferably 1 to 10%, further preferably 2 to 5%. When the soda lime glass contains 5 to 32% of CaO, the melting temperature is lowered, and the amount of CaO mixed into the silicon oxide layer can be appropriately reduced. The content of CaO is more preferably 10 to 30%, further preferably 15 to 28%.

When the soda lime glass contains 0 to 2% of Al ₂ O ₃ , the melting temperature is lowered and the mixing into the silicon oxide layer is small. The content of Al ₂ O ₃ is more preferably from 0.1 to 1.5%, further preferably from 0.5 to 1%. When the soda lime glass contains 0 to 4% of MgO, the melting temperature is lowered and the amount of MgO mixed into the silicon oxide layer can be moderately reduced. The content of MgO is more preferably from 0.1 to 2%, further preferably from 0.5 to 1%.

The soda lime glass may further contain K ₂ O, Fe ₂ O ₃ , TiO _{2 and the} like as optional components for the purpose of adjusting the melting temperature and phase separation characteristics.
In the soda lime glass, the softening point is preferably 700 to 1700 ° C. from the viewpoint of workability as a deposition source.

The vapor deposition material of the present invention when the base material is soda lime glass can be produced, for example, by the method shown below.
First, a raw material mixture of soda lime glass is prepared. The raw material is not particularly limited as long as it is a raw material used for production of ordinary oxide-based glass, and oxides, hydroxides, carbonates, sulfates, nitrates, and the like can be used. Specifically, raw material components include silica sand, calcium carbonate, sodium carbonate, slaked lime, magnesium hydroxide, aluminum hydroxide, sodium metasilicate hydrate, magnesium sulfate, soda ash, talc, aluminum oxide, bow glass, carbonate Examples include potassium and petals. From these raw material components, each component is appropriately selected according to the composition to be obtained and used for preparation.

In the soda lime glass as a base material in the obtained vapor deposition material, the kind and ratio of the raw materials are appropriately adjusted so as to be in the above composition range to obtain a raw material mixture. When preparing the raw material mixture, the platinum group metal is added to the raw material mixture of the base material so that the ratio of the platinum group metal to the silicon oxide is in the above range in the obtained vapor deposition material, and the raw material composition of the vapor deposition material And

The platinum group metal to be added to the raw material mixture of the base material is, for example, a powder of the platinum group metal itself. As for the size of the powder, for example, the average particle diameter is preferably from 0.1 to 100 μm, more preferably from 1 to 10 μm, from the viewpoint of dispersibility and uniformity when the raw material composition is melted.

Next, the raw material composition of the vapor deposition material is heated by a known method such as a high temperature electric furnace to obtain a melt. The temperature for melting by heating (melting temperature) is preferably 700 to 1700 ° C, more preferably 700 to 1600 ° C. The time for heating and melting is preferably 1 to 36 hours, and more preferably 3 to 12 hours.
Thereafter, the melt is cooled and solidified to obtain a molten granule, whereby the vapor deposition material of the present invention is obtained. The cooling method is not particularly limited. The cooling rate can be, for example, about 0.5 to 5 ° C./min. In addition to the method of allowing the melt to flow out onto a cooling plate such as a carbon plate and cooling it at room temperature, a method of quenching by a roll-out machine, a press machine, dripping into a cooling liquid, or the like can be employed.

The vapor deposition material of the present invention may be in any form. For example, a block shape, a plate shape, a thin plate shape (flake shape), a bead shape, a powder shape, and the like may be used. Among these, since the powder is likely to be scattered during vacuum deposition, it is preferable to use it after processing into a pellet form. Although the manufacturing method of a pellet is not ask | required, the method of compacting powder into a pellet-shaped molded object is mentioned, for example. Moreover, it is good also as a granulated body by granulating powder. Furthermore, the pellet-shaped molded body and the granulated body may be fired to obtain a sintered body. The size of the pellet-shaped formed body, granulated body or sintered body is preferably, for example, 0.5 mm or more in diameter or major axis from the viewpoint of suppressing scattering during vacuum deposition. The upper limit is not particularly limited, but is preferably about 1 to 3 cm in diameter or major axis from the viewpoint of the size of the vapor deposition apparatus. The size of the vapor deposition material in the form of a block, plate, flake, bead, etc. can also be the same as in the case of a pellet-shaped molded body.

The substrate for forming the silicon oxide layer using the vapor deposition material of the present invention is not particularly limited. The vapor deposition material of the present invention is usually used for a substrate that requires surface modification (giving specific performance) by a surface layer further provided on a silicon oxide layer. Examples of the material for the substrate include metals, resins, glass (which may be chemically strengthened), sapphire, ceramic, stone, and composite materials thereof. The substrate may have a single layer structure or a laminated structure. The shape, size, etc. of the substrate are not particularly limited. A base material is suitably selected according to the use of the base material with a surface layer mentioned later. The silicon oxide layer using the vapor deposition material of the present invention can be used suitably for a transparent substrate because it can achieve high adhesion to the substrate without impairing the transparency of the substrate when applied to a transparent substrate. It is done.

From the viewpoint of further improving the adhesion between the substrate and the silicon oxide layer, the surface of the substrate may be subjected to an activation treatment, for example, a dry activation treatment or a wet activation treatment. Specific examples of the dry activation process include a process of irradiating the surface of the substrate with active energy rays (for example, ultraviolet rays, electron beams, X-rays), a corona discharge process, a plasma process (vacuum plasma process, atmospheric pressure plasma process) ), Flame treatment, and itro treatment. Specific examples of the wet activation treatment include a treatment in which the substrate surface is brought into contact with an acid or alkali solution. Among the above activation treatments, corona discharge treatment or plasma treatment is preferable because the adhesion between the substrate and the silicon oxide layer is further improved.

Moreover, you may use what has a further layer on the surface of the base-material main body which consists of the material mentioned above as a base material. This layer is preferably a layer having excellent adhesion to the base body from the viewpoint of excellent effects of the present invention, and specific examples include a diamond-like carbon layer.
A diamond-like carbon layer means a film having an amorphous structure in which both bonds of diamond bonds (bonds due to sp ³ hybrid orbitals between carbons) and graphite bonds (bonds due to sp ² hybrid orbitals between carbons) are mixed. . Diamond-like carbon may contain atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, silicon atoms, nitrogen atoms, aluminum atoms, boron atoms, phosphorus atoms).

[Method for producing substrate with silicon oxide layer]
The vapor deposition material used for the manufacturing method of the base material with a silicon oxide layer of this invention is the same as the vapor deposition material of this invention demonstrated above. The base material on which the silicon oxide layer is formed is as described above.

As a vacuum deposition method for forming a silicon oxide layer on a substrate using a deposition material, a normal method using a normal vacuum deposition apparatus can be applied without any particular limitation. Specifically, a base material is installed in an apparatus capable of reducing pressure, and a deposition material container filled with a deposition material is installed at a position facing the silicon oxide layer forming surface of the base material. The size and shape of the vapor deposition material container are not particularly limited. The material for the vapor deposition material container may be any material that does not react with the vapor deposition material under the following vacuum vapor deposition conditions and does not evaporate. Examples thereof include molybdenum, tungsten, and copper.

The evaporation material is usually heated by heating the container material for the evaporation material with an electron gun or resistance heating. The heating temperature of the container for the vapor deposition material is preferably 100 to 3000 ° C, more preferably 1000 to 2000 ° C, and further preferably 1200 to 1800 ° C. The temperature in the apparatus during vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure (absolute pressure) in the apparatus during vacuum deposition is preferably 1 × 10 ⁻¹ Pa or less, particularly preferably 1 × 10 ⁻² Pa or less. The distance between the silicon oxide layer forming surface of the substrate and the vapor deposition material is preferably 100 to 4000 mm, more preferably 200 to 2000 mm. In the case of forming an underlayer using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.

The silicon oxide layer obtained as described above using the vapor deposition material of the present invention is a layer containing 65% by mass of silicon oxide. The composition of the silicon oxide layer is not necessarily the same as the composition of the vapor deposition material. For example, the content of platinum group metal with respect to silicon oxide in the silicon oxide layer tends to increase, and the degree of increase tends to differ depending on the type of platinum group metal. This is presumably because, during vacuum deposition, platinum group metal precipitates as fine particles on the substrate surface, and a dense silicon oxide layer is formed on the substrate surface using the platinum group metal particles as seeds.

In addition, in the case where the base material of the vapor deposition material is a composition containing silicon oxide, the composition other than the platinum group metal is usually due to the difference in adhesion of the silicon oxide and other components to the platinum group metal or the substrate surface. Also, the vapor deposition material and the silicon oxide layer have different compositions. For example, when the base material of the vapor deposition material is soda lime glass, the composition other than the platinum group metal in the obtained silicon oxide layer is usually a composition having a higher silicon oxide content than the composition of the soda lime glass. .

SiO ₂ is 65 to 75%, Na ₂ O is 1 to 20%, CaO is 5 to 32%, and Al ₂ O ₃ is 0 in terms of mass% in terms of oxide, which is a preferable composition as a base material for the vapor deposition material. Taking a soda lime glass having a composition containing ˜2% and MgO as 0-4% as an example, the composition other than the platinum group metal in the obtained silicon oxide layer is generally expressed in mass% in terms of oxide, and SiO ₂ is 65-75%, Na ₂ O 1-20%, CaO 0-32%, Al ₂ O ₃ 0-2%, MgO 0-4%.

The thickness of the silicon oxide layer is preferably 2 to 200 nm, particularly preferably 2 to 20 nm. If thickness is more than the lower limit of the said range, the improvement effect of the base-material adhesiveness by a silicon oxide layer will be fully easy to be acquired. If thickness is below the upper limit of the said range, the abrasion resistance of silicon oxide layer itself will become high. The method for measuring the thickness of the silicon oxide layer is not particularly limited. For example, a method by cross-sectional observation of the silicon oxide layer with an electron microscope (SEM, TEM, etc.), an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, etc. There is a way.

The silicon oxide layer formed on the substrate using the above-described vapor deposition material by the production method of the present invention is formed as a dense layer as described above. Therefore, if the silicon oxide layer is used as a base layer and a surface layer is formed thereon, sufficient durability can be imparted to the resulting surface layer. When the surface layer is formed using an organic compound having a group capable of reacting with silicon oxide, the effect of durability can be exhibited more remarkably. Furthermore, it is more preferable in terms of durability when formed using an organic compound having a reactive silyl group.

[Method for producing substrate with surface layer]
The substrate with a surface layer obtained by the production method of the present invention comprises a substrate, a silicon oxide layer laminated on the substrate, and a surface layer directly formed on the silicon oxide layer. The silicon oxide layer is a layer mainly composed of silicon oxide formed using the vapor deposition material of the present invention described above, and the surface layer is a layer formed using a group capable of reacting with silicon oxide. . The “layer laminated on the base material” is not limited to the case where the layer is directly laminated on the base material, and includes the case where another layer is provided between the base material and the layer. Is the same.

The method for producing a substrate with a surface layer of the present invention comprises a step (a) of obtaining a substrate with a silicon oxide layer by forming a silicon oxide layer on the substrate, and a silicon oxide layer obtained in this step (a) (B) forming a surface layer using an organic compound having a group capable of reacting with silicon oxide on the silicon oxide layer of the attached substrate. (A) A process can be implemented like the manufacturing method of the base material with a silicon oxide layer of the said invention.

Hereinafter, the step (b) will be described. In the step (b), the surface layer is directly formed on the silicon oxide layer. A surface layer is a layer which plays the role which provides specific performance to a base material. The silicon oxide layer is a layer that plays a role of suppressing deterioration of the performance of the surface layer over time and improving the durability of the functional layer. The performance imparted to the base material by the surface layer is not particularly limited, and examples include antifouling properties, chemical resistance, abrasion resistance, weather resistance, hydrophilicity, water repellency, oil repellency, and the like. It is appropriately selected depending on the compound to be used.

The surface layer in the present invention is formed using an organic compound having a group capable of reacting with silicon oxide. In forming the surface layer, at least a part of the group capable of reacting with silicon oxide of the organic compound reacts with silicon oxide of the silicon oxide layer to form a condensate. Thus, since the surface layer and the silicon oxide layer form an extremely inseparable interface, the substrate with the surface layer obtained by the production method of the present invention is excellent in durability.

Examples of the group capable of reacting with silicon oxide include a group having a hydroxyl group, a group capable of generating a hydroxyl group, for example, a group in which the hydroxyl group is protected by an arbitrary protecting group. Among these, a reactive silyl group is preferable from the viewpoint of reactivity with silicon oxide, and a hydrolyzable silyl group is preferable from the viewpoint of storage stability of the compound.

When the group capable of reacting with silicon oxide in the organic compound is a hydrolyzable silyl group, the hydrolyzable silyl group in the organic compound (for example, in the following formula 1 in which L is a hydrolyzable group) Silanol groups (Si—OH) are formed by the hydrolysis reaction of —SiR _n L _3-n ). The resulting silanol group undergoes a condensation reaction between molecules to form a Si—O—Si bond, or the silanol group in the compound reacts with a silanol group (Si—OH) in the silicon oxide layer to form a bond (Si— It is considered that (O—Si bond) is formed. That is, the surface layer in this case contains a condensate obtained by hydrolytic condensation of a compound having a hydrolyzable silyl group. The surface layer may consist only of a condensate of a compound having a reactive silyl group, or may contain an unreacted product of a compound having a reactive silyl group. As described later, unreacted substances can be removed as necessary.

(Compound having a reactive silyl group)
The compound having a reactive silyl group is preferably a fluorine-containing compound having a reactive silyl group (hereinafter also referred to as a fluorine-containing compound) from the viewpoint of obtaining a surface layer having water and oil repellency.
Among the compounds having a reactive silyl group, examples of the compound having no fluorine atom include an organosilane compound having a reactive silyl group, a silane compound having a polydimethylsiloxane chain structure (all of which have no fluorine atom). .

The number of the reactive silyl groups in the compound having a reactive silyl group is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint that the abrasion resistance of the surface layer is further improved. The upper limit is not particularly limited, but 15 is preferable from the viewpoint of ease of production, and 12 is particularly preferable.

Examples of the fluorine-containing compound include a fluorine-containing compound having a fluoroalkyl group and a fluorine-containing compound having an etheric oxygen atom between carbon atoms of the fluoroalkyl group. A fluorine-containing compound having a perfluoroalkyl group and a fluorine-containing compound further having an etheric oxygen atom between the carbon atoms of the perfluoroalkyl group from the viewpoint that a surface layer excellent in water / oil repellency, fingerprint stain removability, lubricity and the like can be formed. Is preferred.

In addition, the fluorine-containing compound is preferably a fluorine-containing compound having a poly (oxyfluoroalkylene) chain from the viewpoint that a surface layer excellent in water / oil repellency, fingerprint stain removability, lubricity and the like can be formed. A fluorine-containing compound having an (alkylene) chain is more preferable.

As the fluorine-containing compound, in particular, a fluorine-containing compound having a fluoroalkyl group and a poly (oxyfluoroalkylene) chain (hereinafter, referred to as a surface layer excellent in water / oil repellency, fingerprint stain removability, lubricity, etc.) It is also referred to as a fluorine-containing ether compound).

The fluoroalkyl group is preferably a fluoroalkyl group having 1 to 20, more preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms from the viewpoint of excellent water and oil repellency. . The fluoroalkyl group may be linear or branched, and is preferably linear. The fluoroalkyl group is preferably a perfluoroalkyl group from the viewpoint of superior physical properties of the surface layer.

Examples of the fluorine-containing compound having a perfluoroalkyl group and a reactive silyl group include compounds represented by the formula (3) described in paragraphs [0010] and [0022] of Japanese Patent Application Laid-Open No. 2009-139530. It is done.

The poly (oxyfluoroalkylene) chain is preferably composed of an oxyperfluoroalkylene group having 1 to 10 carbon atoms, particularly preferably 1 to 10 carbon atoms. From the viewpoint of further excellent wear resistance and fingerprint stain removability of the surface layer, those composed of a plurality of oxyperfluoroalkylene groups having 1 to 10 carbon atoms are preferred.

For example, a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 2 carbon atoms, a plurality of oxyperfluoroalkylene groups having 1 carbon atom, and a plurality of oxyperfluoroalkylene groups having 3 carbon atoms. A plurality of oxyperfluoroalkylene groups having 2 carbon atoms and a plurality of oxyperfluoroalkylene groups having 3 carbon atoms, a plurality of oxyperfluoroalkylene groups having 2 carbon atoms and a plurality of oxyperfluoroalkylene groups having 4 carbon atoms. A plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 5 carbon atoms, a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 6 carbon atoms. Thing, carbon number 1 4 made of a plurality of at least three or more oxyperfluoroalkylene groups selected from and the like.

The arrangement of the plurality of oxyperfluoroalkylene groups may be block, random or alternating. When the oxyperfluoroalkylene group has 2 or more carbon atoms, a straight-chain oxyperfluoroalkylene group is preferable.

As the poly (oxyperfluoroalkylene) chain, a linear oxyperfluoroalkylene group having 1 carbon atom and a linear oxyperfluoroalkylene group having 2 carbon atoms are randomly arranged; Randomly arranged perfluoroalkylene groups and linear oxyperfluoroalkylene groups having 3 carbon atoms, alternating linear oxyperfluoroalkylene groups having 2 carbon atoms and linear oxyperfluoroalkylene groups having 4 carbon atoms Those arranged in are particularly preferred.

When the fluorine-containing compound is a fluorine-containing ether compound, the fluorine-containing ether compound preferably has two or more reactive silyl groups from the viewpoint of high adhesion between the surface layer and the silicon oxide layer.
The number average molecular weight of the fluorinated ether compound is preferably 500 to 20,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 8,000, from the viewpoint of the friction resistance of the surface layer.

As the fluorine-containing ether compound, Compound 1 is preferable in that the water and oil repellency of the surface layer is more excellent.
[AO—Z ¹ — (R ^f O) _m —] _j Z ² [—SiR _n L _3-n ] _q Formula 1
A is a perfluoroalkyl group or a _{-Q [-SiR n L 3-n} ] k. The number of carbon atoms in the perfluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, and particularly preferably from 1 to 3 from the viewpoint that the friction resistance of the surface layer is more excellent. The perfluoroalkyl group may be linear or branched.
However, j is 1 when A is -Q [-SiR _n L _3-n ] _k .

As perfluoroalkyl groups, CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF (CF ₃ ) —, and the like can be given. From the viewpoint of more excellent water and oil repellency of the surface layer, CF ₃ —, CF ₃ CF ₂ —, or CF ₃ CF ₂ CF ₂ — is preferable.

Q is a (k + 1) -valent linking group. As will be described later, k is an integer of 1 to 10. Accordingly, examples of Q include divalent to eleven valent linking groups.
Examples of Q include an etheric oxygen atom or an alkylene group optionally having a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane residue, which will be described later. And groups obtained by removing SiR _n L _3-n from formulas 2-1, 2-2, and 2-1-1 to 2-1-6.

R is a monovalent hydrocarbon group. R is particularly preferably a monovalent saturated hydrocarbon group. The carbon number of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.
L is a hydrolyzable group or a hydroxyl group. The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group becomes a silanol group by a hydrolysis reaction. Silanol groups further react between the silanol groups to form Si—O—Si bonds.

Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy industrial production. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and better storage stability of the compound, and an ethoxy group is particularly preferred when long-term storage stability of the compound is required. A methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0-2. n is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L, the interaction between the surface layer and the silicon oxide layer is good, and the durability of the functional layer of the present invention is excellent.
When n is 1 or less, a plurality of L present in one molecule may be the same as or different from each other. From the viewpoint of availability of raw materials and ease of production, it is preferable that they are the same.

Among the reactive silyl groups (SiR _n L _3-n ), hydrolyzable silyl groups include —Si (OCH ₃ ) ₃ , —SiCH ₃ (OCH ₃ ) ₂ , —Si (OCH ₂ CH ₃ ) ₃ , — SiCl ₃ , —Si (OC (O) CH ₃ ) ₃ , or —Si (NCO) ₃ is preferred. From the viewpoint of easy handling in industrial production, —Si (OCH ₃ ) ₃ is particularly preferable.

Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms (excluding the oxyperfluoroalkylene group. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m ), or a poly (oxyfluoroalkylene) group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms (bonded to (R ^f O) _m oxygen atoms in the oxy-fluoroalkylene group is (R f ^O) binds to _m. oxyfluoroalkylene group bonded to (R f ^O) _m is. poly (oxy-fluoroalkylene comprising one or more hydrogen atoms ) Group includes both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms. May be included.) The oxyfluoroalkylene group or poly (oxyfluoroalkylene) group preferably has 1 to 10 carbon atoms.

Z ¹ may be a single bond, —CHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CHFCF ₂ OCH ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF, because it is easy to produce a compound. ₂ O—, —CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CH ₂ OCH ₂ CF ₂ O—, or — CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O— is preferable (where the left side is bonded to A—O), and a single bond or —CHFCF ₂ OCH ₂ CF ₂ O— is particularly preferable.

R ^f is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 because the water and oil repellency of the surface layer is more excellent. The perfluoroalkylene group may be linear or branched, but is preferably linear because it is more excellent in water and oil repellency of the surface layer.
The plurality of R ^f may be the same or different. That is, (R ^f O) _m may be composed of two or more types of R ^f O having different carbon numbers.

m is an integer of 2 to 200, preferably 5 to 150, particularly preferably 10 to 100. When m is 2 or more, the water and oil repellency of the surface layer is more excellent. If m is 200 or less, the durability of the surface layer is more excellent.
In (R ^f O) _m , when two or more types of R ^f O having different carbon numbers are present, the bonding order of each R ^f O is not limited. For example, when two types of R ^f O are present, the two types of R ^f O may be randomly, alternately, and arranged in blocks.

^(R f _O) as the _m, from the viewpoint of water and oil repellency of the surface layer is more _{excellent, {(CF 2 O) m11} (CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 CF ₂ CF ₂ CF ₂ O) _{m 14} }, (CF ₂ CF ₂ O) _{m 16,} (CF ₂ CF ₂ CF ₂ O) _{m 17} , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 15} ( _{CF 2 CF 2 O), (} CF 2 O-CF 2 CF 2 CF 2 CF 2 CF 2 O) m18 (CF 2 O), (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O) _m19 (CF ₂ CF ₂ O), {(CF ₂ O) _m20 (CF ₂ CF ₂ CF ₂ O) _m21 }, or {(CF ₂ CF ₂ O) _m22 (CF ₂ CF ₂ CF ₂ O) _m23 } Is preferred . _{{(CF 2 O) m11 (} CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 CF 2 CF 2 CF 2 O) m14}, (CF 2 CF 2 O-CF 2 CF 2 _{CF 2 CF 2 O) m15 (} CF 2 CF 2 O), or _{(CF 2 O-CF 2 CF} 2 CF 2 CF 2 CF 2 O) m18 (CF 2 O), (CF 2 CF 2 O-CF 2 CF _{2 CF 2 CF 2 CF 2 CF} 2 O) m19 (CF 2 CF 2 O) are particularly preferred.

However, m11 and m12 are each an integer of 1 or more, m13 and m14 are each an integer of 0 or 1 and m11 + m12 + m13 + m14 is an integer of 2 to 200, m11 CF ₂ O, m12 The bonding order of CF ₂ CF ₂ O, m13 CF ₂ CF ₂ CF ₂ O, and m14 CF ₂ CF ₂ CF ₂ CF ₂ O is not limited. m16 and m17 are each an integer of 2 to 200, and m15 and m18 to m23 are integers of 1 to 99.
In addition _{{(CF 2 O) m11 (} CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 CF 2 CF 2 CF 2 O) m14}, when m13 and m14 is 0, m12 / M11 is preferably from 0.1 to 10, more preferably from 0.2 to 5.0, even more preferably from 0.2 to 2.0, from the point that the friction resistance of the surface layer is further improved, 1.5 is particularly preferred, and 0.2 to 0.85 is most preferred.

Z ² is a (j + q) -valent linking group. Z ² is, for example, an etheric oxygen atom or an alkylene group optionally having a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane residue, which will be described later. And groups obtained by removing SiR _n L _3-n from the formulas 2-1, 2-2, and 2-1-1 to 2-1-6.

j is an integer of 1 or more, preferably 1 to 5 from the viewpoint of more excellent water and oil repellency of the surface layer, and particularly preferably 1 from the viewpoint of easy production of the compound.
q is an integer of 1 or more, and is preferably 2 or more, more preferably 2 to 4, more preferably 2 or 3, and even more preferably 3, from the viewpoint of better water / oil repellency of the surface layer.

Compound 1-1 is preferably Compound 1-1 because the surface layer is more excellent in water and oil repellency.
AOZ ^1- (R ^f O) _m -Z ³ Formula 1-1
In formula 1-1, the definitions of A, Z ¹ , R ^f and m are the same as the definitions of each group in formula 1.
Z ³ is group 2-1 or group 2-2.
-R ^f7 -Q ^a -X (-Q ^b -SiR _n L _3-n ) _h (-R ⁷ ) _i Formula 2-1
_{^{-R f7 -Q 71 - [CH 2}} C (R 71) (- Q 72 -SiR n L 3-n)] y -R 72 Formula 2-2
In formulas 2-1 and 2-2, the definitions of R, L, and n are the same as the definitions of each group in formula 1.

R ^f7 is a perfluoroalkylene group. The perfluoroalkylene group preferably has 1 to 30 carbon atoms, particularly preferably 1 to 6 carbon atoms. The perfluoroalkylene group may be linear or branched.
R ^f7 is preferably —CF ₂ CF ₂ CF ₂ CF ₂ — or —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — from the viewpoint of easy production of the compound.

Q ^a is a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. A divalent saturated carbonization group. The hydrogen group may be linear, branched or cyclic and includes, for example, an alkylene group, preferably having 1 to 20 carbon atoms.
The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. In addition, an alkenylene group having 2 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms may be used. ) A divalent heterocyclic group, —O—, —S—, —SO ₂ —, —N (R ^d ) —, —C (O) —, —Si (R ^a ) ₂ — and these 2 Examples include groups in which more than one species are combined. Here, R ^a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the group in which two or more of these are combined include, for example, —OC (O) —, —C (O) N (R ^d ) —, an alkylene group —O-alkylene group, and an alkylene group —OC (O). -Alkylene group, alkylene group-Si (R ^a ) ₂ -phenylene group-Si (R ^a ) ₂

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a divalent to octavalent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
The alkylene group represented by X preferably has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms.
Examples of the divalent to octavalent organopolysiloxane residues include divalent organopolysiloxane residues and (w + 1) valent organopolysiloxane residues described below.

Q ^b is a single bond or a divalent linking group. Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.
R ⁷ is a hydroxyl group or an alkyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.

When X is a single bond or an alkylene group, h is 1, i is 0,
When X is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, satisfies h + i = 2, and when X is a carbon atom or a silicon atom, h is an integer of 1 to 3. And i is an integer from 0 to 2, satisfies h + i = 3,
When X is a divalent to octavalent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
When there are two or more (—Q ^b —SiR _n L _3-n ), they may be the same or different. When two or more R ⁷ are present, they may be the same or different.

Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group, and is preferably a single bond from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group is preferably 1-10, and particularly preferably 2-6.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of a compound. As the alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, and more preferably 1 to 6. Q ⁷² is preferably a single bond or —CH ₂ — from the viewpoint of easy production of the compound.

R ⁷² is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.
y is an integer of 1 to 10, and an integer of 1 to 6 is preferable.
Two or more [CH ₂ C (R ⁷¹ ) (— Q ⁷² —SiR _n L _3-n )] may be the same or different.

The group 2-1 is preferably any of the following groups 2-1-1 to 2-1-6.
-R ^f7- (X ¹ ) _p -Q ¹ -SiR _n L _3-n Formula 2-1-1
-R ^f7- (X ² ) _r -Q ²¹ -N [-Q ²² -SiR _n L _3-n ] ₂ Formula 2-1-2
-R ^f7 -Q ³¹ -G (R ³ ) [-Q ³² -SiR _n L _3-n ] ₂ formula 2-1-3
_{^{-R f7 - [C (O)}} N (R d)] s -Q 41 - (O) t -C [- (O) u -Q 42 -SiR n L 3-n] 3 Formula 2-1-4
-R ^f7 -Q ⁵¹ -Si [-Q ⁵² -SiR _n L _3-n ] Formula ₃ 2-1-5
-R ^f7- [C (O) N (R ^d )] _v -Q ⁶¹ -Z ³ [-Q ⁶² -SiR _n L _3-n ] _w formula 2-1-6

In formulas 2-1-1 to 2-1-6, the definitions of R ^f7 , R, L, and n are as described above.
In Formula 2-1-1, X ¹ is —O— or —C (O) N (R ^d ) — (wherein N binds to Q ¹ ). The definition of R ^d is as described above. p is 0 or 1.

Q ¹ is an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
In addition, when the alkylene group has —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The alkylene group represented by Q ¹ preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.
As Q ¹ , when p is 0, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ — or —CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ — is preferred. (X ¹ ) When _p is —O—, —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — is preferred. When (X ¹ ) _p is —C (O) N (R ^d ) —, an alkylene group having 2 to 6 carbon atoms is preferred (where N in the formula binds to Q ¹ ). Q ¹ is the compound is likely to manufacture and is these groups.

Specific examples of the group 2-1-1 include the following groups.

In Formula 2-1-2, X ² is —O—, —NH—, or —C (O) N (R ^d ) —.
The definition of R ^d is as described above.
Q ²¹ represents a single bond, an alkylene group, or an etheric oxygen atom, —C (O) —, —C (O) O—, —OC (between a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms. O) — or a group having —NH—.
The number of carbon atoms of the alkylene group represented by Q ²¹ is preferably 1 to 10, and particularly preferably 2 to 6. An etheric oxygen atom, —C (O) —, —C (O) O—, —OC (O) — or —NH between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ²¹ The number of carbons in the group having — is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^21, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 —, —CH ₂ CH ₂ OC (OCH ₂ CH ₂ — is preferred (the right side is bonded to N).
r is 0 or 1 (provided that 0 when Q ²¹ is a single bond). From the viewpoint of easy production of the compound, 0 is preferable.

Q ²² is an alkylene group or a group having a divalent organopolysiloxane residue, an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 2 or more carbon atoms. The alkylene group represented by Q ²² is preferably 1-10, 2-6 being particularly preferred.
The number of carbon atoms of the group having a divalent organopolysiloxane residue, an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ²² is 2 to 10 2 to 6 are particularly preferable.

Q ²² is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (provided that the right side is bonded to Si) from the viewpoint of easy production of the compound.
Two [-Q ²² -SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-2 include the following groups.

In formula 2-1-3, Q ³¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, and is easy to produce a compound From the viewpoint, a single bond is preferable. The alkylene group represented by Q ³¹ is preferably 1-10, 2-6 being particularly preferred.
The number of carbon atoms of the group having an etheric oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ³¹ is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ⁶ is a hydroxyl group or an alkyl group. The alkyl group represented by R ³ preferably has 1 to 4 carbon atoms.
G (R ³ ) is C (OH) or Si (R ^3a ) (provided that R ^3a is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, Group is particularly preferred.).

Q ³² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ³² is preferably 1-10, 2-6 being particularly preferred. Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³² - number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residues between the carbon atoms is 2 to 10 preferably 2 to 6 is particularly preferred.
The Q ^32, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.
Two [—Q ³² —SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-3 include the following groups.

In formula 2-1-4, the definition of R ^d is as described above.
s is 0 or 1.
Q ⁴¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group. The number of carbon atoms of the alkylene group represented by Q ⁴¹ is preferably 1 to 10, and particularly preferably 2 to 6.
The number of carbon atoms of the group having an etheric oxygen atom between the carbon atoms of the alkylene group of 2 or more carbon atoms represented by Q ⁴¹ is preferably 2 to 10, and particularly preferably 2 to 6.
t is 0 or 1 (provided that 0 when Q ⁴¹ is a single bond).
—Q ⁴¹ — (O) _t — represents a compound that is easy to produce. When s is 0, a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ O—, —CH ₂ OCH ₂ CH ₂ OCH ₂ —, or —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ — is preferred (where the left side is bonded to R ^f7 ), and when s is 1 , A single bond, —CH ₂ —, or —CH ₂ CH ₂ — is preferred.

Q ⁴² is an alkylene group, and the alkylene group is —O—, —C (O) N (R ^d ) — [R ^{d is} as defined above. ], May have a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.
In the case where the alkylene group has —O— or a silphenylene skeleton group, it is preferable to have —O— or a silphenylene skeleton group between carbon atoms. Further, when the alkylene group has —C (O) N (R ^d ) —, a dialkylsilylene group or a divalent organopolysiloxane residue, the terminal on the side bonded to the carbon atom-carbon atom or (O) _u1 side It is preferable to have these groups.
The alkylene group represented by Q ⁴² is preferably 1-10, 2-6 being particularly preferred.

u is 0 or 1.
As — (O) _u —Q ⁴² —, since it is easy to produce a compound, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ — is preferred (the right side is bonded to Si).
The three [— (O) _u -Q ⁴² -SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-4 include the following groups.

In formula 2-1-5, Q ⁵¹ represents an alkylene group or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms. The number of carbon atoms of the alkylene group represented by Q ⁵¹ is preferably 1 to 10, and particularly preferably 2 to 6.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group of 2 or more carbon atoms represented by Q ⁵¹ is preferably 2 to 10, and particularly preferably 2 to 6.
Q ⁵¹ is —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, or —CH _{2 because} it is easy to produce a compound. CH ₂ CH ₂ — is preferred (however, the right side is bonded to Si).

Q ⁵² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of a C 2 or more alkylene group. The number of carbon atoms of the alkylene group represented by Q ⁵² is preferably 1 to 10, and particularly preferably 2 to 6.
The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group of 2 or more carbon atoms represented by Q ⁵² is preferably 2 to 10. 6 is particularly preferred.
Q ⁵² is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (provided that the right side is bonded to SiR _n L _3-n from the viewpoint of easy production of the compound). .)
The three [—Q ⁵² —SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-5 include the following groups.

In formula 2-1-6, the definition of R ^d is as described above.
v is 0 or 1.
Q ⁶¹ is an alkylene group or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group. The number of carbon atoms of the alkylene group represented by Q ⁶¹ is preferably 1 to 10, and particularly preferably 2 to 6.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group of 2 or more carbon atoms represented by Q ⁶¹ is preferably 2 to 10, and particularly preferably 2 to 6.
Q ⁶¹ represents —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, or —CH _{2 because} it is easy to produce a compound. CH ₂ CH ₂ — is preferred (where the right side is bonded to Z ³ ).

Z ³ is a (w + 1) valent organopolysiloxane residue.
w is an integer of 2 to 7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. However, R ^a in the following formula is as described above.

Q ⁶² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ⁶² is preferably 1-10, 2-6 being particularly preferred. Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶² - number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residues between the carbon atoms is 2 to 10 preferably 2 to 6 is particularly preferred.
The Q ^62, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 - is preferred.
The w [—Q ⁶² —SiR _n L _3-n ] may be the same or different.

Specific examples of Compound 1 include International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication. No. 2015/087902, Japanese Unexamined Patent Publication No. 2014-080473, Japanese Unexamined Patent Publication No. 2015-199906, International Publication No. 2017/038830, International Publication No. 2017/038832 and International Publication No. 2017/187775. Fluorinated ether compounds, perfluoro (poly) ethers described in Japanese Patent Application Laid-Open No. 11-029585, International Publication No. 2017/022437, International Publication No. 2018/079743, International Publication No. 2018/143433 Silane compound , A fluorooxyalkylene group-containing polymer described in Patent Document 2, a silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715, an organic silicon compound described in Japanese Unexamined Patent Publication No. 2000-144097, and Japanese Unexamined Patent Publication 2000- Perfluoropolyether-modified aminosilane described in Japanese Patent No. 327772, fluorinated siloxane described in Japanese Patent Special Publication No. 2002-506687, organosilicone compound described in Japanese Special Patent Publication No. 2008-534696, and Japanese Patent No. 4138936 The fluorinated modified hydrogen-containing polymer described in the above, the compound described in US Patent Application Publication No. 2010/0129672, the organosilicon compound described in International Publication No. 2011/060047, and described in International Publication No. 2011/059430 Organosilicon Compound, fluorine-containing organosilane compound described in International Publication No. 2012/064649, fluorooxyalkylene group-containing polymer described in Japanese Patent Application Laid-Open No. 2012-72272, compound described in International Publication No. 2014/122604, Japan Compounds described in JP-A-2014-070163, fluoropolyether group-containing polymer-modified silane described in JP-A-2016-204656, and fluoropolyether group-containing polymer-modified described in JP-A-2016-210854 Silane, fluoropolyether group-containing polymer-modified silane described in Japanese Patent Application Laid-Open No. 2016-222859, International Publication No. 2018/216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019 / 039 No. 186, International Publication No. 2019/044479, and Japanese Unexamined Patent Publication No. 2019-44158, and the like.

Commercially available products can be used as the fluorine-containing ether compound. For example, KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., OPTOOL (trade name) DSX, AES, UF503, UD509 manufactured by Daikin Industries, and Afluid manufactured by AGC ( (Registered trademark) S550.

(Method for forming surface layer)
The method for forming the surface layer using an organic compound having a group capable of reacting with silicon oxide may be wet coating or dry coating.
Examples of the dry coating include physical vapor deposition (vacuum vapor deposition, ion plating, sputtering), chemical vapor deposition (thermal CVD, plasma CVD, photo CVD), and ion beam sputtering. In the case of an organic compound having a group capable of reacting with silicon oxide, when the group is a reactive silyl group, the vacuum vapor deposition method is particularly preferable from the viewpoint of suppressing the decomposition of the compound and the simplicity of the apparatus.

Specifically, vacuum deposition is performed by placing a substrate with a silicon oxide layer in an apparatus capable of reducing pressure, and forming a group capable of reacting with silicon oxide at a position facing the surface of the silicon oxide layer of the substrate with a silicon oxide layer. An evaporation container containing an organic compound or a composition containing the organic compound or a solution or dispersion obtained by adding a solvent to the organic compound is installed. For the vapor deposition container, an organic compound having a group capable of reacting with silicon oxide or a composition containing the same, or a pellet or impregnated metal porous body such as iron or steel impregnated with a solution or dispersion obtained by adding a solvent to these compounds A state substance may be accommodated.

The size and shape of the deposition container are not particularly limited. Examples of the material for the vapor deposition container include molybdenum, tungsten, and copper. During vacuum deposition, the container for deposition is heated by an electron gun or resistance heating. The heating temperature of the container for deposition is preferably 20 to 1000 ° C, more preferably 200 to 700 ° C, and further preferably 300 to 500 ° C.

The temperature in the apparatus during vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure in the apparatus during vacuum deposition is preferably 1 × 10 ⁻¹ Pa or less, particularly preferably 1 × 10 ⁻² Pa or less. The distance between the surface of the silicon oxide layer of the substrate with the silicon oxide layer, the organic compound having a group capable of reacting with silicon oxide or a composition containing the same, or a solution or dispersion obtained by adding a solvent to these is 100 to 4000 mm. Is preferable, and 200 to 2000 mm is more preferable.

In dry coating, one type of organic compound having a group capable of reacting with silicon oxide may be used alone or as a mixture of two or more types, and an organic compound having a group capable of reacting with silicon oxide and other components (however, And the solvent may be used as a composition or a dispersion obtained by adding a solvent to these.

Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples thereof include a coating method.
In the wet coating, a surface layer forming coating solution is preferably used. The surface layer forming coating liquid is a solution or dispersion containing an organic compound having a group capable of reacting with silicon oxide and a solvent.

The solvent is appropriately selected according to the type of organic compound having a group capable of reacting with silicon oxide. When the compound is a fluorine-containing compound, the solvent is preferably an organic solvent. The organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or may include both solvents. Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, Examples include ether organic solvents and ester organic solvents.

In addition to the organic compound having a group capable of reacting with silicon oxide and the solvent, the surface layer forming coating solution contains other components and impurities (by-products generated in the production process of the compound having a reactive silyl group). May be included. As other components, for example, in an organic compound having a group capable of reacting with silicon oxide, when the group is a hydrolyzable silyl group, an acid catalyst that promotes hydrolysis and condensation reaction of the hydrolyzable silyl group And known additives such as basic catalysts.

The solid content concentration of the coating solution for forming the surface layer is preferably 0.001 to 50% by mass, particularly preferably 0.05 to 30% by mass. The solid content concentration is a value calculated from the mass of the surface layer forming coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120 ° C.

<Post-processing>
In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the organic compound having a group capable of reacting with silicon oxide and the silicon oxide layer may be performed as necessary. Examples of the operation include heating, humidification, and light irradiation. For example, in an organic compound having a group capable of reacting with silicon oxide, when the group is a hydrolyzable silyl group, the substrate with the silicon oxide layer on which the surface layer is formed is heated in an atmosphere having moisture. The hydrolysis reaction of hydrolyzable silyl groups into silanol groups, the formation of siloxane bonds by the condensation reaction of silanol groups, the silanol groups on the surface of the silicon oxide layer and the silanol groups of compounds having hydrolyzable silyl groups Reactions such as condensation reactions can be promoted.

After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the silicon oxide layer may be removed as necessary. Specific examples of the method include a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.

The thickness of the surface layer is preferably from 0.1 to 100 nm, particularly preferably from 0.1 to 50 nm. If the thickness of the surface layer is 0.1 nm or more, the effect of the surface treatment can be easily obtained. If the thickness of the surface layer is 100 nm or less, the utilization efficiency is high.

Thus, the substrate with a surface layer obtained by the present invention is an article having excellent durability in which the deterioration of the performance of the surface layer over time is suppressed by having the silicon oxide layer. For example, when the surface layer has water and oil repellency, a water contact angle may be mentioned as an index for achieving water repellency. The water contact angle on the air side surface of the surface layer is preferably 100 degrees or more, more preferably 105 degrees or more, further preferably 110 degrees or more, and particularly preferably 115 degrees or more. When the water contact angle is 100 degrees or more, the water repellency of the surface layer is excellent. Since the water contact angle of the surface layer is preferably as high as possible, the upper limit is not particularly limited. The water contact angle is measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.).

The base material with a surface layer according to the present invention is, for example, a reciprocating traverse tester (manufactured by Daiei Seiki Co., Ltd.) according to JIS L0849: 2013 (ISO 105-X12: 2001) on the air side surface of the surface layer. It is possible to maintain a water contact angle of 100 degrees or more after a steel wool bonster (count: # 0000, dimensions: 5 mm × 10 mm × 10 mm) is reciprocated 3,000 times at a load of 9.8 N and a speed of 80 rpm. Preferably, it can hold | maintain also at 105 degree | times or more.

The substrate with a surface layer according to the present invention is, for example, a value obtained by subtracting the water contact angle of the surface layer after 3,000 reciprocations from the initial water contact angle for the air-side surface of the surface layer (contact angle reduction amount). ) Is preferably 25 degrees or less, more preferably 15 degrees or less, and particularly preferably 10 degrees or less. Since the contact angle reduction amount is preferably as small as possible, the lower limit value is not particularly limited.

The base material with a surface layer according to the present invention is assumed to be excellent in durability since the hardness measured on the air side surface of the surface layer, for example, Martens hardness is high. In the base material with a surface layer according to the present invention, an indentation test device (Fischer, Picodenter HM500) is used for the air side surface of the surface layer, the indentation load is 0.03 mN, the holding time is 5 seconds, the load speed and The Martens hardness measured as an unloading speed of 0.05 mN / 5 seconds is preferably 8,500 MPa or more, and more preferably 10,000 MPa or more.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Examples 1 to 6 are examples, and examples 7 to 9 are comparative examples.

In each example, a vapor deposition material was prepared as follows. Furthermore, using the following materials, a substrate with a surface layer comprising a silicon oxide layer on a glass substrate and a surface layer having water and oil repellency as performance on the silicon oxide layer is manufactured, and the following physical properties Measurements and evaluations were made.

[material]
Glass substrate: Dragontrail (registered trademark of AGC), Size: 50 mm long x 50 mm wide, 0.5 mm thick
Organic compound having a group capable of reacting with silicon oxide: a fluorinated ether compound represented by the following chemical formula (number average molecular weight: 4,920) produced by the method for synthesizing compound (ii-2) in WO2014 / 1226064 (Hereinafter referred to as fluorine-containing ether compound F).
_{CF 3 CF 2 OCF 2 CF 2} O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) 13 CF 2 CF 2 CF 2 C (O) NHCH 2 CH 2 CH 2 Si (OCH 3) 3

(Initial water contact angle)
The contact angle when 2 μL of distilled water was dropped onto the air side surface of the surface layer was measured at 20 ° C. using a contact angle measuring device (DM-701, Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the surface layer, and the average value was calculated.

(Steel wool wear test)
For the surface layer, in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), using a reciprocating traverse tester (manufactured), a steel wool bonster (counter: # 0000, dimensions: 5 mm × 10 mm × 10 mm) It was reciprocated at a load of 9.8 N and a speed of 80 rpm. The water contact angle of the water / oil repellent layer was measured every 1000 times of wear of the steel wool, and the number of times the water contact angle became less than 100 degrees was defined as wear resistance.

[Example 1]
(Preparation of vapor deposition material)
Silica sand, calcium carbonate, sodium carbonate, and platinum powder (average particle size: 7 μm) were mixed to prepare a raw material composition of a vapor deposition material. The mixing ratio of silica sand, calcium carbonate, and sodium carbonate is that the components other than platinum in the obtained vapor deposition material are expressed in mass% in terms of oxide, SiO ₂ is 70%, Na ₂ O is 3%, and CaO is 27%. Each was adjusted to contain. The platinum content was set to an amount of 0.05 mass ppm as a ratio to the silicon oxide in the vapor deposition material.

The above raw material composition was put in a crucible and heated to 1500 ° C. in an electric furnace to obtain a melt. The obtained melt was poured onto a carbon plate, cooled and solidified at room temperature to obtain a plate-like vapor deposition material. The cooling rate was 1 ° C./min. The obtained plate-shaped vapor deposition material was pulverized with a hammer to obtain a flake-shaped vapor deposition material (1) having an average major axis of 3 mm. In addition, the average major axis of the vapor deposition material (1) was measured with a saw. As a result of ICP analysis of the obtained vapor deposition material (1), it was confirmed that the vapor deposition material having the composition as set above was obtained.

(Washing substrate (removing impurities))
One surface of the glass substrate was subjected to corona discharge treatment under conditions of 80 V and 3.5 A using a high-frequency power source (CG102A manufactured by Kasuga Electric Co., Ltd.).
(Formation of silicon oxide layer and surface layer)
Two molybdenum boats A and B were placed in a vacuum evaporation system (VTR-350M manufactured by ULVAC Kiko Co., Ltd.). In boat A, 0.5 g of the vapor deposition material (1) was accommodated, and in boat B, 0.5 g of the fluorinated ether compound F was accommodated.

The discharge-treated glass substrate was placed in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure (absolute pressure) of 5 × 10 ⁻³ Pa or less. After disposing the boat A at a distance of 1000 mm so as to face the glass substrate, the boat A was heated to 1000 ° C. with an electron gun, the vapor deposition material (1) was vacuum deposited, and the thickness was 10 nm on the glass substrate. The silicon oxide layer was formed by vapor deposition. In addition, the temperature of vapor deposition material (1) is 1300 degreeC similarly to the heating temperature of the said boat A. As shown in FIG.

Next, after the boat B is disposed at a distance of 1000 mm so as to face the surface of the silicon oxide layer of the glass substrate on which the silicon oxide layer is formed, the boat B is heated to 300 ° C. by resistance heating, and the fluorine-containing ether compound F was vacuum evaporated to form a deposited film having a thickness of 10 nm. The temperature of the fluorinated ether compound F was 300 ° C., similar to the heating temperature of the boat B. Thereafter, the obtained glass substrate with a deposited film was heated (post-treatment) at a temperature of 200 ° C. for 30 minutes, and the glass substrate with a surface layer (1) having a silicon oxide layer and a surface layer in that order on the glass substrate. )

[Example 2]
A vapor deposition material (2) was prepared in the same manner as in Example 1, except that the platinum powder was changed to rhodium powder (average particle size: 7 μm). Further, a glass substrate with a surface layer (2) was produced in the same manner as in Example 1 except that the vapor deposition material (1) was changed to the vapor deposition material (2).

[Examples 3 to 9]
Example 3 was carried out in the same manner as in Example 1 except that the platinum powder or rhodium powder used in Example 1 or Example 2 was adjusted so that the ratio of platinum or rhodium to silicon oxide in the vapor deposition material was the amount shown in Table 1. Vapor deposition materials (3) to (8), (10), and (11) of ˜8, 10, and 11 were prepared. In Example 9, a vapor deposition material (9) was prepared in the same manner as in Example 1 using only silica sand, calcium carbonate, and sodium carbonate without adding platinum powder or rhodium powder. Further, glass substrates with surface layers (3) to (11) were produced in the same manner as in Example 1 except that the vapor deposition material (1) was changed to the vapor deposition materials (3) to (11).

[Example 12]
Except for adjusting the compounding ratio of silica sand and sodium carbonate so that the components other than platinum in the obtained vapor deposition material contain 90% of SiO ₂ and 10% of Na ₂ O in terms of mass% in terms of oxides. In the same manner as in Example 3, a vapor deposition material (12) was prepared. Further, a glass substrate with a surface layer (12) was produced in the same manner as in Example 1 except that the vapor deposition material (1) was changed to the vapor deposition material (12).

[Evaluation]
(Composition of silicon oxide layer)
In each of the above examples, the content ratio [mass ppm] of platinum (Pt) or rhodium (Rh) to silicon oxide in the silicon oxide layer of the glass substrate with a silicon oxide layer was determined by double convergence dynamic SIMS. The results are shown in Table 1 together with the platinum group metal content (mass ppm vs. SiO ₂ ) in the vapor deposition material. Further, in Examples 1 to 11, the composition of components other than the platinum group metal in the silicon oxide layer was measured by the same method. The composition was expressed in mass% in terms of oxide, and each of SiO ₂ was 96%, The composition contained 2.6% Na ₂ O and 1.4% CaO. In Example 12, the composition contained 88% SiO ₂ and 12% Na ₂ O.

(Silicon oxide layer composition)
With respect to the glass substrates (1) to (12) with a surface layer, the initial water contact angle was measured and the steel wool abrasion test was evaluated by the above method. The results are shown in Table 1.

As is apparent from Table 1, the glass substrates with surface layers (1) to (8) and (12) obtained in Examples 1 to 8 and 12, which are examples, have a high initial contact angle, The water contact angle after the steel wool abrasion test can be maintained at a high level.

The substrate with a surface layer according to the present invention is an article for transport equipment, an article for precision equipment, an article for optical equipment, an article for construction or an article for electronic equipment, and further, the substrate with a surface layer according to the present invention is the above-mentioned Used for goods other than various devices.
Specific examples of articles for transportation equipment include exterior members, interior members, glass (for example, windshields, side glasses, and rear glasses), mirrors, and tire wheels in trains, automobiles, ships, airplanes, and the like. As a specific example of the precision instrument article, a window material in a photographing instrument can be cited. A lens is mentioned as a specific example of the article for optical instruments. Specific examples of building articles include windows, flooring materials, wall materials, and door materials. Specific examples of the electronic device article include display glass, display protective film, antireflection film, and fingerprint sensor in a communication terminal or image display device.

Note that the entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-103786 filed on May 30, 2018 is cited herein as the disclosure of the specification of the present invention. Incorporate.

Claims (15)

1. A vapor deposition material containing silicon oxide as a main component and containing 0.03 to 800 ppm by mass of a platinum group metal in a ratio to the silicon oxide.
2. The vapor deposition material according to claim 1, wherein a ratio of the silicon oxide to the total amount of the vapor deposition material is 65 to 99 mass%.
3. The vapor deposition material according to claim 1 or 2, wherein a ratio of the platinum group metal to the total amount of the vapor deposition material is 0.02 to 800 ppm by mass.
4. The vapor deposition material according to any one of claims 1 to 3, further comprising at least one of sodium oxide and calcium oxide.
5. The vapor deposition material according to claim 4, wherein the total of the sodium oxide and calcium oxide with respect to the silicon oxide is 0.1 to 13% by mass.
6. Components obtained by removing the platinum group metal from the vapor deposition material are expressed in terms of mass% in terms of oxide, SiO ₂ is 65 to 95%, Na ₂ O is 0 to 20%, CaO is 0 to 32%, Al ₂ O. The vapor deposition material according to any one of claims 1 to 5, comprising ₃ to 0 to 15% and MgO to 0 to 4%.
7. Components obtained by removing the platinum group metal from the vapor deposition material are expressed in terms of mass% in terms of oxide, SiO ₂ is 65 to 75%, Na ₂ O is 1 to 20%, CaO is 5 to 32%, Al ₂ O. The vapor deposition material according to any one of claims 1 to 6, which is soda lime glass containing 0 to 2% of ₃ and 0 to 4% of MgO.
8. The vapor deposition material according to any one of claims 1 to 7, wherein the platinum group metal is at least one selected from platinum and rhodium.
9. Silicon oxide containing silicon oxide as a main component and forming a silicon oxide layer on a substrate by vacuum deposition using a vapor deposition material containing 0.03 to 800 ppm by mass of a platinum group metal in a ratio to the silicon oxide. The manufacturing method of a base material with a layer.
10. Production of a substrate with a surface layer, wherein a surface layer is formed using an organic compound having a group capable of reacting with silicon oxide on the silicon oxide layer of the substrate with a silicon oxide layer obtained by the production method according to claim 9. Method.
11. The method for producing a substrate with a surface layer according to claim 10, wherein the organic compound contains a fluorine-containing compound.
12. The method for producing a substrate with a surface layer according to claim 11, wherein the fluorine-containing compound has a poly (oxyperfluoroalkylene) chain.
13. The method for producing a substrate with a surface layer according to any one of claims 9 to 12, wherein the fluorine-containing compound is a fluorine-containing ether compound represented by the following formula 1.
    [AO—Z ¹ — (R ^f O) _m —] _j Z ² [—SiR _n L _3-n ] _q Formula 1
    However, A is a perfluoroalkyl group or a _{-Q [-SiR n L 3-n} ] k. Q is a (k + 1) -valent linking group, and k is an integer of 1 to 10. R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer of 0-2.
    Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms or a poly (oxyfluoroalkylene) group in which one or more hydrogen atoms are substituted with fluorine atoms. R ^f is a perfluoroalkylene group. m is an integer of 2 to 200. Z ² is a (j + q) -valent linking group, j is an integer of 1 or more, and q is an integer of 1 or more.
14. The method for producing a substrate with a surface layer according to any one of claims 9 to 13, wherein a surface layer is formed on the silicon oxide layer by a vacuum deposition method using an organic compound having a group capable of reacting with silicon oxide. .
15. The method for producing a substrate with a surface layer according to any one of claims 9 to 14, wherein the thickness of the surface layer is 0.1 to 100 nm.