JP2013244470A - Coating method for fluorine-containing dry coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating method for a fluorine-containing dry coating agent not influenced by lots of a fluorine-containing organic silane compound, and capable of uniformly and widely forming a film on a substrate.SOLUTION: A coating method for a fluorine-containing dry coating agent is characterized by carrying out dry coating on a substrate by using a coating agent which is prepared by diluting 100 pts.mass of a fluorine-containing organic silane compound with 100 to 99,900 pts.mass of a solvent for the fluorine-containing dry coating agent, the solvent for the fluorine-containing dry coating agent containing (A) at least one kind selected from fluorine-based solvents having a boiling point of 100°C or higher and less than 135°C under normal pressure, and (B) at least one kind selected from fluorine-based solvents having a boiling point of 80°C or higher and less than 200°C under normal pressure, and different from the (A) component, and having a mass ratio of (A)/(B) of 95/5 to 5/95.

Description

  The present invention relates to a coating method for depositing a fluorine-containing dry coating agent uniformly and over a wide range on a substrate.

  Conventionally, an optical member with an antireflection film such as a lens or a polarizing plate is likely to be contaminated by sweat, fingerprints, sebum, cosmetics, etc. when used by humans. Because of the unevenness, it is not easy to remove the dirt. Furthermore, only the portion where such dirt is attached becomes highly reflective, and the dirt is conspicuous, which is a problem.

  As means for solving such a problem, a method of forming a thin film of a fluorine-containing compound having antifouling property or water repellency on the surface of an optical member has been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 5-215905), a vacuum deposition method using an evaporation source in which a sintered filter made of metal powder is impregnated with fluoroalkylsilazane or the like is disclosed in Patent Document 2 (Japanese Patent Application Laid-Open No. 5-215905) (Kaihei 8-143332) discloses a vacuum deposition method using an evaporation source in which steel wool is impregnated with fluoroalkylsilazane.

  For the impregnation of the fluorine-containing compound into the vapor deposition source used in such a vacuum evaporation method, a fluorine-containing compound diluted with a solvent is used, but materials having excellent antifouling properties generally have a large molecular weight. Since it does not dissolve, it is common to use a fluorinated solvent. This impregnation vapor deposition source once evaporates the fluorine-based solvent that is a dilution solvent, and then forms an antifouling layer on the substrate to be treated by a vacuum vapor deposition method, but this dilution solvent does not evaporate completely, It has been confirmed that the remaining solvent has a significant effect on the transpiration during vacuum deposition.

  On the other hand, in the method of depositing the antifouling layer on the substrate to be processed by the batch type vacuum deposition method, particularly in the case of a high molecular weight fluorine-containing compound, the adhesion of the outer periphery of the substrate to be processed is small. The transpiration may vary between lots, and in this case, a treatment such as reprocessing is required, which is a big problem in terms of productivity.

JP-A-5-215905 JP-A-8-143332

  The present invention has been made in view of the above circumstances, and provides a coating method of a fluorine-containing dry coating agent that can be uniformly and widely formed on a substrate without being affected by the lot of the fluorine-containing organosilane compound. Objective.

  As a result of intensive studies to achieve the above object, the present inventor has obtained a fluorine-containing dry coating in which a fluorine-containing organosilane compound is diluted with a mixed solvent of two or more types of fluorine-based solvents having a specific boiling range. By carrying out vacuum deposition using an agent, it was found that the lack of transpiration caused by production lot blurring of the fluorine-containing organosilane compound can be resolved, and it is possible to form a film on the substrate uniformly and over a wide range, thus forming the present invention. It came to.

（式中、Ｘは加水分解性基であり、Ｒ¹は炭素数１〜１０の一価炭化水素基であり、Ｒ²は水素原子又は炭素数１〜１０の一価炭化水素基であり、ＱはＮＨ基を介在してもよい炭素数１〜１０のアルキレン基である。ｍは１５〜５０の整数であり、ｎは２又は３である。）

（式中、Ｒｆ¹は、−（Ｃ_tＦ_2t）Ｏ−（ｔは１〜６の整数）で表される単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基を示し、Ｒ³は炭素数１〜１０の一価炭化水素基を示し、Ｘ¹は加水分解性基又はハロゲン原子を示す。ｐは独立に０、１又は２、ｑは独立に１〜５の整数、ｒ及びｓはそれぞれ２又は３を示す。）

（式中、Ｒｆ²はパーフルオロアルキル基であり、Ｘ²は水素原子、臭素原子又はヨウ素原子であり、Ｙは水素原子又は低級アルキル基であり、Ｚはフッ素原子又はトリフルオロメチル基であり、Ｒ⁴は水酸基又は加水分解可能な基であり、Ｒ⁵は水素原子又は炭素数１〜１０の一価炭化水素基である。また、ａ、ｂ、ｃ、ｄ、ｅは０又は１以上の整数で、ａ＋ｂ＋ｃ＋ｄ＋ｅは少なくとも１以上であり、ａ、ｂ、ｃ、ｄ、ｅの各繰り返し単位はランダムに結合されていてよい。ｆは０、１又は２であり、ｇは１、２又は３であり、ｈは１以上の整数である。） Accordingly, the present invention provides a method for coating a fluorine-containing dry coating agent described below.
[1]
A method for coating a fluorine-containing dry coating agent,
100 parts by mass of a fluorine-containing organosilane compound
(A) At least one selected from fluorine-based solvents having a boiling point of 100 ° C. or more and less than 135 ° C., and (B) Fluorine-based solvent having a boiling point of 80 ° C. or more and 200 ° C. or less under normal pressure. 100-99,900 masses of the diluent for fluorine-containing dry-coating agents containing at least 1 sort (s) different from (A) component chosen from these, and the mass ratio of (A) / (B) being 95 / 5-5 / 95 A method for coating a fluorine-containing dry coating agent, comprising preparing a fluorine-containing dry coating agent by diluting in part, and dry-coating the substrate using the coating agent.
[2]
The method for coating a fluorine-containing dry coating agent according to [1], wherein the fluorine-based solvent of the component (A) in the diluent for fluorine-containing dry coating agent is selected from perfluorotripropylamine and m-xylene hexafluoride. .
[3]
[1] or [2], wherein the difference in boiling point between component (A) and component (B) under normal pressure in the diluent for fluorine-containing dry coating agent is 10 ° C. or more and 80 ° C. or less. Dry coating agent coating method.
[4]
The fluorine-containing dry silane according to any one of [1] to [3], wherein the fluorine-containing organic silane compound has a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography in the range of 1,000 to 8,000. Coating method of coating agent.
[5]
The coating of the fluorine-containing dry coating agent according to any one of [1] to [4], wherein the fluorine-containing organic silane compound has a fluorine atom weight determined by ¹⁹ F-NMR in the range of 50 to 80% by mass. Method.
[6]
The coating method of the fluorine-containing dry coating agent according to any one of [1] to [5], wherein the fluorine-containing organic silane compound is represented by the following general formulas (1) to (3).

(In the formula, X is a hydrolyzable group, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, Q is an alkylene group having 1 to 10 carbon atoms which may interpose an NH group, m is an integer of 15 to 50, and n is 2 or 3.

(In the formula, Rf ¹ includes a unit represented by — (C _t F _2t ) O— (t is an integer of 1 to 6) and has a linear perfluoropolyalkylene ether structure having no branch. R 1 represents a divalent group, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, X ¹ represents a hydrolyzable group or a halogen atom, p is independently 0, 1 or 2, q is independently And an integer of 1 to 5, r and s each represent 2 or 3.)

(Wherein Rf ² is a perfluoroalkyl group, X ² is a hydrogen atom, a bromine atom or an iodine atom, Y is a hydrogen atom or a lower alkyl group, and Z is a fluorine atom or a trifluoromethyl group. , R ⁴ is a hydroxyl group or a hydrolyzable group, R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, c, d and e are 0 or 1 or more. Wherein a + b + c + d + e is at least 1 or more and each repeating unit of a, b, c, d, e may be randomly bonded, f is 0, 1 or 2, and g is 1, 2 or 3 and h is an integer of 1 or more.)

  By using the coating method of the present invention, the fluorine-containing dry coating agent can be uniformly and widely formed on the substrate without being affected by the lot blurring of the fluorine-containing organic silane compound.

It is the schematic which shows the base-material attachment board for vapor deposition used in the Example of this invention.

Hereinafter, the present invention will be described in more detail.
The coating method of the fluorine-containing dry coating agent of the present invention,
Fluorine-containing organosilane compound
(A) At least one selected from fluorine-based solvents having a boiling point of 100 ° C. or more and less than 135 ° C., and (B) Fluorine-based solvent having a boiling point of 80 ° C. or more and 200 ° C. or less under normal pressure. A fluorine-containing dry coating agent is prepared by diluting with a diluent for fluorine-containing dry coating agent containing at least one kind different from the component (A) selected from the above, and dry-coating on the substrate using the coating agent It is characterized by.

  As the fluorine-containing organosilane compound used in the present invention, various compounds can be used. Preferably, the number average molecular weight in terms of polystyrene determined by gel permeation chromatography is 1,000 or more and 8,000 or less, particularly It is desirable to use a fluorine-containing organosilane compound in the range of 2,000 to 6,000. If the number average molecular weight is less than 1,000, the water / oil repellency and antifouling characteristics of the perfluoropolyalkylene ether structure may not be fully exhibited. If the number average molecular weight exceeds 8,000, dry coating cannot be performed. There is.

The number average molecular weight referred to in the present invention refers to the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measured under the following conditions (hereinafter the same).
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector Column: TSKgel Multipore HXL-M manufactured by Tosoh Corporation
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.3 mass%)

As the fluorine-containing organosilane compound used in the present invention, it is preferable to use a compound having a fluorine atom weight determined by ¹⁹ F-NMR in the range of 50% by mass to less than 80% by mass, particularly 55 to 70% by mass. If the amount of fluorine atoms is less than 50% by mass, the desired properties such as water and oil repellency and antifouling properties may not be obtained, and if it is 80% by mass or more, the desired adhesion and durability may not be obtained. is there.

（式中、Ｘは加水分解性基であり、Ｒ¹は炭素数１〜１０の一価炭化水素基であり、Ｒ²は水素原子又は炭素数１〜１０の一価炭化水素基であり、ＱはＮＨ基を介在してもよい炭素数１〜１０のアルキレン基である。ｍは１５〜５０の整数であり、ｎは２又は３である。） Specific examples of such fluorine-containing organosilane compounds include those represented by the following general formulas (1) to (3).

(In the formula, X is a hydrolyzable group, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, Q is an alkylene group having 1 to 10 carbon atoms which may interpose an NH group, m is an integer of 15 to 50, and n is 2 or 3.

（式中、Ｒｆ¹は、−（Ｃ_tＦ_2t）Ｏ−（ｔは１〜６の整数）で表される単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基を示し、Ｒ³は炭素数１〜１０の一価炭化水素基を示し、Ｘ¹は加水分解性基又はハロゲン原子を示す。ｐは独立に０、１又は２、ｑは独立に１〜５の整数、ｒ及びｓはそれぞれ２又は３を示す。）

(In the formula, Rf ¹ includes a unit represented by — (C _t F _2t ) O— (t is an integer of 1 to 6) and has a linear perfluoropolyalkylene ether structure having no branch. R 1 represents a divalent group, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, X ¹ represents a hydrolyzable group or a halogen atom, p is independently 0, 1 or 2, q is independently And an integer of 1 to 5, r and s each represent 2 or 3.)

（式中、Ｒｆ²はパーフルオロアルキル基であり、Ｘ²は水素原子、臭素原子又はヨウ素原子であり、Ｙは水素原子又は低級アルキル基であり、Ｚはフッ素原子又はトリフルオロメチル基であり、Ｒ⁴は水酸基又は加水分解可能な基であり、Ｒ⁵は水素原子又は炭素数１〜１０の一価炭化水素基である。また、ａ、ｂ、ｃ、ｄ、ｅは０又は１以上の整数で、ａ＋ｂ＋ｃ＋ｄ＋ｅは少なくとも１以上であり、ａ、ｂ、ｃ、ｄ、ｅの各繰り返し単位はランダムに結合されていてよい。ｆは０、１又は２であり、ｇは１、２又は３であり、ｈは１以上の整数である。）

(Wherein Rf ² is a perfluoroalkyl group, X ² is a hydrogen atom, a bromine atom or an iodine atom, Y is a hydrogen atom or a lower alkyl group, and Z is a fluorine atom or a trifluoromethyl group. , R ⁴ is a hydroxyl group or a hydrolyzable group, R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, c, d and e are 0 or 1 or more. Wherein a + b + c + d + e is at least 1 or more and each repeating unit of a, b, c, d, e may be randomly bonded, f is 0, 1 or 2, and g is 1, 2 or 3 and h is an integer of 1 or more.)

  In the above formula (1), examples of the hydrolyzable group of X include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, particularly an alkoxy group having 1 to 4 carbon atoms, a methoxymethoxy group and a methoxy group. Examples thereof include an alkoxy group having 2 to 6 carbon atoms such as an ethoxy group, particularly an alkoxyalkoxy group having 2 to 4 carbon atoms, an acyloxy group such as an acetoxy group, and an alkenyloxy group such as an isopropenoxy group. Among these, a methoxy group, an ethoxy group, and an isopropenoxy group are preferable.

In addition, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R ¹ include an alkyl group and an aryl group, but a lower alkyl group or a phenyl group is particularly preferable, and specifically, a methyl group or an ethyl group. Propyl group, butyl group, pentyl group, hexyl group, phenyl group and the like. Among these, a methyl group is preferable.

R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples of the monovalent hydrocarbon group of R ² include an alkyl group and an aryl group, preferably a hydrogen atom or a lower alkyl group. Or it is a phenyl group and is the same as that of R < ¹ > as a specific example. Among these, a hydrogen atom and a methyl group are preferable.

Q is an alkylene group having 1 to 10 carbon atoms, particularly 2 to 8 carbon atoms, and this alkylene group may be interposed with an NH group, but is preferably a CH ₂ CH ₂ CH ₂ group or a CH ₂ CH ₂ NHCH ₂ CH. ₂ CH ₂ groups, and these may be mixed.

  m is an integer of 15 to 50, preferably 20 to 40. If it is smaller than this range, the characteristics as a perfluoropolyether group will not be sufficiently exhibited. If it is larger than this range, alkoxysilyl occupying the entire molecule. Since the ratio of groups becomes extremely small, the condensation reaction of alkoxysilyl groups is difficult to proceed, which is not preferable in forming a film. n is 2 or 3.

In the above formula (2), Rf ¹ is
-(C _t F _2t ) O-
(T is an integer of 1-6.)
Is a divalent group having a linear perfluoropolyalkylene ether structure having no branch, and preferably the following.
_{-CF 2 CF 2 O (CF 2} CF 2 CF 2 O) i CF 2 CF 2 -
(In the formula, i is 1 or more, preferably 1 to 50, more preferably an integer of 10 to 40.)
_{-CF 2 (OC 2 F 4)} j - (OCF 2) k -
(In the formula, j and k are each 1 or more, preferably 1 to 50, more preferably an integer of 10 to 40, and the sum of j + k is 10 to 100, preferably 20 to 90, more preferably 40 to 40. (It is an integer of 80, and the arrangement of the repeating units is random.)

R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof are the same as those exemplified for R ¹ in the above formula (1). Among these, a methyl group is preferable.

X ¹ is a hydrolyzable group or a halogen atom, and examples of the hydrolyzable group are the same as those exemplified for X in the above formula (1). Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is preferable.

  p is independently 0, 1 or 2, preferably 1, and q is independently an integer of 1 to 5, preferably 2 to 4. r and s are 2 or 3, respectively.

In the above formula (3), Rf ² is a perfluoroalkyl group, and specific examples include CF ₃ —, C ₂ F ₅ —, C ₃ F ₇ — and the like.

Y is a hydrogen atom or a lower alkyl group. Specific examples of the lower alkyl group include those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.
R ⁴ is a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples thereof include an alkoxyalkoxy group having 2 to 6 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, particularly an acylalkoxy group such as an acetoxy group, and an alkenyloxy group such as an isopropenoxy group. R ⁴ is preferably a methoxy group, an ethoxy group, or an isopropenoxy group.

R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the monovalent hydrocarbon group having 1 to 10 carbon atoms is the same as that exemplified for R ¹ in the above formula (1). Can be illustrated. R ⁵ is preferably a methyl group.

  A, b, c, d and e are 0 or an integer of 1 or more, preferably a is an integer of 0 to 50, b is an integer of 0 to 50, c is an integer of 0 to 50, and d is 0. An integer of ˜50, e is an integer of 0 to 50, and a + b + c + d + e is at least 1 or more. In addition, each repeating unit of a, b, c, d, and e may be combined at random. f is 0, 1 or 2, g is 1, 2 or 3, and h is an integer of 1 or more.

  Next, the fluorine-based solvents (A) and (B) that are diluents for the fluorine-containing dry coating agent for diluting the fluorine-containing organic silane compound will be described. The fluorinated solvent referred to in the present invention refers to an organic compound that is liquid at 25 ° C. and contains at least one fluorine atom in the molecule.

(A) component is at least 1 sort (s) chosen from the fluorine-type solvent whose boiling point under a normal pressure is 100 degreeC or more and less than 135 degreeC.
Examples of the fluorine-based solvent having the above boiling point include perfluorooctane (bp: 104 ° C.), perfluorononane (bp: 125 ° C.), perfluoro-2-butyltetrahydrofuran (bp: 102 ° C.), perfluorotripropylamine ( Examples thereof include fully fluorinated solvents such as bp: 128 ° C. and partially fluorinated solvents such as m-xylene hexafluoride (bp: 116 ° C.) and benzotrifluoride (bp: 102 ° C.).

In addition, a commercial item can be used as (A) component.
As the component (A), perfluorotripropylamine, m-xylene hexafluoride, and benzotrifluoride are preferable from the viewpoint of cost, solubility, and availability, and perfluorotripropylamine, m-xylene hexafluoro. Rides are more preferred.

  (B) component is at least 1 sort (s) chosen from the fluorine-type solvent whose boiling point under a normal pressure is 80 degreeC or more and 200 degrees C or less, especially 80 degreeC or more and less than 200 degreeC. The component (B) may have a boiling point overlapping with the component (A), that is, a boiling point of 100 ° C. or higher and lower than 135 ° C., but is different from the fluorine-based solvent used as the component (A). Use solvent.

  Examples of the fluorine-based solvent having a boiling point of 80 ° C. or higher and 200 ° C. or lower include perfluoroheptane (bp: 82 ° C.), perfluorooctane (bp: 104 ° C.), perfluorononane (bp: 125 ° C.), perfluoro- Perfluorinated solvents such as 2-butyltetrahydrofuran (bp: 102 ° C.), perfluorotripropylamine (bp: 128 ° C.), perfluorotributylamine (bp: 174 ° C.), and pentafluorocyclopentane (bp: 82.82 ° C.). 5 ° C.), m-xylene hexafluoride (bp: 116 ° C.), benzotrifluoride (bp: 102 ° C.) and the like.

In addition, a commercial item can be used as (B) component, As such a fluorine-type solvent, Asahi Clin AC-6000 (Asahi Glass Co., Ltd., bp: 114 degreeC), Novec 7300 (Sumitomo 3M), for example. And the like, bp: 98 ° C.).
As the component (B), perfluorotripropylamine, perfluorotributylamine, perfluoro-2-butyltetrahydrofuran, Asahiclin AC-6000, and Novec 7300 are preferable because of price, solubility, and availability.

  In the present invention, as the component (A) and the component (B), the components (A) and (B) having different boiling points are evaporated at the same time, so that a stable evaporation amount can be obtained for a certain period of time. From the viewpoint of exhibiting the maximum effect, it is preferable to use those in which the difference in boiling point between the component (A) and the component (B) is 10 ° C. or more and 80 ° C. or less, particularly 10 ° C. or more and 60 ° C. or less. It is preferable to use each of these. When the difference in boiling point between the components (A) and (B) is less than 10 ° C., the components (A) and (B) evaporate at a time, and the time during which the evaporation amount is stable is shortened. The effect of component system may be lost, and if there is too much difference in boiling point, for example, only component (A) evaporates first to become only component (B), and the effect of using solvent as a two-component system is lost There is.

  As for the mixing ratio (mass ratio) of both the components (A) and (B), (A) / (B) is 95/5 to 5/95, preferably 85/15 to 15/85. When the ratio exceeds 95/5 or falls below 5/95, it is difficult to obtain a uniform and wide-area coating film.

  The fluorine-containing dry coating agent of the present invention is a mixture of the above components (A) and (B) so that the fluorine-containing organic silane compound is 0.1 to 50% by mass, preferably 1 to 30% by mass as a solid content. It is used after diluted with a fluorine-based solvent (diluent for fluorine-containing dry coating agent). When the solid content of the fluorine-containing organic silane compound is less than the lower limit value, it is difficult to form a coating film having a sufficient film thickness, and when the upper limit value is exceeded, impregnation into the vapor deposition source becomes insufficient.

The coating method of the fluorine-containing dry coating agent of the present invention is performed by dry coating.
The dry coating referred to in the present invention refers to a method of depositing and depositing a vapor phase material on the film formation surface. Examples of the dry coating include a vacuum deposition method, a sputtering method, a PVD method such as an ion beam method, an ionization deposition method, and a CVD method. More specifically, a resistance heating method, an electron beam beam method, a high frequency heating method, a molecular beam epitaxy method, or the like can be used as the vacuum deposition method, and the CVD method can be a plasma CVD method, a photo CVD method, a thermal method, or the like. A CVD method, an MOCVD method, or the like can be used.
The dry coating can be performed by a conventionally known method and conditions.

  Here, the base material on which the fluorine-containing dry coating agent of the present invention is coated is not particularly limited, and examples thereof include various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, and quartz.

  As for the film thickness to the base material of the fluorine-containing organosilane compound coated using the fluorine-containing dry coating agent of this invention, 1-50 nm is preferable, More preferably, it is 5-30 nm.

  It is preferable to cure the fluorine-containing organic silane compound in the deposited coating agent after dry coating, and the curing condition is preferably in the range of room temperature to 80 ° C., and it is performed under humidification to promote the reaction. desirable.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Examples 1-7, Comparative Examples 1-5]
Preparation of fluorine-containing dry coating agent Fluorine- containing organosilane compound (number average molecular weight: 4,310, fluorine atom weight: 66 mass%) represented by the following formula (I) is diluted to 20 mass% with the solvent composition shown in Table 1. This was used as a fluorine-containing dry coating agent.

The solubility of the obtained fluorine-containing dry coating agent was evaluated by the method shown below. The results are also shown in Table 1.
Characteristic Evaluation (a) Solubility The appearance of the fluorine-containing dry coating agent was visually examined.
Evaluation criteria ○: Uniform transparency
×: Turbid

Preparation of heating evaporation source Steel wool (# 0000, Nippon Steel Wool Co., Ltd., wire diameter 0.012 mm) 0.005 parts by mass of open cylindrical copper container (inner diameter 6 mm × height 1.5 mm, capacity 40 μL), and 4 μL of the fluorine-containing dry coating agent prepared above was used as a deposition source.

As shown in FIG. 1, slide glass (76 mm × 76 mm) is formed on the base plate mounting plate for the vapor deposition processing small vacuum deposition apparatus DEPOX VTR-350M / ERH (manufactured by ULVAC KIKOH Co., Ltd.) at a distance of 80 mm from the center. 26 mm × 1 mm) and the substrate mounting plate was installed at a position where the vapor deposition distance of the vapor deposition apparatus was 100 mm. Next, the vapor deposition source is installed on the resistance heating tungsten board, and the pressure is reduced to 2.5 × 10 ⁻³ Pa, and then the tungsten board is heated by applying a current of 67.5 A to obtain a fluorine-containing dry coating agent. The fluorine-containing organic silane compound in the inside was vapor-deposited and coated on the base material to obtain a vapor-deposited base material (deposition film thickness: 10 nm). Subsequently, it hardened | cured on the conditions of 40 degreeC / 80% RH * 16 hours, and the characteristic evaluation was performed by the method shown below.

Characteristic evaluation (b) Static contact angle for water Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), a water droplet of 1.2 μL of liquid volume is made on the needle tip at room temperature, and this is brought into contact with the surface of the vapor deposition substrate. Made droplets. The angle between the droplet generated at this time and the surface was measured to obtain a static contact angle. The results are also shown in Table 1. In addition, A, B, C, and D shown in Table 1 correspond to each base material shown in FIG.

(C) Measurement of releasability Measurement was performed under the following conditions using Autograph AG-IS (manufactured by Shimadzu Corporation).
Adhesive treatment (adhesive tape is affixed to the test piece): Nitto No. 31B (width 19 mm, manufactured by Nitto Denko Corporation)
Crimping condition: 20 g / cm ² Load aging: 25 ° C./24 hours Peeling speed: 300 mm / min, 180 ° direction

(D) Magic ink wiping property Oil-based magic (Zebra Co., Ltd. “Himackey”) is applied to the treated surface, and tissue paper (Kami Shoji Co., Ltd. “Elmore”) is used to remove the magic ink. Visual evaluation was performed using an index.
◎ Easy and complete wiping by one wiping operation.
○: A little ink remains after one wiping operation.
Δ: About half remains after one wiping operation.
X: It cannot wipe off at all.

(A-1) m-xylene hexafluoride (bp: 116 ° C.)
(A-2) Perfluorotripropylamine (bp: 128 ° C.)
(B-1) Perfluorotripropylamine (bp: 128 ° C.)
(B-2) Perfluorotributylamine (bp: 174 ° C.)
(B-3) Perfluoro-2-butyltetrahydrofuran (bp: 102 ° C.)
(B-4) Asahiklin AC-6000 (Asahi Glass Co., bp: 114 ° C.)
(B-5) Novec 7300 (Sumitomo 3M, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, bp : 98 ° C)
(B-6) Novec 7200 (manufactured by Sumitomo 3M, C ₄ F ₉ OC ₂ H ₅ , bp: 78 ° C.)
(B-7) Perfluorotripentylamine (bp: 215 ° C.)

[Examples 8 to 11 and Comparative Examples 6 to 9]
Preparation of a fluorine-containing dry coating agent prepared by diluting 4 lots of the fluorine-containing organosilane compound represented by the formula (I) (physical properties are shown in Table 2) to 20% by mass with the solvent composition shown in Table 3. Dry coating was performed in the same manner as described above, and evaluation was performed in the same manner as described above. The evaluation results are also shown in Table 3.

官能基変性率：含フッ素基(パーフルオロポリエーテル基)に変性されているメトキシ基の
理論量に対し、¹Ｈ-ＮＭＲで求めた実際の変性量の割合を百分率にて求めた値

Functional group modification rate: The value obtained by calculating the percentage of the actual modification amount obtained by ¹ H-NMR with respect to the theoretical amount of methoxy group modified by fluorine-containing group (perfluoropolyether group)

Claims (6)

A method for coating a fluorine-containing dry coating agent,
100 parts by mass of a fluorine-containing organosilane compound
(A) At least one selected from fluorine-based solvents having a boiling point of 100 ° C. or more and less than 135 ° C., and (B) Fluorine-based solvent having a boiling point of 80 ° C. or more and 200 ° C. or less under normal pressure. 100-99,900 masses of the diluent for fluorine-containing dry-coating agents containing at least 1 sort (s) different from (A) component chosen from these, and the mass ratio of (A) / (B) being 95 / 5-5 / 95 A method for coating a fluorine-containing dry coating agent, comprising preparing a fluorine-containing dry coating agent by diluting in part, and dry-coating the substrate using the coating agent.   The method for coating a fluorine-containing dry coating agent according to claim 1, wherein the fluorine-based solvent of component (A) in the diluent for fluorine-containing dry coating agent is selected from perfluorotripropylamine and m-xylene hexafluoride. .   The fluorine-containing dry coating according to claim 1 or 2, wherein the difference in boiling point between the components (A) and (B) under normal pressure in the diluent for fluorine-containing dry coating agent is 10 ° C or higher and 80 ° C or lower. Agent coating method.   The fluorine-containing dry coating according to any one of claims 1 to 3, wherein the fluorine-containing organic silane compound has a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography in a range of 1,000 to 8,000. Agent coating method. The method for coating a fluorine-containing dry coating agent according to any one of claims 1 to 4, wherein the fluorine-containing organic silane compound has a fluorine atom amount determined by ¹⁹ F-NMR in a range of 50 mass% or more and less than 80 mass%. . The method for coating a fluorine-containing dry coating agent according to any one of claims 1 to 5, wherein the fluorine-containing organic silane compound is represented by the following general formulas (1) to (3).

(In the formula, X is a hydrolyzable group, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, Q is an alkylene group having 1 to 10 carbon atoms which may interpose an NH group, m is an integer of 15 to 50, and n is 2 or 3.

(In the formula, Rf ¹ includes a unit represented by — (C _t F _2t ) O— (t is an integer of 1 to 6) and has a linear perfluoropolyalkylene ether structure having no branch. R 1 represents a divalent group, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, X ¹ represents a hydrolyzable group or a halogen atom, p is independently 0, 1 or 2, q is independently And an integer of 1 to 5, r and s each represent 2 or 3.)

(Wherein Rf ² is a perfluoroalkyl group, X ² is a hydrogen atom, a bromine atom or an iodine atom, Y is a hydrogen atom or a lower alkyl group, and Z is a fluorine atom or a trifluoromethyl group. , R ⁴ is a hydroxyl group or a hydrolyzable group, R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, c, d and e are 0 or 1 or more. Wherein a + b + c + d + e is at least 1 or more and each repeating unit of a, b, c, d, e may be randomly bonded, f is 0, 1 or 2, and g is 1, 2 or 3 and h is an integer of 1 or more.)

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