JP2008237957A - Water-repellent treatment method and substrate having water-repellent silica layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent treatment method capable of performing water-repellent treatment of substrate surface with preferable durability, and to provide a substrate having a water-repellent surface excellent in durability. <P>SOLUTION: The water-repellent treatment method of the substrate surface comprises: a process (1) of forming a coated film of polysilazane by applying polysilazane having -SiH<SB>2</SB>-NH- unit onto the surface of the substrate; a process (2) of attaching hydrophobic organosilane or hydrophobic polyorganosiloxane having silanol group or silicon atom-bound hydrolyzable group to the coated film; and a subsequent process (3) of converting the coated film into a silica layer and binding the organosilane or the polyorganosiloxane to silica of the silica layer by heating the substrate which undergoes the processes (1), (2). The substrate having water-repellent surface in which the silica layer derived from the polysilazan is formed on the surface of the substrate, and organosilane or polyorganosiloxane is bound to the silica of the silica layer is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for water-repellent treatment of a substrate surface and a substrate having a water-repellent silica layer.

Conventionally, many methods have been proposed for forming a silica coating on the surface of an inorganic substrate such as silicon or metal and modifying the surface. For example, Japanese Patent Laid-Open No. 62-88327 (Patent Document 1) discloses that a toluene solution of a polymer obtained from organocyclosilazane is applied on a silicon wafer, dried at room temperature, and then in the presence of oxygen or water vapor. Teaches a method of forming a silica film by high-temperature firing. Japanese Patent Application Laid-Open No. 9-157594 (Patent Document 2) applies a xylene solution of perhydropolysilazane on a stainless steel plate or metal, glass, ceramic, etc., and heats it at 450 ° C. in the air to form a silica film. Teaches how to do. Japanese Patent Laid-Open No. 10-194753 (Patent Document 3) teaches a method in which a xylene solution of perhydropolysilazane is applied on a silicon wafer, brought into contact with an amine compound and water vapor at room temperature, and then baked to form a silica film. is doing. Japanese Patent Application Laid-Open No. 2004-155834 teaches a method of forming a silica layer by applying a xylene solution of perhydropolysilazane containing an amine catalyst to the surface of metal, glass, ceramic, plastic, etc. and leaving it at room temperature. is doing.

However, these methods all relate to a method of forming a silica layer on the surface of an inorganic or organic base material such as silicon, metal, glass, ceramic, plastic, etc., and modifying it to a surface having heat resistance, wear resistance, and corrosion resistance. The surface of the substrate obtained by these methods does not have sufficient water repellency, for example, a substrate that frequently comes into contact with water or a hydrated material, a substrate used outdoors, and around the water It is not satisfactory as a base material used in the above.

On the other hand, the surface of an inorganic base material such as glass or metal is treated as a water repellent treatment method, for example, a method in which a liquid polydimersiloxane solution is coated on glass and baked, or a polymethylhydrogensiloxane solution containing a condensation reaction catalyst. A method of coating and heat treatment, (A) polydiorganosiloxane having a molecular chain terminal having a viscosity of 20 to 20,000 mPa · s blocked with a silanol group or a silicon atom-bonded hydrolyzable group, and (B) a hydrolyzable group-containing silane A method (Patent Document 5) of coating and curing a curable silicone composition comprising a system cross-linking agent, (C) a catalyst for condensation reaction, (D) an organic solvent, and the like is known and partly put into practical use. However, these water-repellent treatment methods hardly improve the heat resistance, wear resistance, and corrosion resistance of the surface of an inorganic base material such as glass or metal.

JP-A-62-88327 Japanese Patent Laid-Open No. 9-157594 Japanese Patent Laid-Open No. 10-194753 Japanese Patent Application Laid-Open No. 2004-155834 JP 2002-241695 A

As a result of intensive studies on methods for improving water repellency as well as heat resistance, wear resistance, and corrosion resistance on the surface of inorganic substrates such as metals, glass, and ceramics, the present inventors have found that a polysilazane coating is formed on the substrate surface. If it is formed, a hydrophobic organosilane having a silanol group or a silicon atom-bonded hydrolyzable group or a polyorganosiloxane having a hydrophobic property is attached thereto, followed by heating to convert the polysilazane coating to a silica coating. The present inventors have found that a substrate having an excellent water-repellent surface simultaneously with excellent heat resistance, wear resistance, and corrosion resistance and a surface with excellent water repellency durability can be obtained. That is, the object of the present invention is to improve the heat resistance, wear resistance, and corrosion resistance of the substrate surface and at the same time perform a water repellency treatment with excellent durability; excellent heat resistance, wear resistance, corrosion resistance and excellent water repellency; The object is to provide a substrate having a surface with excellent durability.

Furthermore, if a polysilazane film is formed on the surface of the substrate, a polyorganosiloxane having a hydroxyalkylene group or a hydroxyalkyleneoxyalkylene group is adhered thereto, and then heated to convert the polysilazane film to a silica film, it is excellent. The inventors have found that a substrate having an excellent water-repellent surface as well as heat resistance, wear resistance and corrosion resistance can be obtained, and the present invention has been achieved. That is, the object of the present invention is to improve the heat resistance, wear resistance and corrosion resistance of the substrate surface and at the same time perform a water repellent treatment; a group having an excellent water repellent surface simultaneously with excellent heat resistance, wear resistance and corrosion resistance. To provide materials.

で表される単位を有するポリシラザンの被膜を形成する工程、
(2) 該ポリシラザン被膜に、シラノール基またはケイ素原子結合加水分解性基を有する疎水性オルガノシランまたは疎水性ポリオルガノシロキサンを付着させる工程、
ついで、
(3) 前記工程を経た基材を加熱して、該ポリシラザン被膜をシリカ層に転化せしめ、該オルガノシランまたは該ポリオルガノシロキサンを該シリカ層のシリカに結合させる工程。
[2] ポリシラザンが、式(1):

で表される繰り返し単位からなる[1]請求項１記載の撥水処理方法。
[3] ポリシラザンが触媒量のシリカ転化促進触媒を含有するものである[2]に記載の撥水処理方法。
[4] シリカ転化促進触媒がアミン系触媒である[3]に記載の撥水処理方法。
[5] 疎水性オルガノシランが、一般式(2)：R_nX_(4-n)
（式中、Rは一価炭化水素基または疎水性基で置換された一価炭化水素基であり、Xはシラノール基またはケイ素原子結合加水分解性基であり、ｎは２または３である）で示されるものであることを特徴とする[1] 、[2] または[3]記載の撥水処理方法。
[6] ケイ素原子結合加水分解性基を有する疎水性ポリオルガノシロキサンの該ケイ素原子結合加水分解性基が、一般式(3)：

(式中、ＲとＲ¹は一価炭化水素基であり、Ｘ¹はケイ素原子結合加水分解基であり、Ｙは酸素原子またはアルキレン基であり、aは１または２である）で示されるものであることを特徴とする[1] 、[2] または[3]記載の撥水処理方法。
[7] ケイ素原子結合加水分解性基が、アルコキシ基、Ｎ−アルキルアミノ基、ジオルガノケトキシム基，Ｎ，Ｎ−ジアルキルアミノキシ基、アルケニルオキシ基、Ｎ−オルガノアシルアミド基、アシロキシ基、水素原子またはハロゲン原子であることを特徴とする[5]または[6]記載の撥水処理方法。
[8] 疎水性ポリオルガノシロキサンのポリオルガノシロキサンが、直鎖状ポリジオルガノシロキサンまたは分岐鎖状ポリオルガノシロキサンであり、シラノール基またはケイ素原子結合加水分解性基は分子鎖末端に位置することを特徴とする[1] 、[2] または[3]記載の撥水処理方法。
[9] 疎水性ポリオルガノシロキサンは、常温で液状であり、２５℃における粘度が１〜１００，０００ｍＰａ・ｓであることを特徴とする[1]または [8]記載の撥水処理方法。
[10] 直鎖状ポリジオルガノシロキサンが、両末端シラノール基封鎖ポリジオルガノシロキサンまたは片末端シラノール基封鎖ポリジオルガノシロキサンである[8] または[9]記載の撥水処理方法。
[11] 直鎖状ポリジオルガノシロキサンが、ポリジメチルシロキサン、ポリメチルフェニルシロキサンまたはポリメチルパーフロロアルキルシロキサンである[10]に記載の撥水処理方法。
[12] 基材が金属、ガラスまたはセラミックである[1]〜[11]のいずれかに記載の撥水処理方法。
[13] 金属がステンレススチールである[12]に記載の撥水処理方法。」に関する。 The present invention
“[1] A method for water-repellent treatment of a substrate surface, comprising the following steps.
(1) Formula (1) on the surface of the substrate:

Forming a polysilazane film having a unit represented by:
(2) attaching a hydrophobic organosilane or hydrophobic polyorganosiloxane having a silanol group or a silicon atom-bonded hydrolyzable group to the polysilazane coating;
Next,
(3) A step of heating the substrate having undergone the above step to convert the polysilazane film into a silica layer and bonding the organosilane or the polyorganosiloxane to the silica of the silica layer.
[2] Polysilazane has the formula (1):

[1] The water repellent treatment method according to claim 1, comprising a repeating unit represented by:
[3] The water-repellent treatment method according to [2], wherein the polysilazane contains a catalytic amount of a catalyst for promoting silica conversion.
[4] The water-repellent treatment method according to [3], wherein the silica conversion promotion catalyst is an amine catalyst.
[5] Hydrophobic organosilane is represented by the general formula (2): R _n X _(4-n)
(Wherein R is a monovalent hydrocarbon group substituted with a monovalent hydrocarbon group or a hydrophobic group, X is a silanol group or a silicon atom-bonded hydrolyzable group, and n is 2 or 3) The water-repellent treatment method according to [1], [2] or [3], wherein
[6] The silicon atom-bonded hydrolyzable group of the hydrophobic polyorganosiloxane having a silicon atom-bonded hydrolyzable group has the general formula (3):

Wherein R and R ¹ are monovalent hydrocarbon groups, X ¹ is a silicon-bonded hydrolyzing group, Y is an oxygen atom or an alkylene group, and a is 1 or 2. The water-repellent treatment method according to [1], [2] or [3], wherein
[7] The silicon-bonded hydrolyzable group is an alkoxy group, an N-alkylamino group, a diorganoketoxime group, an N, N-dialkylaminoxy group, an alkenyloxy group, an N-organoacylamide group, an acyloxy group, The water repellent treatment method according to [5] or [6], which is a hydrogen atom or a halogen atom.
[8] The polyorganosiloxane of the hydrophobic polyorganosiloxane is a linear polydiorganosiloxane or a branched polyorganosiloxane, and a silanol group or a silicon atom-bonded hydrolyzable group is located at a molecular chain end. The water repellent treatment method according to [1], [2] or [3].
[9] The water repellent treatment method according to [1] or [8], wherein the hydrophobic polyorganosiloxane is liquid at room temperature and has a viscosity of 1 to 100,000 mPa · s at 25 ° C.
[10] The water-repellent treatment method according to [8] or [9], wherein the linear polydiorganosiloxane is a silanol group-capped polydiorganosiloxane or a one-end silanol group-capped polydiorganosiloxane.
[11] The water-repellent treatment method according to [10], wherein the linear polydiorganosiloxane is polydimethylsiloxane, polymethylphenylsiloxane, or polymethylperfluoroalkylsiloxane.
[12] The water repellent treatment method according to any one of [1] to [11], wherein the substrate is a metal, glass, or ceramic.
[13] The water repellent treatment method according to [12], wherein the metal is stainless steel. ".

で表される単位を有するポリシラザンから誘導されたシリカ層が形成されており、該シリカ層の該シリカにSiOSi結合またはSiOSiASi (Aはアルキレン基である)結合により疎水性オルガノシランまたは疎水性ポリオルガノシロキサンが結合していることを特徴とする撥水性シリカ層を有する基材。
[15] 疎水性ポリオルガノシロキサンのポリオルガノシロキサンが直鎖状ポリジオルガノシロキサンまたは分岐鎖状ポリオルガノシロキサンであることを特徴とする[14]に記載の撥水性シリカ層を有する基材。
[16] 基材が金属、ガラスまたはセラミックであり、直鎖状ポリジオルガノシロキサンが直鎖状のポリジメチルシロキサン、ポリメチルフェニルシロキサンまたはポリメチルパーフロロアルキルシロキサンであることを特徴とする[15] または [16]記載の撥水性シリカ層を有する基材。
[17] シリカ層表面の水に対する接触角が８５〜１０５度である[14] 、[15] または[16]記載の撥水性シリカ層を有する基材。」に関する。 The present invention further relates to “[14] on the surface of the substrate, the formula (1):

A silica layer derived from polysilazane having a unit represented by formula (1) is formed, and a hydrophobic organosilane or a hydrophobic polyorganoorganism is formed on the silica of the silica layer by a SiOSi bond or SiOSiASi (A is an alkylene group) bond. A base material having a water-repellent silica layer, wherein siloxane is bonded.
[15] The substrate having a water-repellent silica layer according to [14], wherein the polyorganosiloxane of the hydrophobic polyorganosiloxane is a linear polydiorganosiloxane or a branched polyorganosiloxane.
[16] The substrate is a metal, glass or ceramic, and the linear polydiorganosiloxane is a linear polydimethylsiloxane, polymethylphenylsiloxane or polymethylperfluoroalkylsiloxane [15] Or A substrate having the water-repellent silica layer according to [16].
[17] A substrate having a water-repellent silica layer according to [14], [15] or [16], wherein the contact angle of water on the surface of the silica layer is 85 to 105 degrees. ".

で表される単位を有するポリシラザンを塗布してポリシラザン被膜を形成する工程、
(2) 該ポリシラザン被膜に、ヒドロキシアルキレン基もしくはヒドロキシアルキレンオキシアルキレン基を有するポリオルガノシロキサンを付着させる工程、
ついで、
(3) 前記工程を経た基材を加熱して、該ポリシラザン被膜をシリカ層に転化せしめ、該ポリオルガノシロキサンを該シリカ層のシリカに結合させる工程。
[19] 該ポリシラザンが、式(1)：

で表される繰り返し単位からなるペルヒドロポリシラザンであり、触媒量のシリカ転化促進触媒を含有するものである[18]記載の撥水処理方法。 [20] ヒドロキシアルキレン基がヒドロキシプロピレン基であり、ヒドロキシアルキレンオキシアルキレン基がヒドロキシエチレンオキシプロピレン基であり、ポリオルガノシロキサンがポリジオルガノシロキサンであり、ヒドロキシアルキレン基がポリジオルガノシロキサンの両末端または片末端に結合している[18] または[19]記載の撥水処理方法。」に関する。 The present invention further includes “[18] A method for water-repellent treatment of a substrate surface, comprising the following steps.
(1) On the surface of the substrate, the formula (1):

Applying polysilazane having a unit represented by the following to form a polysilazane film:
(2) attaching a polyorganosiloxane having a hydroxyalkylene group or a hydroxyalkyleneoxyalkylene group to the polysilazane coating;
Next,
(3) A step of heating the base material after the step to convert the polysilazane film into a silica layer and bonding the polyorganosiloxane to the silica of the silica layer.
[19] The polysilazane has the formula (1):

The water repellent treatment method according to [18], which is a perhydropolysilazane composed of a repeating unit represented by formula (1) and contains a catalytic amount of a catalyst for promoting silica conversion. [20] The hydroxyalkylene group is a hydroxypropylene group, the hydroxyalkyleneoxyalkylene group is a hydroxyethyleneoxypropylene group, the polyorganosiloxane is a polydiorganosiloxane, and the hydroxyalkylene group is at both ends or one end of the polydiorganosiloxane. The water repellent treatment method according to [18] or [19], wherein ".

で表される単位を有するポリシラザンから誘導されたシリカ層が形成されており、該シリカ層の該シリカにSiOC結合またはSiOAOC (Aはアルキレン基である)結合により疎水性ポリオルガノシロキサンが結合していることを特徴とする撥水性シリカ層を有する基材。」に関する。 The present invention further provides “[21] On the surface of the substrate, the formula (1):

A silica layer derived from polysilazane having a unit represented by the following formula is formed, and a hydrophobic polyorganosiloxane is bonded to the silica of the silica layer by a SiOC bond or SiOAOC (A is an alkylene group). A base material having a water-repellent silica layer. ".

According to the water repellent treatment method of the present invention, the water repellency can be remarkably improved while simultaneously improving the heat resistance, wear resistance and corrosion resistance of the surface of an inorganic base material such as metal, glass and ceramic. Moreover, the durability of water repellency is excellent.
The substrate having the water-repellent silica layer of the present invention has an excellent water-repellent surface as well as excellent heat resistance, wear resistance and corrosion resistance. Moreover, the durability of water repellency is excellent.

で表される単位を有するポリシラザンの被膜を形成する工程、
(2) 該ポリシラザン被膜に、シラノール基またはケイ素原子結合加水分解性基を有する疎水性オルガノシランまたは疎水性ポリオルガノシロキサンを付着させる工程、
ついで、
(3) 前記工程を経た基材を加熱して、該ポリシラザン被膜をシリカ層に転化せしめ、該オルガノシランまたはポリオルガノシロキサンを該シリカ層のシリカに結合させる工程。 The water-repellent treatment method for a substrate surface according to the present invention comprises the following steps.
(1) Formula (1) on the surface of the substrate:

Forming a polysilazane film having a unit represented by:
(2) attaching a hydrophobic organosilane or hydrophobic polyorganosiloxane having a silanol group or a silicon atom-bonded hydrolyzable group to the polysilazane coating;
Next,
(3) A step of heating the base material after the step to convert the polysilazane film into a silica layer and bonding the organosilane or polyorganosiloxane to the silica of the silica layer.

In the water-repellent treatment method of the present invention, there are various inorganic base materials (materials) and organic base materials (materials) as base materials to be subjected to the water-repellent treatment. Examples of the material of the inorganic base material include metals such as steel, stainless steel, aluminum, deuralumin, titanium, titanium alloy, and silver; glass, quartz, ceramic, ceramics, stones; silicon, and compound semiconductors. Synthetic resins such as polyethylene resin, polypropylene resin, acrylic resin, polyamide resin, polyester resin, polycarbonate resin, polyvinyl alcohol, poval resin, ABS resin, polyimide resin, epoxy resin, polyurethane resin, etc .; synthetic wood; bamboo Examples include natural materials such as wood.

Examples of the shape of the inorganic base material and the organic base material include plates, sheets, films, foils, tapes, blocks, tubes, cloths, container shapes, component shapes, member shapes, and article shapes. Such a base material is appropriately selected and used depending on the location to which the water-repellent-treated base material of the present invention is applied and the use of parts, members, articles and the like.

で表される単位を有することが好ましい。Ｓｉ−Ｎ（ケイ素−窒素）結合のＳｉ原子に２個の水素原子が結合していると、シリカへの転化が容易である。
このようなポリシラザンの分子構造は、直鎖状、分岐した直鎖状、分岐状、環状、架橋構造を有するもの、あるいは分子内にこれらの複数の構造を同時に有するものがある。本発明においては、これらを単独で、あるいは混合物で使用できる。これらポリシラザンの代表例としては、下記一般式(4)で示されるシラザン単位を繰り返し単位とする重合体等がある。ここで重合体はオリゴマーをも意味する。 In the step (1), the polysilazane covering the substrate surface is a polymer in which Si—N (silicon-nitrogen) bonds are repeated in the molecule, and the type thereof is not particularly limited as long as it can be easily converted to silica. . However, at least one formula (1) in the molecule:

It is preferable to have a unit represented by: When two hydrogen atoms are bonded to Si atoms of Si—N (silicon-nitrogen), conversion to silica is easy.
Such polysilazane has a molecular structure having a linear structure, a branched linear structure, a branched structure, a cyclic structure, a crosslinked structure, or a structure having a plurality of these structures simultaneously in the molecule. In the present invention, these can be used alone or in a mixture. Typical examples of these polysilazanes include a polymer having a silazane unit represented by the following general formula (4) as a repeating unit. Here, the polymer also means an oligomer.

（式中、Ｒ^１、Ｒ^２およびＲ^３は、水素原子またはメチル基、エチル基、プロピル基、ブチル基のような炭素原子数１〜８のアルキル基である。） General formula (4):

(Wherein R ¹ , R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group.)

From the viewpoint of easy conversion to silica, those containing units in which both R ¹ and R ² are hydrogen atoms are preferred, and those in which R ¹ and R ² in the molecule are all hydrogen atoms, particularly R ¹ , More preferably, R ² and R ³ are all hydrogen atoms. Polysilazane in which R ¹ , R ² and R ³ are all hydrogen atoms has a repeating unit represented by the following formula (5) and is called perhydropolysilazane or perhydropolysilazane.
Formula (5):

Perhydropolysilazane is said to have a chemical structure represented by the following formula (6).

The perhydropolysilazane may be one in which a part of hydrogen atoms bonded to a silicon atom is substituted with a hydroxyl group. Perhydropolysilazane can be easily synthesized by reacting dihydrogendichlorosilane with an organic base (for example, pyridine or picoline) to form an adduct, and reacting the adduct with ammonia.

The number average molecular weight of such polysilazane, especially perhydropolysilazane, is usually 100 to 50,000, and 200 to 2,500 is more preferable in terms of non-volatility during heating and solubility in a solvent.

Polysilazane, especially perhydropolysilazane, may contain a small amount of a catalyst for promoting the conversion of silica. Examples of the silica conversion promotion catalyst include organic amine compounds, organic acids, inorganic acids, carboxylic acid metal salts, and organic metal complex salts. Organic amine compounds are preferred, 1-methylpiperazine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 4,4′-trimethylenebis (1-methylpiperidine), diazabicyclo- [2,2,2]. Octane, cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4′- Nitrogen-containing cyclic organic amines such as trimethylenedipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, 1-methylpyrrolidine; methylamine, dimethylamine , Trimethylamine, ethylamine, die Ruamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, Aliphatic or aromatic amines such as octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine; DBU (1,8-diazabicyclo [5,4,0] 7-undecene), DBN (1 , 5-diazabicyclo [4,3,0] 5-nonene), 1,5,9-triazacyclododecane and 1,4,7-triazacyclononane.
The content of the silica conversion accelerating catalyst in the polysilazane, particularly perhydropolysilazane is preferably 0.1 to 10% by weight, more preferably 0.1 to 3% by weight.

In the step (2), when polysilazane, particularly perhydropolysilazane, is coated on the substrate, that is, coated, it is preferable to dissolve polysilazane, particularly perhydropolysilazane, in an organic solvent to prepare a solution. The organic solvent for that purpose is not particularly limited as long as it dissolves polysilazane, particularly perhydropolysilazane, imparts fluidity to the solution, and does not alter or decompose polysilazane, particularly perhydropolysilazane. Examples of such organic solvents include aromatic hydrocarbons such as toluene, xylene and hexylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; ethers such as dipropyl ether, dibutyl ether, dioxane, tetrahydrofuran and ethylene glycol diethyl ether. And ketones such as acetone and methyl ethyl ketone. These organic solvents are used alone or in combination of two or more.

Since water in the organic solvent hydrolyzes polysilazane, especially perhydropolysilazane, it is preferable to perform dehydration and drying in advance.
The solid content concentration of such polysilazane, especially polysilazane in the perhydropolysilazane solution, particularly perhydropolysilazane is preferably 0.1 to 35% by weight, and preferably 0.2 to 10% by weight. More preferred.

In step (1), in order to form a polysilazane, particularly a perhydropolysilazane film on the surface of the substrate, a liquid polysilazane, particularly perhydropolysilazane, or a solution of polysilazane, particularly perhydropolysilazane, is formed on the surface of the substrate. Apply and coat. Conventional coating methods and coating methods, that is, dip coating, roll coating, blade coating, brush coating, spraying, flow coating, spin coating and the like are used.

If the substrate is ground, degreased and surface-treated by various blasts before coating, the adhesion of polysilazane, particularly perhydropolysilazane, is improved.
Moreover, the produced | generated silica layer tends to adhere | attach the thing whose humidity was adjusted in the air of humidity 40-60% RH rather than what dried the base material.

When a polysilazane solution, particularly a perhydropolysilazane solution, is applied and coated, the organic solvent is evaporated by air drying, hot air drying, drying under reduced pressure, or the like after application and coating.

The thickness of the polysilazane on the substrate surface, particularly the perhydropolysilazane coating, may be appropriately selected according to the thickness of the target silica layer.
When the thickness of the silica layer on the surface of the substrate is 1 to 3000 nm, preferably 10 to 1500 nm, the thickness of the polysilazane, particularly the perhydropolysilazane coating, may be selected accordingly.

Next, the polysilazane coating on the surface of the substrate that has undergone the step (1), in particular the perhydropolysilazane coating, is a hydrophobic organosilane or hydrophobic polyorganosiloxane having silanol groups or silicon atom-bonded hydrolyzable groups, that is, silanol. A hydrophobic organosilane having a group, a hydrophobic organosilane having a silicon atom-bonded hydrolyzable group, a hydrophobic polyorganosiloxane having a silanol group, or a hydrophobic polyorganosiloxane having a silicon atom-bonded hydrolyzable group is attached.

Hydrophobic organosilanes have the general formula (3): R _a X _(4-a)
Wherein R is a monovalent hydrocarbon group substituted with a monovalent hydrocarbon group or a hydrophobic group, X is a silanol group or a hydrolyzable group, and a is 2 or 3. Is.
R is a monovalent hydrocarbon group substituted with a monovalent hydrocarbon group or a hydrophobic group. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, hexyl and decyl group; alkenyl groups such as vinyl group, allyl group and hexenyl; and phenyl group. As the monovalent hydrocarbon group substituted with a hydrophobic group, a perfluoroalkyl group such as 3,3,3-trifluoropropyl group, 4,4,4,3,3-pentafluorobutyl group, and a cyanoalkyl group are included. Illustrated.

As the number of carbon atoms of a monovalent hydrocarbon group substituted with a monovalent hydrocarbon group and a hydrophobic group increases, the hydrophobicity is improved, but if it is too large, it may become solid at room temperature. preferable.
X is a silanol group or a hydrolyzable group, and the hydrolyzable group is exemplified by the same group as X ¹ described later.
a is 2 or 3, but 3 is preferred in terms of hydrophobicity.
Preferred examples include dimethylalkylhydroxysilane, dimethylalkylchlorosilane, dimethylperfluoroalkylhydroxysilane, and dimethylperfluoroalkylchlorosilane.
Two or more hydrophobic organosilanes may be used in combination. Moreover, you may use together with hydrophobic polyorganosiloxane.

(式中、ＲとＲ¹は一価炭化水素基であり、Ｘ¹はケイ素原子結合加水分解性基であり、Ｙはアルキレン基または酸素原子であり、ａは１または２である。）で示される。
上式中、ＲとＲ¹である一価炭化水素基として、メチル基，エチル基，プロピル基，ブチル基等のアルキル基、ビニル基，アリル基等のアルケニル基、フェニル基が例示される。ともにメチル基が好ましい。ａは１または２であるが、１のほうが好ましい。 The silicon atom-bonded hydrolyzable group of the hydrophobic polyorganosiloxane having a silicon atom-bonded hydrolyzable group has the general formula (3):

Wherein R and R ¹ are monovalent hydrocarbon groups, X ¹ is a silicon-bonded hydrolyzable group, Y is an alkylene group or an oxygen atom, and a is 1 or 2. Indicated.
In the above formula, examples of the monovalent hydrocarbon group represented by R and R ¹ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as vinyl group and allyl group, and phenyl group. Both are preferably methyl groups. a is 1 or 2, but 1 is preferred.

X ¹ is a silicon atom-bonded hydrolyzable group such as an alkoxy group, an N-alkylamino group, a diorganoketoxime group, an N, N-dialkylaminoxy group, an alkenyloxy group, an N-organoacylamide group, an acyloxy group. , A hydrogen atom or a halogen atom. Hydrolyzable groups are preferred in which the by-product compound when hydrolyzed is volatile at room temperature or when heated.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a methoxyethoxy group, and a methoxypropoxy group.
Examples of the diorganoketoxime group include a methylketoxime group and a methylethylketoxime group. Examples of the acyloxy group include an acetoxy group and a propionoxy group. Examples of the N-alkylamino group include N-butylamino group, N-cyclohexylamino group, and N, N-diethylamino group.
Examples of the N-organoacylamide group include N-methylacetamide group and N-vinylacetamide group. Examples of N, N-dialkylaminoxy groups include N, N-diethylaminoxy groups. A propenoxy group is illustrated as an alkenyloxy group.

Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the halogen atom include chlorine and bromine.
Preferred examples of the siloxy group represented by the general formula (2) include dimethylmethoxysiloxy group, dimethylethoxysiloxy group, dimethylchlorosiloxy group, methyldimethoxysiloxy group, methylethoxysiloxy group, methyldichlorosiloxy group, dimethylmethoxysilylethyl Examples include a dimethylsiloxy group and a dimethylethoxysilylethyldimethylsiloxy group.

The polyorganosiloxane of the hydrophobic polyorganosiloxane is preferably a linear polydiorganosiloxane or a branched polyorganosiloxane in terms of water repellency, and a silanol group or a silicon atom bond in terms of the ability to bind to silica. The hydrolyzable group is preferably located at the end of the molecular chain.

（式中、Ｒは一価炭化水素基であり、ｎは０以上の数である）で表すことができる。 Polydiorganosiloxanes having silanol groups at both ends of the molecular chain are represented by molecular structural formula (7):

(Wherein, R is a monovalent hydrocarbon group, and n is a number of 0 or more).

In the above formula, R is a monovalent hydrocarbon group such as an alkyl group, an alkenyl group, a phenyl group, a perfluoroalkyl group, specifically, an alkyl group such as a methyl group, an ethyl group, or a propyl group; a vinyl group And an alkenyl group such as an allyl group; a phenyl group; a perfluoroalkyl group such as a 3,3,3-trifluoropropyl group and a 4,4,4,3,3-pentafluorobutyl group. Among these, at least 50 mol% is preferably a methyl group, more preferably a methyl group, a methyl group and a phenyl group, or a methyl group and a perfluoroalkyl group. n is a number of 0 or more, but is preferably a number that is liquid at room temperature and has a viscosity at 25 ° C. of 1 to 100,000 mPa · s. Usually, it is in the range of 1 to 2,000.

As specific examples of polydiorganosiloxane having silanol groups at both ends of the molecular chain, dimethylhydroxysiloxy group-blocked polydimethylsiloxane at both ends (the dimethylhydroxysiloxy group-blocked at both ends is also referred to as a silanol-blocked at both ends. ), Both ends dimethylhydroxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both ends dimethylhydroxysiloxy group-blocked methylphenylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / diphenylsiloxane copolymer And methyl (3,3,3-trifluoropropyl) polysiloxane and dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer blocked with dimethylhydroxysiloxy groups at both ends. Among these, polydimethylsiloxane, methylphenylpolysiloxane (including the above-described copolymer type) and polymethylperfluoroalkylsiloxane (including the above-mentioned copolymer type) having dimethylhydroxysiloxy group-blocked at both ends are preferable. The said polydiorganosiloxane may be used individually by 1 type, and may mix and use 2 or more types.

（式中、Ｒは一価炭化水素基であり、ｎは０以上の数である）で表すことができる。Ｒおよびｎは、分子構造式()について記載したものと同様である。 The polydiorganosiloxane having a silanol group at one end of the molecular chain is a polydiorganosiloxane in which one terminal hydroxyl group is substituted with R in the above molecular structural formula, and the molecular structural formula (8):

(Wherein, R is a monovalent hydrocarbon group, and n is a number of 0 or more). R and n are the same as those described for the molecular structural formula ().

A branched polyorganosiloxane having a silanol group at the end of the molecular chain is composed mainly of R ₂ SiO units in the main chain, but also RSiO _3/2 units, SiO _4/2 units, or RSiO _3/2 units and SiO. _This is a polyorganosiloxane composed of _4/2 units and having HOSiO _1/2 units bonded to the molecular chain ends (where R is a monovalent hydrocarbon group).

（式中、ＲとＲ¹は一価炭化水素基であり、Ｘ¹はケイ素原子結合加水分解性基であり、Ｙはアルキレン基または酸素原子であり、ａは１または２である。）で表すことができる。 The linear polydiorganosiloxane having a hydrolyzable group at the molecular chain end is
Molecular structural formula (9):

Wherein R and R ¹ are monovalent hydrocarbon groups, X ¹ is a silicon atom-bonded hydrolyzable group, Y is an alkylene group or an oxygen atom, and a is 1 or 2. Can be represented.

(式中、ＲとＲ¹は一価炭化水素基であり、Ｘ¹はケイ素原子結合加水分解性基であり、Ｙはアルキレン基または酸素原子であり、ａは１または２である。）で表わされるシロキサン単位が結合したポリオルガノシロキサンである。 A branched polyorganosiloxane having a hydrolyzable group at the end of the molecular chain has a main chain mainly composed of R ₂ SiO units, but also RSiO _3/2 units, SiO _4/2 units, or RSiO _3/2 units. And SiO _4/2 units, and at the molecular chain end, the formula (3):

Wherein R and R ¹ are monovalent hydrocarbon groups, X ¹ is a silicon-bonded hydrolyzable group, Y is an alkylene group or an oxygen atom, and a is 1 or 2. It is a polyorganosiloxane in which the represented siloxane units are bonded.

The silanol groups of polyorganosiloxanes having silanol groups at the molecular chain ends and the hydrolyzable groups of polyorganosiloxanes having silicon atom-bonded hydrolyzable groups at the molecular chain ends are generated by conversion of polysilazane, especially perhydropolysilazane. It is a functional group necessary for bonding with silica. The silicon atom-bonded hydrolyzable group is hydrolyzed to form a silanol group, which is bonded to silica produced by conversion of polysilazane, particularly perhydropolysilazane.

Hydrophobic polyorganosiloxanes such as linear polyorganosiloxanes and branched polyorganosiloxanes are liquid at normal temperature and have a viscosity at 25 ° C. in terms of applicability to the surface of polysilazanes, especially perhydropolysilazane coatings. It is preferably 1 to 100,000 mPa · s, and more preferably 5 to 20,000 mPa · s. When the viscosity at 25 ° C. exceeds 100,000 mPa · s, the applicability to the surface of the polysilazane, particularly the perhydropolysilazane coating, is improved by reducing the viscosity by heating or adding a volatile organic solvent.
Two or more hydrophobic polyorganosiloxanes may be used in combination. Moreover, you may use together with hydrophobic organosilane.

The hydroxyalkylene group of the polyorganosiloxane having a hydroxyalkylene group at the terminal can be represented by the formula: HO (CH ₂ ) _x- (wherein x is a number of 1 to 6). Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. The polyorganosiloxane is typically a linear polydiorganosiloxane. The hydroxyalkylene group is bonded to silicon atoms at both ends of the linear polydiorganosiloxane, or bonded to a silicon atom at one end. The polyorganosiloxane may be branched.

The hydroxyalkyleneoxyalkylene group of the polyorganosiloxane having a hydroxyalkyleneoxyalkylene group at both ends has the formula: HO (R ² O) _y (CH ₂ ) _x- (wherein R ² has 2 to 4 carbon atoms) An alkylene group, and y is a number of 1 to 6). Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group, and examples of the alkylene group include an ethylene group, a propylene group, and a butylene group.
The polyorganosiloxane is typically a linear polydiorganosiloxane. The hydroxyalkyleneoxyalkylene group is bonded to silicon atoms at both ends of the linear polydiorganosiloxane, or bonded to a silicon atom at one end. The polyorganosiloxane may be branched.

These linear polydiorganosiloxane and branched polyorganosiloxane are the same as the linear polydiorganosiloxane and branched polyorganosiloxane having a silanol group bonded to the terminal.

The hydroxyalkylene group of the polyorganosiloxane having a hydroxyalkylene group at the terminal and the hydroxyalkyleneoxyalkylene group of the polyorganosiloxane having a hydroxyalkyleneoxyalkylene group at the terminal are formed by conversion of polysilazane, particularly perhydropolysilazane. It is a functional group necessary for bonding. Polysilazane, particularly perhydropolysilazane, binds to the silica produced by conversion.

The polyorganosiloxane having a hydroxyalkylene group at the end and the polyorganosiloxane having a hydroxyalkyleneoxyalkylene group at the end are liquid at room temperature in terms of applicability to the surface of polysilazane, particularly perhydropolysilazane coating, The viscosity is preferably 1 to 100,000 mPa · s, more preferably 5 to 20,000 mPa · s. When the viscosity at 25 ° C. exceeds 100,000 mPa · s, the applicability to the surface of the polysilazane, particularly the perhydropolysilazane coating, is improved by reducing the viscosity by heating or adding a volatile organic solvent.
Two or more hydrophobic polyorganosiloxanes may be used in combination

The method for attaching the hydrophobic organosilane or hydrophobic polyorganosiloxane to the polysilazane formed on the substrate surface in the step (1), particularly the surface of the perhydropolysilazane coating, is not particularly limited. There are usual coating methods (coating methods), that is, dipping, brushing, spraying, flow coating, spin coating, roll coating, blade coating and the like. Of these, dipping, spraying, flow coating, and spin coating are preferred because they do not damage the polysilazane, particularly the perhydropolysilazane coating.

After coating, in order to increase the reactivity between polysilazane, particularly perhydropolysilazane, and hydrophobic organosilane or hydrophobic polyorganosiloxane, it is preferable to leave it for a while, for example, for 10 to 60 minutes. Further, when the hydrophobic organosilane or hydrophobic polyorganosiloxane is dissolved and diluted in a solvent and then applied, the solvent is preferably volatilized and removed before heating.

Finally, in the step (3), the polysilazane, particularly perhydropolysilazane, is converted into silica by heating the base material that has undergone the above two steps. The heating temperature at this time is preferably within a range of 100 ° C to 400 ° C, and more preferably within a range of 100 to 300 ° C. When polysilazane, especially perhydropolysilazane contains a silica conversion promoting catalyst, the heating temperature may be lower than the above temperature range, and is preferably about 50 to 230 ° C. The heating temperature and heating time are such that when the condensation reaction of polysilazane, especially perhydropolysilazane, and hydrophobic organosilane or hydrophobic polyorganosiloxane is sufficiently advanced and the substrate is organic, the substrate is thermally decomposed. It is preferable to select a condition that does not change or deteriorate.
Heating may be performed twice or more. The heating time depends on the heating temperature and is difficult to define, but is, for example, 10 minutes to 3 hours. The shorter the time, the higher the temperature.

Since heating includes oxygen gas and water vapor, heating in air is preferable. Instead of air, oxygen gas-containing nitrogen gas, water vapor-containing nitrogen gas, oxygen gas and water vapor-containing nitrogen gas, or ozone-containing air may be used.
Polysilazane, especially perhydropolysilazane, can also be converted to silica by electron beam irradiation.

The conversion rate from polysilazane, particularly perhydropolysilazane to silica is preferably 80% or more, more preferably 90% or more, and most preferably 98 to 100%.

After step (3), the hydrophobic organosilane or hydrophobic polyorganosiloxane is attached to the silica layer to which the hydrophobic organosilane or hydrophobic polyorganosiloxane is bonded, and bonded to the silica layer by heating or the like. The water repellency of the silica layer on the surface of the material is further improved. When using a hydrophobic polyorganosiloxane having two or more silanol groups or silicon atom-bonded hydrolyzable groups in one molecule in step (2), silanol groups or silicon atom-bonded hydrolyzable groups that do not bond to silica. Therefore, it is preferable to use a hydrophobic organosilane represented by the general formula (1) in which a = 1, or a one-end silanol-blocked polydiorganosiloxane. Further, hexaorganodisilazane such as hexamethyldisilazane may be used.

Next, the base material having a modified surface according to the present invention will be described. In the modified base material of the present invention, a silica layer, preferably a thin silica layer, that is, a thin silica layer is formed on the surface of the base material, and the silica layer adheres to or is bonded to the surface of the base material. . Hydrophobic organosilane or hydrophobic polyorganosiloxane is bonded to the silica of the silica layer by SiOSi bond or SiOSiA (A is an alkylene group) bond.
There is a silica layer on the surface of the substrate, and the proportion of silica to which hydrophobic organosilane or hydrophobic polyorganosiloxane is bonded increases as the surface of the silica layer is approached. Or the silica which hydrophobic organosilane or hydrophobic polyorganosiloxane couple | bonded exists substantially uniformly from the deep part of the silica layer to the surface.

The silica of the silica layer has a tetrafunctional siloxane unit represented by the formula: SiO _4/2 as a repeating unit. Examples of the method for forming such a silica layer include a method of hydrolytic condensation of tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane, a method of converting from polysilazane, particularly perhydropolysilazane, and the like. Among these, a silica layer converted from polysilazane, particularly perhydropolysilazane is preferable.

The thickness of the silica layer on the substrate surface is preferably 1 to 3000 nm, and more preferably 10 to 1500 nm. However, it is preferably 1 to 500 nm depending on the type of substrate and the surface condition. When the thickness is less than 1 nm, it is not easy to completely cover the surface when the surface of the substrate is uneven, and functions such as hydrophilicity tend to decrease. This is because if the thickness exceeds 3000 nm, the uniformity of the silica layer may be lowered, and the silica layer may be easily cracked. In addition, the thickness of the silica layer in the following Example is about 120-150 nm.
The thickness of the silica layer on the substrate surface can be determined by observing the cut surface with a field emission scanning electron microscope.

The hydrophobic organosilane or hydrophobic polyorganosiloxane is not simply physically attached to the silica of the silica layer. The silicon atom of the hydrophobic organosilane is bonded to the silicon atom of silica through an oxygen atom. That is, SiOSi bonds are generated. The silicon atom of the hydrophobic polyorganosiloxane is bonded to the silicon atom of silica through an oxygen atom. Alternatively, it is bonded to the silicon atom of silica via ASiO (A is an alkylene group). That is, a SiASiOSi bond is generated.

The polyorganosiloxane having a hydroxyalkylene group at the end and the polyorganosiloxane having a hydroxyalkyleneoxyalkylene group at the end are not merely physically attached to the silica of the silica layer. The carbon atom to which the hydroxyl group of the hydroxyalkylene group was bonded is bonded to the silicon atom of silica through the oxygen atom. That is, a COSi bond is generated. In addition, the carbon atom to which the hydroxyl group of the hydroxyalkyleneoxyalkylene group is bonded is bonded to the silicon atom of silica through the oxygen atom. That is, a COSi bond is generated.

The chemical bond of the hydrophobic organosilane, hydrophobic polyorganosiloxane or polyorganosiloxane to the silica of the silica layer, in particular the covalent bond to the silicon atom of the silica (Manufactured by JASCO Corporation, general-purpose Fourier transform infrared absorptiometer, RAS measurement (high sensitivity measurement), PAS measurement (photoacoustic method), X-ray photoelectron analyzer ESCA (Shimadzu ESCA- manufactured by Shimadzu Corporation) 1000AX), and can be estimated from the test results of Example 6.

The contact angle of water on the surface of the silica layer to which the hydrophobic organosilane, hydrophobic polyorganosiloxane or polyorganosiloxane is bonded is about 85 to 105 degrees, preferably about 90 to 105.
When the SiOSi bond is generated and when the SiASiOSi bond is generated, the substrate surface is not only excellent in water repellency but also excellent in durability. That is, even when washed repeatedly with an organic solvent such as xylene and toluene, the water repellency does not decrease, and even if the surface is rubbed strongly with a cloth, it does not peel off. Moreover, even if it immerses in water for a long time, a silica layer rarely peels off and water repellency hardly falls.

The formation of a silica layer on the surface of the substrate can be estimated by an increase in pencil hardness (pencil scratch value) according to 8.4.2 of JIS K5400. The pencil hardness of the stainless steel (SUS304) test plate surface is 6B, but a perhydropolysilazane film is formed on the stainless steel (SUS304) test plate surface, and a hydrophobic organosilane or hydrophobic polyorganosiloxane is applied on it. The pencil hardness on the surface of the specimen after heating at 150 ° C. for 30 minutes is 2H to 3H, which is greatly improved. Therefore, the modified substrate surface layer is excellent in wear resistance.

The silica layer on the surface of the substrate having the water-repellent silica layer and the binding of the hydrophobic organosilane, hydrophobic polyorganosiloxane or polyorganosiloxane to the silica of the silica layer can be known by glow discharge emission analysis. .
That is, it can be known by glow discharge on the silica layer on the surface of the specimen and measuring the change in light intensity of each element such as silicon, carbon, oxygen, hydrogen and the like with the sputtering time.

The substrate surface having the water-repellent silica layer is also excellent in chemical resistance. The chemical resistance can be known by immersing the test specimen in a chemical or a solution thereof and leaving it after standing for a predetermined time, and observing the surface state of the test specimen, or measuring the contact angle with water. The chemicals that can be tolerated by the modified substrate surface include polysilazane, hydrophobic organosilane, hydrophobic polyorganosiloxane, various organic solvents for dissolving polyorganosiloxane (xylene, toluene, perchloroethylene, trichloroethane), ethanol, Examples are mineral oil, hot water, saline, and physiological saline.

The substrate surface having the water-repellent silica layer has good release properties and lubricity.
The improvement in releasability can be evaluated by pressing an adhesive tape and measuring the peel resistance of the tape. The improvement in lubricity can be known by finger touch.

The compatibility of the modified substrate surface with the human body, particularly the biocompatibility, can be evaluated by a platelet adhesion test on the surface of the test body. That is, after the platelet-rich plasma obtained from human blood was brought into contact with the specimen surface at 37 ° C. for 1 hour, the specimen surface was washed with water to remove the platelet-rich plasma, and after air drying, a scanning electron microscope (SEM) To observe the degree of adhesion of platelets and proteins to the surface of the specimen. If platelets and proteins are not attached or if they are attached, contact compatibility with the human body (biocompatibility) is good, and a large number of platelets and proteins are attached, or even a small number of platelets If particles or / and protein particles are attached, it can be determined that the contact compatibility (biocompatibility) with the human body is poor.

Moreover, it can evaluate by the protein adsorption test to the test body surface. In other words, the specimen is immersed in an albumin aqueous solution or fibrinogen aqueous solution to adsorb proteins, immersed in a dilute aqueous solution of caustic soda containing a small amount of surfactant to remove the protein, and the removed protein aqueous solution becomes fluorescent. Add dye solution and measure fluorescence. If the fluorescence intensity is low, the amount of adsorbed protein is small, and it can be judged that the contact compatibility (biocompatibility) with the human body is good. When the fluorescence intensity is high, many proteins are adsorbed, and therefore it can be determined that the contact compatibility (biocompatibility) with the human body is poor.

Examples of the substrate on which the silica layer is laminated are the same as those exemplified in the water repellent treatment method for the substrate surface.

Since the substrate having the water-repellent silica layer of the present invention as described above has a surface having excellent water repellency, durability, abrasion resistance and chemical resistance, such as a metal column, capillary, filler, tube, etc. It is suitable as a member for analytical instruments. Moreover, it is suitable as physics and chemistry equipments such as laboratory glassware, stainless steel spatula, and fungus culture dishes. Moreover, it is suitable as household goods, such as tableware, a knife, a fork, and a spoon. Moreover, it is suitable as housing environmental materials, such as a tile, a pipe, plate glass, and a screen door.

Furthermore, since proteins in blood and body fluids are difficult to adsorb, it is used for medical purposes such as injection needles, catheters, scalpels, scissors, clips, artificial joints, artificial bones, screws, nuts, plates, fixing devices, wires, and stents. It is suitable as a member for treating teeth such as an implant or a bracket, a tool or instrument; a member for ornaments such as earrings, earrings, necklaces, watches, etc .: a barber / beauty salon or the like.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. In Examples and Comparative Examples, the molecular structural formula is an average formula. The surface characteristics of the specimen were measured, evaluated and observed as follows.
[Contact angle of water on the specimen surface]
A water drop was dropped on the surface of the specimen at 25 ° C., and the contact angle with respect to the water drop was measured using a QI optical mirror type contact angle meter {manufactured by Kyowa Interface Science Co., Ltd.}. The contact angle was measured by measuring the angle θ1 of the straight line connecting the left and right end points and the vertex of the droplet with respect to the substrate surface, and using a θ / 2 method in which the contact angle θ is a value obtained by doubling the angle.
The test specimen immersed in water was air-dried and the contact angle was measured.

[Pencil hardness of the specimen surface (pencil scratch value)]
The surface of the test specimen was scratched with a pencil core having a hardness of 6B to 9H according to JIS K5400 8.4.2, and indicated as the maximum hardness of the pencil with no scratches.

[Physical modification state of specimen surface]
The roughness of the surface of the test specimen was observed using an atomic force surface roughness meter {manufactured by Seiko Instruments Inc., atomic force surface roughness meter Nanopics NPX100}.

[Platelet adhesion test on specimen surface]
Platelet-rich plasma obtained from human blood was brought into contact with the specimen surface at 37 ° C. for 1 hour, then the specimen surface was washed with water to remove the platelet-rich plasma, and air-dried and then tested with a scanning electron microscope (SEM) The degree of adhesion of platelets and proteins to the body surface was observed.

[Protein adsorption test on specimen surface]
The test specimen was immersed in a PBS buffer solution for 12 hours and removed, and then the test specimen was immersed in a 1.0 mg / ml albumin aqueous solution or a 0.2 mg / ml fibrinogen aqueous solution at 30 ° C. for 1 hour to adsorb proteins to the specimen surface. .
After rinsing the test sample on which protein was adsorbed with deionized water, the sample was immersed in 0.01N NaOH aqueous solution containing 1% by weight of Triton X-100 and 1% by weight of sodium dodecyl sulfate, and placed in a centrifuge at 100 rpm. The protein adsorbed on the surface of each specimen was desorbed over 1 hour.
The test body was taken out from the 0.01N NaOH aqueous solution containing the desorbed protein, and 0.05M boric acid KCl aqueous solution was added to the aqueous solution to adjust to pH 9.3 (weakly basic).
Add 2 ml of this weakly basic aqueous solution into the 4-way cell of the fluorescence spectrophotometer, and then add 0.5 ml of a fluorescamine solution dissolved in an acetone aqueous solution (acetone: water mixing ratio = 3: 2), and then measure the fluorescence. went.
Albumin was measured for fluorescence under the conditions of a fluorescence wavelength of 590 nm and an excitation wavelength of 520 nm, and fibrinogen with a fluorescence wavelength of 490 nm and an excitation wavelength of 430 nm.

（粘度90〜120mPa・s：、分子量；4200、水酸基含有量：0.8〜0.9％）
を塗布し、室温にて大気中に１時間放置した。 [Example 1]
Perhydropolysilazane (trade name N-P110, manufactured by Clariant Japan Co., Ltd., amine type) having-(SiH ₂ -NH)-as a repeating unit on the surface of a stainless steel (SUS304) test plate (contact angle with water: 79 degrees) 2 wt% xylene solution of catalyst) was applied. The coating amount at this time was an amount by which a perhydropolysilazane film having a thickness of 100 to 180 nm was formed. The test plate was allowed to stand and air dried.
Immediately after the xylene is removed, both ends of the silanol group-blocked polydimethylsiloxane having the following molecular structural formula (10) are sold on the perhydropolysilazane coating (available from Gelest. The following properties are disclosed by Gelest. Is a characteristic)
Molecular structural formula (10):

(Viscosity 90 to 120 mPa · s :, molecular weight; 4200, hydroxyl group content: 0.8 to 0.9%)
Was applied and left in the atmosphere at room temperature for 1 hour.

Next, this test plate was put in an electric furnace and heated in air at 150 ° C. for 30 minutes. After cooling, xylene was allowed to flow over the surface of the silica layer of this test plate to wash away polydimethylsiloxane not bonded to the silica layer. Furthermore, the silica layer surface of the test plate was wiped with a tissue to remove polydimethylsiloxane not bonded to the silica layer.
Subsequently, it was left to stand in the atmosphere at room temperature for 24 hours and air-dried.
After confirming that there was no xylene odor, the test plate was placed in an electric furnace and heated in air at 150 ° C. for 30 minutes.
The obtained test body was allowed to cool and then immersed in xylene at 25 ° C. for 24 hours and taken out. When the contact angle with respect to water of the surface of the silica layer (to which the polydimethylsiloxane was bonded) was measured, it was the same as before immersion.

About the obtained test body, when the pencil hardness of the silica layer (The said polysiloxane layer has couple | bonded with this) was measured, it was 4H or more.
About the obtained test body, even if the surface of the silica layer was rubbed with Kimwipe (registered trademark of Kimbarik Clark Worldwide, non-woven fabric) more than 10 times in running water, the surface silica layer was not peeled off.

[Comparative Example 1]
In Example 1, 2% by weight xylene solution of perhydropolysilazane (manufactured by Clariant Japan Co., Ltd., trade name NP110, containing amine catalyst) on the surface of a stainless steel (SUS304) test plate (contact angle with water: 79 degrees) Except for not coating, both ends silanol group-blocked polydimethylsiloxane were coated under the same conditions, but the coating was difficult.

[Example 2]
In Example 1, instead of a stainless steel (SUS304) test plate, a glass test plate (contact angle with water: 43 °) was used, and the other conditions were the same as those for the coating of perhydropolysilazane and polydimethylsiloxane, and heat treatment. And water repellent treatment. About the obtained test body, immediately after preparation, after immersion for 1 day, 2 days, 3 days, 4 days, 7 days, 14 days and 21 days in 25 ° C. pure water, and in air at 25 ° C. for 2 days The contact angle with water of the surface of the silica layer (to which the polydimethylsiloxane was bound) was measured after standing on the 3rd, 4th, 7th, 14th and 21st. The measurement results are shown in FIG.
The obtained specimen was allowed to cool and then immersed in warm water at 50 ° C. for 24 hours, but there was no change in the silica layer (to which the polysiloxane was bound).
Even if the obtained specimen was allowed to cool and then immersed in xylene at 25 ° C. for 24 hours, the silica layer (to which the polydimethylsiloxane was bonded) did not change, and the contact angle with water ( 96 degrees) did not decrease.

[Comparative Example 2]
In Example 2, both terminal silanol groups were used under the same conditions except that a 2% by weight xylene solution of perhydropolysilazane (manufactured by Clariant Japan Co., Ltd., trade name NP110, containing amine catalyst) was not applied to the glass test plate surface. Capped polydimethylsiloxane was applied and heat treated. About the obtained test body, immediately after preparation, after immersion for 1 day, 2 days, 3 days, 4 days, 7 days, 14 days and 21 days in 25 ° C. pure water, and in air at 25 ° C. for 2 days The contact angle with water of the surface of the silica layer (to which the polydimethylsiloxane was bound) was measured after standing on the 3rd, 4th, 7th, 14th and 21st. The measurement results are shown in FIG.

[Example 3]
In Example 2, instead of polydimethylsiloxane, a polymethylphenylsiloxane-polydimethylsiloxane copolymer of the following molecular structural formula (11) (abbreviated as PMPS-PDMS) or a polymethyl (3 , 3,3-trifluoropropyl) siloxane (abbreviated as PTFS), a test specimen was prepared under the same conditions, and the water on the surface of the silica layer (to which the polysiloxane was bonded) was prepared. The contact angle with respect to was measured.

（粘度；2000〜3000 mPa・s、分子量；35000、水酸基含有量：0.7〜1.3％、ジフェニルシロキサン単位：2.5〜3.5モル％）
分子構造式(12)

（粘度；150〜250 mPa・s、分子量；800〜1200、水酸基含有量：3〜5％） Molecular structural formula (11):

(Viscosity: 2000 to 3000 mPa · s, molecular weight: 35000, hydroxyl group content: 0.7 to 1.3%, diphenylsiloxane unit: 2.5 to 3.5 mol%)
Molecular structural formula (12)

(Viscosity: 150-250 mPa · s, molecular weight: 800-1200, hydroxyl group content: 3-5%)

The contact angle with respect to water of the surface of the silica layer (to which the polysiloxane was bonded) of the test specimen prepared using PMPS-PDMS was 96 degrees. The contact angle with water on the surface of the silica layer (to which the polysiloxane was bonded) of the specimen prepared using PTFS was 96 degrees.
A specimen prepared using PTFS was immersed in warm water at 50 ° C. for 24 hours, but there was no change in the silica layer (to which the polysiloxane was bonded).

[Comparative Example 3]
Perhydropolysilazane (made by Clariant Japan Co., Ltd., trade name N-) having-(SiH ₂ -NH)-as a repeating unit on the surface of a glass test plate and stainless steel (SUS304) test plate (contact angle with water: 79 degrees) 2 wt% xylene solution of P110, containing amine catalyst) was applied. The coating amount at this time was an amount by which a perhydropolysilazane film having a thickness of 100 to 180 nm was formed. The test plate was allowed to stand and air dried.
After xylene was removed, the test plate was placed in an electric furnace and heated in air at 150 ° C. for 30 minutes. After cooling, xylene was allowed to flow over the surface of the silica layer of the test plate, and left in the air at room temperature for 24 hours to be air-dried.
After confirming that there was no xylene odor, the test plate was placed in an electric furnace and heated in air at 150 ° C. for 30 minutes.
The obtained glass specimen and stainless steel specimen were allowed to cool and the contact angles of the test specimen with respect to the silica layer surface to water were measured to be 98 degrees and 80 degrees, respectively.

[Comparative Example 4]
A 2% by weight xylene solution of perhydropolysilazane (manufactured by Clariant Japan Co., Ltd., trade name N-P110, containing amine catalyst) was applied to the surface of a stainless steel (SUS304) test plate (contact angle with water: 79 degrees). . The coating amount was such that a perhydropolysilazane film having a thickness of 100 to 180 nm was formed. The test plate was allowed to stand and air dried. It was 71 degree | times when the contact angle with respect to the water of the obtained test body surface was measured.

[Example 54]
The silica layer of the test specimen prepared in Example 2 (to which the polydimethylsiloxane was bonded) (contact angle with water: 96 degrees) was immersed in a toluene solution containing trimethylchlorosilane and triethylamine, and about 5 Heated to reflux for hours. After completion of the reaction, the sample was sequentially washed with THF, MeOH, and 50% MeOH aqueous solution, and finally the test specimen was immersed in 50% MeOH aqueous solution and heated and washed at 50 ° C. for 3 hours. It was 98 degree | times when the contact angle with respect to the water of the obtained test body surface was measured.

または、下記式で表される両末端ヒドロキシエチレンオキシプロピレン基封鎖ポリジメチルシロキサン（Polymer Source社製、商品名P4319-DMS2OH、数平均分子量；4500、Mn/Mw = 1.5）
分子構造式（14）：

を使用し、その他は同一条件で試験体を作成した。作成直後と、２５℃の水に１日間浸漬後と、２５℃の水に５日間浸漬後に、そのシリカ層（これには上記ポリジメチルシロキサンが結合している）の水に対する接触角を測定した。 [Example 5]
The test specimen prepared in Example 2 (to which the above-mentioned polydimethylsiloxane was bonded) (contact angle with water: 96 degrees) was mixed with low-viscosity silanol group-blocked polydimethylsiloxane (viscosity: 16 to 32 mPa). S, molecular weight: 400 to 700, hydroxyl group content: 4.5 to 7.5%) was applied and allowed to stand in the atmosphere at room temperature for 1 hour to air dry.
Next, the test specimen was placed in an electric furnace and heated in air at 150 ° C. for 30 minutes. After cooling, the water repellency of the silica layer surface was evaluated.

[Example 6]
In Example 2, instead of both-end silanol group-capped polydimethylsiloxane, one-end hydroxyethyleneoxypropylene group-capped polydimethylsiloxane (DMSOH) represented by the following molecular structural formula (13) (trade name, manufactured by Polymer Source) P4318-DMSOH, number average molecular weight; 5000, Mn / Mw = 1.1)
Molecular structural formula (13):

Alternatively, both end hydroxyethyleneoxypropylene group-blocked polydimethylsiloxane represented by the following formula (manufactured by Polymer Source, trade name P4319-DMS2OH, number average molecular weight; 4500, Mn / Mw = 1.5)
Molecular structural formula (14):

The test specimens were prepared under the same conditions. Immediately after preparation, after immersion in water at 25 ° C. for 1 day, and after immersion in water at 25 ° C. for 5 days, the contact angle of the silica layer (to which the polydimethylsiloxane was bonded) was measured. .

Also for the glass specimen prepared in Example 2, immediately after the preparation, after immersion in water at 25 ° C. for 1 day, and after immersion in water at 25 ° C. for 5 days, the silica layer (with polydimethylsiloxane bonded thereto) The contact angle with water was measured. The measurement results are shown in Table 1.

[Comparative Example 5]
In Example 6, 2% by weight xylene solution of perhydropolysilazane (manufactured by Clariant Japan Co., Ltd., trade name NP110, containing amine catalyst) was not applied to the surface of the glass test plate (contact angle with water: 43 degrees). Apply the single-end hydroxyethyleneoxypropylene group-blocked polydimethylsiloxane (P4318-DMSOH) or both-end hydroxyethyleneoxypropylene group-blocked polydimethylsiloxane (P4319-DMS2OH) under the same conditions and heat-treat the test specimen. Created. About the obtained glass test body, immediately after preparation, after immersion for 1 day in water at 25 ° C. and after immersion for 5 days in water at 25 ° C., the silica layer (to which the polydimethylsiloxane is bonded) The contact angle of water with respect to water was measured. The measurement results are shown in Table 2.

About the glass test body created in Comparative Example 2, immediately after creation, after immersion in water at 25 ° C. for 1 day, and after immersion in water at 25 ° C. for 5 days, the silica layer (with polydimethylsiloxane bonded thereto) The contact angle with water was measured. The measurement results are shown in Table 2.

[Example 7]
The glass test plate used in Example 2, the glass test sample prepared in Comparative Example 3 (having a silica layer derived from perhydropolysilazane on the surface), and the glass test sample prepared in Example 2 (perhydropolysilazane on the surface) A protein adsorption test on the surface of the test specimen was conducted on a silica layer having a derived silica layer and polydimethylsiloxane bonded thereto, and the results are shown in Table 3.

A glass test plate surface used in Example 2, - _(SiH 2 -NH) - perhydropolysilazane to repeating unit (AZ Electronic Materials Co., Ltd., trade name: NP110, amine catalyst content) 2 wt% A xylene solution was applied. The coating amount at this time was an amount by which a perhydropolysilazane film having a thickness of 100 to 180 nm was formed. The test plate was allowed to stand and air dried.
Immediately after the xylene was removed, polydimethylsiloxane in which one chlorine atom was bonded to silicon atoms at both ends on the perhydropolysilazane coating (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight 3000, viscosity 3 mPa · s). ) And left in the atmosphere at room temperature for 1 hour.
Next, this test plate was put in an electric furnace and heated in air at 150 ° C. for 30 minutes. After cooling, xylene was allowed to flow on the surface of the silica layer of the test plate to wash away the polydimethylsiloxane not bonded to the silica layer. Further, the silica layer surface of the test plate was wiped with a tissue to remove the polydimethylsiloxane not bonded to the silica layer. Subsequently, it was left to stand in the atmosphere at room temperature for 24 hours and air-dried. The contact angle of water on the silica layer surface with respect to water was 90 degrees.

Since the substrate having a water-repellent treated surface of the present invention has a surface having excellent water repellency, durability, abrasion resistance and chemical resistance, an analytical instrument such as a metal column, capillary, filler, tube, etc. It is suitable as a member for use. Moreover, it is suitable as physics and chemistry equipments such as laboratory glassware, stainless steel spatula, and fungus culture dishes. Moreover, it is suitable as household goods, such as tableware, a knife, a fork, and a spoon. Moreover, it is suitable as housing environmental materials, such as a tile, a pipe, plate glass, and a screen door.

Furthermore, since proteins in blood and body fluids are difficult to adsorb, it is used for medical purposes such as injection needles, catheters, scalpels, scissors, clips, artificial joints, artificial bones, screws, nuts, plates, fixing devices, wires, and stents. It is suitable as a member for treating teeth such as an implant or a bracket, a tool or instrument; a member for ornaments such as earrings, earrings, necklaces, watches, etc .: a barber / beauty salon or the like.

It is a graph which shows the measurement result of the contact angle with respect to the water of the silica layer of the test body obtained in Example 2 and Comparative Example 2.

Claims (21)

A water-repellent treatment method for a substrate surface, comprising the following steps.
(1) Formula (1) on the surface of the substrate:

Forming a polysilazane film having a unit represented by:
(2) attaching a hydrophobic organosilane or hydrophobic polyorganosiloxane having a silanol group or a silicon atom-bonded hydrolyzable group to the polysilazane coating;
Next,
(3) A step of heating the substrate having undergone the above step to convert the polysilazane film into a silica layer and bonding the organosilane or the polyorganosiloxane to the silica of the silica layer. Polysilazane has the formula (1):

The water-repellent treatment method according to claim 1, comprising a repeating unit represented by: The water repellent treatment method according to claim 2, wherein the polysilazane contains a catalytic amount of a catalyst for promoting silica conversion. The water repellent treatment method according to claim 3, wherein the silica conversion promotion catalyst is an amine catalyst. Hydrophobic organosilane is represented by the general formula (2): R _n X _(4-n)
(Wherein R is a monovalent hydrocarbon group substituted with a monovalent hydrocarbon group or a hydrophobic group, X is a silanol group or a silicon atom-bonded hydrolyzable group, and n is 2 or 3) The water repellent treatment method according to claim 1, wherein The silicon atom-bonded hydrolyzable group of the hydrophobic polyorganosiloxane having a silicon atom-bonded hydrolyzable group has the general formula (3):

Wherein R and R ¹ are monovalent hydrocarbon groups, X ¹ is a silicon-bonded hydrolyzing group, Y is an oxygen atom or an alkylene group, and a is 1 or 2. The water repellent treatment method according to claim 1, wherein the water repellent treatment method is used. A silicon atom-bonded hydrolyzable group is an alkoxy group, N-alkylamino group, diorganoketoxime group, N, N-dialkylaminoxy group, alkenyloxy group, N-organoacylamide group, acyloxy group, hydrogen atom or The water repellent treatment method according to claim 5, wherein the water repellent treatment method is a halogen atom. The polyorganosiloxane of the hydrophobic polyorganosiloxane is a linear polydiorganosiloxane or a branched polyorganosiloxane, and a silanol group or a silicon atom-bonded hydrolyzable group is located at a molecular chain end. Item 4. The water repellent treatment method according to Item 1. The water-repellent treatment method according to claim 1 or 8, wherein the hydrophobic polyorganosiloxane is liquid at room temperature and has a viscosity of 1 to 100,000 mPa · s at 25 ° C. The water-repellent treatment method according to claim 8, wherein the linear polydiorganosiloxane is a silanol group-blocked polydiorganosiloxane or a terminal silanol-blocked polydiorganosiloxane. The water repellent treatment method according to claim 10, wherein the linear polydiorganosiloxane is polydimethylsiloxane, polymethylphenylsiloxane, or polymethylperfluoroalkylsiloxane. The water repellent treatment method according to claim 1, wherein the substrate is metal, glass, or ceramic. The water repellent treatment method according to claim 12, wherein the metal is stainless steel. Formula (1) on the surface of the substrate:

A silica layer derived from polysilazane having a unit represented by formula (1) is formed, and a hydrophobic organosilane or a hydrophobic polyorganoorganism is formed on the silica of the silica layer by a SiOSi bond or SiOSiASi (A is an alkylene group) bond. A base material having a water-repellent silica layer, wherein siloxane is bonded. The substrate having a water-repellent silica layer according to claim 14, wherein the polyorganosiloxane of the hydrophobic polyorganosiloxane is a linear polydiorganosiloxane or a branched polyorganosiloxane. 16. The repellent material according to claim 15, wherein the substrate is metal, glass or ceramic, and the linear polydiorganosiloxane is linear polydimethylsiloxane, polymethylphenylsiloxane or polymethylperfluoroalkylsiloxane. A substrate having an aqueous silica layer. The substrate having a water-repellent silica layer according to claim 14, wherein a contact angle of water on the surface of the silica layer is 85 to 105 degrees. A water-repellent treatment method for a substrate surface, comprising the following steps.
(1) On the surface of the substrate, the formula (1):

Applying polysilazane having a unit represented by the following to form a polysilazane film:
(2) attaching a polyorganosiloxane having a hydroxyalkylene group or a hydroxyalkyleneoxyalkylene group to the polysilazane coating;
Next,
(3) A step of heating the base material after the step to convert the polysilazane film into a silica layer and bonding the polyorganosiloxane to the silica of the silica layer. The polysilazane has the formula (1):

The water-repellent treatment method according to claim 18, which is a perhydropolysilazane composed of a repeating unit represented by formula (1) and contains a catalytic amount of a catalyst for promoting silica conversion. The hydroxyalkylene group is a hydroxypropylene group, the hydroxyalkyleneoxyalkylene group is a hydroxyethyleneoxypropylene group, the polyorganosiloxane is a polydiorganosiloxane, and the hydroxyalkylene group is bonded to both ends or one end of the polydiorganosiloxane. The water repellent treatment method according to claim 18. Formula (1) on the surface of the substrate:

A silica layer derived from polysilazane having a unit represented by the following formula is formed, and a hydrophobic polyorganosiloxane is bonded to the silica of the silica layer by a SiOC bond or SiOAOC (A is an alkylene group). A base material having a water-repellent silica layer.

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