JP2005154787A - Thin film formation method and thin film formation body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film formation method capable of stably forming a soil-resistant film having high uniformity, excellent water repellency, oil repellency, sebum and ink wiping properties and repetitive durability thereof even if long-term thin film formation is performed continuously, and to provide a thin film formation body obtained by the same. <P>SOLUTION: The thin film formation method forms a thin film on a base material by introducing thin film forming gas into a discharge space consisting of an electrode pair facing each other under the atmospheric pressure or a pressure near the atmospheric pressure and exciting the gas. The thin film forming gas contains an organometallic compound having an organic group including a fluorine atom. The electrode pair has cleaning films for preventing the electrode pair from being exposed to the excited thin film forming gas. The cleaning films are heated stepwise or continuously before arriving at a discharge surface on an upstream side in a transport direction and are transported while being held in tight contact with the discharge surface and at least part of the electrode pair surfaces exclusive of the discharge surface and continuing to the discharge surface. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel antifouling film thin film forming method and a thin film formed body, and more specifically, a substrate is formed by exciting a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom in a discharge space. The present invention relates to a thin film forming method for forming a high-function antifouling film by exposure and a thin film formed body obtained thereby.

  Currently, the surface of an image display device such as a touch panel directly touched by human fingers, the surface of an image display device such as a CRT or a liquid crystal display, the surface of a lens, the surface of a lens, or a transparent material such as a solar cell or window glass that is easily exposed to the outside air. It is known to provide an antifouling film on the surface that protects the surface, prevents adhesion of dirt and dust that impairs visibility, or easily removes adhering dirt and dust. It has been.

  Conventionally, as a method for forming an antifouling film, a method of applying a liquid material for forming an antifouling film to the surface of an article has been widely known and put into practical use (see Patent Document 1). As an example, there is a method of improving the antifouling property on the surface by coating the surface of an antireflection film used in a liquid crystal display or the like with a terminal silanol organic polysiloxane by a coating method (see Patent Document 2).

  However, the method of forming an antifouling film by a coating method requires chemical resistance to the solvent constituting the coating solution, so that the material of the base material that can be used is limited, and a drying process is required after coating Therefore, when the manufacturing process is costly loaded, and the target substrate surface has irregularities, leveling may occur in the drying process after coating, and the wettability of the coating liquid may vary depending on the material. There is a problem that it becomes inadequate, causing coating unevenness and repellency failure, and it is difficult to form an antifouling film having a uniform film thickness.

Based on the above problems, a method of easily forming an antifouling film using atmospheric pressure plasma CVD has been proposed (see Patent Document 3). According to this method, it is possible to stably form an antifouling film having a uniform thickness even on a substrate having an uneven surface shape without requiring a drying step.
JP 2000-144097 A (Claims) JP-A-2-36921 (Claims) JP 2003-98303 A (Claims)

  However, in the above method, when a thin film is continuously formed for a long period of time, dirt gradually adheres to the electrode surface, resulting in an unstable discharge state and a non-uniform flow of excited gas. In particular, in the formation of an antifouling film that requires high uniformity, the discharge is relatively low, so that the discharge does not partially occur due to dirt adhering to the electrode surface, and the resulting antifouling film has a reduced performance or thin film. Has the problem of non-uniformity.

  The present invention has been made in view of the above problems, and its object is to achieve high water repellency, oil repellency, and sebum and ink wiping even when a long-term thin film is continuously formed. It is providing the thin film formation method which can form stably the antifouling film which has property, and the thin film formation body obtained by it.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
A thin film forming gas is introduced into a discharge space composed of electrode pairs facing each other at atmospheric pressure or near atmospheric pressure, the thin film forming gas is excited, and the substrate is exposed to the excited thin film forming gas. In the thin film formation method of forming a thin film on the substrate,
The thin film forming gas contains an organometallic compound having an organic group having a fluorine atom,
The electrode pair has a cleaning film that prevents direct exposure to the excited thin film forming gas, and the cleaning film is heated stepwise or continuously upstream in the transport direction until reaching the discharge surface. And a method of forming a thin film, wherein the thin film is transported in close contact with the discharge surface and at least a part of the surface of the electrode pair other than the discharge surface continuous with the discharge surface.
(Claim 2)
The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (1).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. j represents an integer of 0 to 150. ]
(Claim 3)
The thin film forming method according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group or an aryl group. K represents an integer of 0 to 50, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be linked to form a ring. ]
(Claim 4)
The thin film forming method according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₂ represents an alkyl group, an alkenyl group, or an aryl group, and k represents an integer of 0 to 50. ]
(Claim 5)
The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (4).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. j represents an integer of 0 to 150. ]
(Claim 6)
The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (5).

General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
[Wherein, M represents In, Al, Sb, Y or La, and Rf represents an alkyl group or an alkenyl group in which at least one hydrogen atom is substituted with a fluorine atom. X represents a simple bond or a divalent group, and Y represents a simple bond or an oxygen atom. R ₈ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R ₉ represents a substituted or unsubstituted alkyl group or alkenyl group. k represents an integer of 0 to 50, m + n + p = 3, m is at least 1, and n and p each represent an integer of 0 to 2. ]
(Claim 7)
The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (6).

General formula (6)
^{_{R f1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3
[Wherein, R ^f1 represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1 to 50 An integer, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0. ]
(Claim 8)
The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (7).

[Wherein, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1, m and n Represents an integer of 0 to 2, and p represents an integer of 1 to 10. ]
(Claim 9)
The thin film forming method according to claim 1, wherein the discharge space is formed by applying a high-frequency electric field between the pair of electrodes.
(Claim 10)
The thin film forming method according to claim 1, wherein the thin film forming gas contains 50% by volume or more of a rare gas and / or nitrogen.
(Claim 11)
The thin film forming method according to claim 1, wherein the thin film forming gas contains 0.01 to 10% by volume of a reducing gas.
(Claim 12)
The thin film forming method according to claim 11, wherein at least one of the reducing gases is hydrogen gas.
(Claim 13)
The thin film forming method according to claim 1, wherein the thin film forming gas contains 0.01 to 10% by volume of an oxidizing gas.
(Claim 14)
The thin film forming method according to claim 13, wherein at least one of the oxidizing gases is oxygen gas.
(Claim 15)
The thin film is formed on the substrate by exposing the substrate to a discharge space or an excited discharge gas and performing a pretreatment and then exposing the substrate to the excited thin film forming gas. The thin film formation method of any one of 1-14.
(Claim 16)
The method of forming a thin film according to claim 1, wherein the surface of the substrate on which the thin film is formed contains an inorganic compound.
(Claim 17)
The thin film forming method according to any one of claims 1 to 15, wherein a main component of a surface of the base material forming the thin film is a metal oxide.
(Claim 18)
A thin film formed body obtained by the thin film forming method according to claim 1.
(Claim 19)
It is a thin film formation body obtained by the thin film formation method of any one of Claims 1-17, Comprising: The surface specific resistance value of the thin film surface formed on the base material is 23 degreeC, 55% RH conditions A thin film forming body characterized in that it is 1 × 10 ¹² Ω / □ or less below.

  According to the present invention, an antifouling film having high uniformity and excellent water repellency, oil repellency, sebum and ink wiping property and repeated durability even when a thin film is continuously formed for a long period of time. It is possible to provide a thin film forming method that can be stably formed and a thin film formed body obtained thereby.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  In the thin film forming method of the present invention, a thin film forming gas is introduced into a discharge space composed of electrode pairs facing each other under atmospheric pressure or a pressure near atmospheric pressure, the thin film forming gas is excited, and the excitation is performed. In the thin film forming method of forming a thin film on the base material by exposing the base material to the thin film forming gas, the thin film forming gas contains an organometallic compound having an organic group having a fluorine atom, and the electrode pair Has a cleaning film that prevents direct exposure to the excited thin film forming gas, the cleaning film being heated stepwise or continuously upstream in the conveying direction until reaching the discharge surface, and It is transported in close contact with the discharge surface and at least a part of the surface of the electrode pair other than the discharge surface continuous with the discharge surface.

  First, the details of the organometallic compound having an organic group having a fluorine atom contained in the thin film forming gas according to the present invention will be described.

  In the organometallic compound having an organic group having a fluorine atom according to the present invention, examples of the organic group having a fluorine atom include organic groups containing a fluorine atom-containing alkyl group, alkenyl group, aryl group, etc. The organometallic compound having an organic group having a fluorine atom used in the invention is an organic group having these fluorine atoms, such as silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium, It is an organometallic compound that is directly bonded to a metal such as lanthanum, iron, neodymium, copper, gallium, or half-new. Of these metals, silicon, titanium, germanium, zirconium, tin and the like are preferable, and silicon and titanium are more preferable. These fluorine-containing organic groups may be bonded to the metal compound in any form. For example, when a compound having a plurality of metal atoms such as siloxane has these organic groups, at least one metal atom is fluorine. The position may be any as long as it has an organic group having.

  According to the thin film forming method of the present invention, it is estimated that an organometallic compound having an organic group having a fluorine atom can easily form a bond with a substrate such as silica or glass, and can exert the excellent effect of the present invention. Yes.

  As the organometallic compound having an organic group having a fluorine atom used in the present invention, a compound represented by the general formula (1) is preferable.

In the general formula (1), M represents Si, Ti, Ge, Zr or Sn. R _{1 to} R ₆ each represent a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is an organic group having a fluorine atom, for example, having a fluorine atom. An organic group containing an alkyl group, an alkenyl group or an aryl group is preferable. Examples of the alkyl group having a fluorine atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and 4,4. , 3, 3, 2, 2, 1, 1-octafluorobutyl group and the like, as the alkenyl group having a fluorine atom, for example, a group such as 3, 3, 3-trifluoro-1-propenyl group In addition, examples of the aryl group having a fluorine atom include groups such as a pentafluorophenyl group. In addition, an alkyl group, an alkenyl group, an alkoxy group formed from an aryl group, an alkenyloxy group, an aryloxy group, or the like can also be used.

  Further, in the alkyl group, alkenyl group, aryl group, etc., any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, but preferably at least one is bonded. . The carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.

Of the groups represented by R _{1 to} R ₆ , other than the organic group having a fluorine atom represents a hydrogen atom or a monovalent group, and examples of the monovalent group include a hydroxy group, an amino group, and an isocyanate group. , Halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, and the like, but are not limited thereto. j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.

  Of the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. Among the alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, and aryloxy groups that are the monovalent groups, preferred are an alkoxy group, an alkenyloxy group, and an aryloxy group.

  Of the metal atoms represented by M, Si and Ti are preferable.

  The monovalent group may be further substituted with other groups, and is not particularly limited. Preferred substituents include amino groups, hydroxyl groups, isocyanate groups, fluorine atoms, chlorine atoms, bromine atoms and the like. Atom, alkyl group, cycloalkyl group, aryl group such as alkenyl group, phenyl group, alkoxy group, alkenyloxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, alkaneamide group, arylamide group, alkylcarbamoyl And groups such as an arylcarbamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Further, the organic group having a fluorine atom or other groups represented by these R ₁ to R _6, and ^{is, R 1 R 2 R 3 M-} (M represents the metal atom, R ^1, R ² R ³ represents a monovalent group, and the monovalent group represents an organic group having the fluorine atom or a group other than the organic group having the fluorine atom exemplified as R _{1 to} R ₆ . A structure having a plurality of metal atoms further substituted by the group represented may be used. Examples of these metal atoms include Si and Ti, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Examples of the alkyl group, alkenyl group, and the alkoxy group formed from these, the alkyl group in the alkenyloxy group, and the alkenyl group, which are the groups having fluorine atoms mentioned in R _{1 to} R ₆ , include the following general formula (F) The group represented by these is preferable.

Formula (F)
_{Rf-X- (CH 2) k} -
Here, Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted by a fluorine atom. For example, Rf represents a perfluoro group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, or a heptafluoropropyl group. Groups such as alkyl groups, groups such as 3,3,3-trifluoropropyl groups, 4,4,3,3,2,2,1,1-octafluorobutyl groups, and 1,1,1 -An alkenyl group substituted by a fluorine atom such as trifluoro-2-chloropropenyl group is preferred, among which a group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, a heptafluoropropyl group, 3,3,3-trifluoropropyl group, 4,4,3,3,2,2,1,1-octafluorobutyl group, etc. Alkyl group preferably has at least two or more fluorine atoms.

X is a simple bond or a divalent group. The divalent group is a group such as —O—, —S—, —NR— (R represents a hydrogen atom or an alkyl group), —CO—, and the like. , -CO-O -, - CONH -, - SO 2 NH -, - SO 2 -O -, - OCONH-,

Represents a group such as

  k represents an integer of 0 to 50, preferably 0 to 30.

In addition to the fluorine atom, other substituents may be substituted in Rf, and examples of the substitutable group include the same groups as those exemplified as the substituents in R _{1 to} R ₆ . The skeletal carbon atom in Rf is another atom, for example, —O—, —S—, —NR ₀ — (R ₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and the general formula (F Or a group represented by carbonyl group, —NHCO—, —CO—O—, —SO ₂ NH— or the like.

  Of the compounds represented by the general formula (1), a compound represented by the following general formula (2) is preferable.

General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
In general formula (2), M represents the same metal atom as in general formula (1), Rf and X represent the same groups as Rf and X in general formula (F), and k represents the same integer. Represent. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group, or an aryl group, each of which is the same as the group exemplified as the substituent for R _{1 to} R _{6 in} the general formula (1). May be substituted, but preferably represents an unsubstituted alkyl group or alkenyl group. Further, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be linked to form a ring.

  Of the general formula (2), more preferred are compounds represented by the following general formula (3).

General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
Here, Rf, X and k are as defined in the general formula (2). R _{12 is} also synonymous with R ₁₁ in the general formula (2). Further, M is the same as M in the general formula (2), but Si and Ti are particularly preferable, and Si is most preferable.

  In the present invention, another preferred example of the organometallic compound having a fluorine atom includes a compound represented by the general formula (4).

In the general formula (4), R ₁ to R ₆ have the same meanings as R ₁ to R ₆ in the general formula (1). Also in this case, at least one of R _{1 to} R ₆ is an organic group having the fluorine atom, and a group represented by the general formula (F) is preferable. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. J represents an integer of 0 to 100, preferably 0 to 50, and most preferably j is in the range of 0 to 20.

  Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the general formula (5).

General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
In the general formula (5), M represents In, Al, Sb, Y, or La. Rf and X represent the same groups as Rf and X in formula (F), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, and is preferably an integer of 30 or less. R ₉ represents an alkyl group or an alkenyl group, and R ₈ represents an alkyl group, an alkenyl group, or an aryl group, each of which is the same as the group listed as the substituent for R _{1 to} R _{6 in} the general formula (1). May be substituted. Moreover, in General formula (5), it is m + n + p = 3, m is at least 1, n represents 0-2, p represents the integer of 0-2. It is preferable that m + p = 3, that is, n = 0.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (6).

General formula (6)
^{_{R f1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3
In the general formula (6), R ^f1 represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1 An integer of ˜50, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0.

As for carbon number of the linear or branched perfluoroalkyl group which can be introduce ^| transduced into Rf1, 1-16 are more preferable, and 1-3 are the most preferable. Therefore, the _{^{R f1, -CF 3, -C 2}} F 5, -C 3 F 7 and the like are preferable.

Examples of the hydrolyzable group that can be introduced into R ² include —Cl, —Br, —I, —OR ¹¹ , —OCOR ¹¹ , —CO (R ¹¹ ) C═C (R ¹² ) ₂ , —ON═C (R _{^{11) 2, -ON = CR 13}} , -N (R 12) 2, are preferred, such as -R ¹² NOCR ^11. R ¹¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R ¹² represents a carbon such as a hydrogen atom or an alkyl group. R 1 represents an aliphatic hydrocarbon having 1 to 5 carbon atoms, and R ¹³ represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. Among these hydrolyzable groups, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OCOCH ₃ and —NH ₂ are preferable.

  As for m1 in the said General formula (6), it is more preferable that it is 1-30, and it is still more preferable that it is 5-20. n1 is more preferably 1 or 2, and p1 is more preferably 1 or 2. Further, q1 is more preferably 1 to 3.

  Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the general formula (7).

In the general formula (7), Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trimethyl group. A fluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1 , M and n are integers of 0 to 2, and p is an integer of 1 to 10.

In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group. It is. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms.

Examples of the hydrolyzable group of R ²¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, R ²³ O group, R ²³ COO group, (R ²⁴ ) ₂ C═C (R ²³ ) CO group, ( R ²³ ) ₂ C═NO group, R ²⁵ C═NO group, (R ²⁴ ) ₂ N group, and R ²³ CONR ²⁴ group are preferred. Here, R ²³ is usually an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group usually having 6 to 20 carbon atoms such as a phenyl group, and R ²⁴ is a hydrogen atom or an alkyl group. Usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ²⁵ is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. More preferred are a chlorine atom, a CH ₃ O group, a C ₂ H ₅ O group, and a C ₃ H ₇ O group.

R ²² is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is 5 × 10 ² to 1 × 10 ⁵ , preferably 1 × 10 ³ to 1 × 10 ⁴ .

Further, as a preferred structure of the silane compound represented by the general formula (7), Rf is C ₃ F ₇ group, a is an integer of 1 to 50, b, c and d is 0 , E is 1, Z is a fluorine atom, and n is 0.

  In the present invention, typical examples of the organometallic compound having an organic group having fluorine, which is preferably used as the silane compound having a fluorine atom, and the compounds represented by the general formulas (1) to (7) are listed below. However, the present invention is not limited to these compounds.

1: (CF ₃ CH ₂ CH ₂ ) ₄ Si
2: (CF ₃ CH ₂ CH ₂ ) ₂ (CH ₃ ) ₂ Si
_{3: (C 8 F 17 CH} 2 CH 2) Si (OC 2 H 5) 3
_{4: CH 2 = CH 2 Si} (CF 3) 3
5: (CH ₂ = CH ₂ COO) Si (CF ₃ ) ₃
6: (CF ₃ CH ₂ CH ₂ ) ₂ SiCl (CH ₃ )
7: C ₈ F ₁₇ CH ₂ CH ₂ Si (Cl) _{3
8: (C 8 F 17 CH} 2 CH 2) 2 Si (OC 2 H 5) 2
9: CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
10: CF ₃ CH ₂ CH ₂ SiCl ₃
11: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCl ₃
12: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃
13: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
14: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
15: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
16: CF ₃ (CF ₂ ) ₈ CH ₂ Si (OC ₂ H ₅ ) ₃
17: CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
18: CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
19: CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃
20: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
21: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
22: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
23: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
24: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OC ₃ H ₇ ) ₂
25: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OC ₃ H ₇
26: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂
27: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₂ H ₅ ) ₂
28: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂
29: (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
30: C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
31: C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
32: C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
33: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
34: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
35: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
36: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂
37: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂
38: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
39: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
40: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
41: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
42: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
43: CF ₃ (CF ₂ ) ₂ O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) _{3
44: C 7 F 15 CH 2} O (CH 2) 3 Si (OC 2 H 5) 3
45: C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
46: C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃
47: CF ₃ (CF ₂ ) ₅ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) ₃
48: CF ₃ (CF ₂ ) ₃ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) _{3
49: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 CH 2 Si (OCH 3) 3
50: CF ₃ CO—O—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
51: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl
52: CF ₃ CH ₂ CH ₂ (CH ₃ ) Si (OCH ₃ ) _{2
53: CF 3 CO-O-} Si (CH 3) 3
54: CF ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl _{2
55: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OCH 3) 3
_{56: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OC 6 H 5) 3
_{57: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CH 3) 3
_{58: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CF 3 C 2 H 4) (CH 3) 2
_{59: CF 3 (OC 3 F} 6) 24 -O- (CF 2) 2 -CH 2 -O-CH 2 Si (OCH 3) 3
_{60: CF 3 O (CF (} CF 3) CF 2 O) m CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (m = 11~30),
_{61: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCOCF 2 O (CF 2 O) n (CF 2 CF 2 O) p CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (n / p = About 0.5, number average molecular weight = about 3000)
_{62: C 3 F 7 - (} OCF 2 CF 2 CF 2) q-O- (CF 2) 2 - [CH 2 CH {Si- (OCH 3) 3}] 9 -H (q = about 10)
63: F (CF (CF ₃ ) CF ₂ O) ₁₅ CF (CF ₃ ) CONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
64: F (CF ₂ ) ₄ [CH ₂ CH (Si (OCH ₃ ) ₃ )] _2.02 OCH _{3
65: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCO- [CF 2 (OC 2 F 4) 10 (OCF 2) 6 OCF 2] -CONHC 3 H 6 Si (OC 2 H 5) 3
_{66: C 3 F 7 (OC} 3 F 6) 24 O (CF 2) 2 CH 2 OCH 2 Si (OCH 3) 3
67: CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃
68: (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) _{2
69: CF 3 (CF 2)} 3 (C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
70: CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ Si (OC ₂ H ₅ ) ₃
71: CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si (NCO) ₃
72: CF ₃ (CF ₂ ) ₅ C ₂ H ₄ Si (NCO) ₃
73: C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
74: C ₉ F ₁₉ CONH (CH ₂ ) ₃ SiCl ₃
75: C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) _{3
76: C 3 F 7 O (} CF (CF 3) CF 2 O) 2 -CF (CF 3) -CONH (CH 2) Si (OC 2 H 5) 3
77: CF ₃ O (CF (CF ₃ ) CF ₂ O) ₆ CF ₂ CONH (CH ₂ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ (CH ₂ ) ₃ NHCOCF ₂ (OCF ₂ CF (CF ₃ )) ₆ OCF _{Three
78: C 3 F 7 COOCH 2} Si (CH 3) 2 OSi (CH 3) 2 CH 2 OCOC 3 F 7
_{79: CF 3 (CF 2)} 7 CH 2 CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 3 OCH 2 CH 2 (CF 2) 7 CF 3
_{80: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) 2 (OC 2 H 5)
_{81: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) (OC 2 H 5) 2
_{82: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (OC 2 H 5)
In addition to the compounds exemplified above, as fluorine-substituted alkoxysilanes,
83: (Perfluoropropyloxy) dimethylsilane 84: Tris (perfluoropropyloxy) methylsilane 85: Dimethylbis (nonafluorobutoxy) silane 86: Methyltris (nonafluorobutoxy) silane 87: Bis (perfluoropropyloxy) diphenylsilane 88: Bis (perfluoropropyloxy) methylvinylsilane 89: Bis (1,1,1,3,3,4,4,4-octafluorobutoxy) dimethylsilane 90: Bis (1,1,1,3,3) , 3-Hexafluoroisopropoxy) dimethylsilane 91: Tris (1,1,1,3,3,3-hexafluoroisopropoxy) methylsilane 92: Tetrakis (1,1,1,3,3,3-hexafluoro Isopropoxy) silane 93: dimethylbis (nonaf) (Luoro-t-butoxy) silane 94: bis (1,1,1,3,3,3-hexafluoroisopropoxy) diphenylsilane 95: tetrakis (1,1,3,3-tetrafluoroisopropoxy) silane 96: Bis [1,1-bis (trifluoromethyl) ethoxy] dimethylsilane 97: Bis (1,1,1,3,3,4,4,4-octafluoro-2-butoxy) dimethylsilane 98: Methyltris [2 , 2,3,3,3-pentafluoro-1,1-bis (trifluoromethyl) propoxy] silane 99: diphenylbis [2,2,2-trifluoro-1- (trifluoromethyl) -1-tolyl Ethoxy] silane and the following compounds,
100: (CF ₃ CH ₂ ) ₃ Si (CH ₂ —NH ₂ )
_{101: (CF 3 CH 2)} 3 Si-N (CH 3) 2

  Furthermore,

Silazanes such as
106: CF ₃ CH ₂ —CH ₂ TiCl ₃
107: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ TiCl ₃
108: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Ti (OCH ₃ ) ₃
109: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ TiCl ₃
110: Ti (OC ₃ F ₇ ) ₄
111: (CF ₃ CH ₂ —CH ₂ O) ₃ TiCl _{3
112: (CF 3 C 2 H} 4) (CH 3) 2 Ti-O-Ti (CH 3) 3
Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organometallic compounds as follows.

113: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ O (CH ₂ ) ₃ GeCl
114: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCH ₂ Ge (OCH ₃ ) ₃
115: (C ₃ F ₇ O) ₂ Ge (OCH ₃ ) ₂
116: [(CF ₃ ) ₂ CHO] ₄ Ge
117: [(CF ₃ ) ₂ CHO] ₄ Zr
_{118: (C 3 F 7 CH} 2 CH 2) 2 Sn (OC 2 H 5) 2
_{119: (C 3 F 7 CH} 2 CH 2) Sn (OC 2 H 5) 3
120: Sn (OC ₃ F ₇ ) ₄
121: CF ₃ CH ₂ CH ₂ In (OCH ₃ ) ₂
122: In (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
123: Al (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
124: Al (OC ₃ F ₇ ) ₃
125: Sb (OC ₃ F ₇ ) ₃
126: Fe (OC ₃ F ₇ ) ₃
127: Cu (OCH ₂ CH ₂ OC ₃ F ₇ ) ₂
128: C ₃ F ₇ (OC ₃ F ₆ ) ₂₄ O (CF ₂ ) ₂ CH ₂ OCH ₂ Si (OCH ₃ ) ₃

  The compounds listed in these specific examples are Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries Co., Ltd. (for example, OPTOOL DSX), and Gelest Inc. In addition to being marketed by Solvay Solexis Co., Ltd., etc., they can be easily obtained. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J.M. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No. 3,668,233, etc., JP-A 58-122979, JP-A 7-242675, JP-A 9-61605, etc. 11-29585, JP-A No. 2000-64348, JP-A No. 2000-144097 and the like, or a synthesis method based on the synthesis method.

  Next, other elements constituting the thin film forming gas will be described.

  The thin film forming gas according to the present invention contains 50% by volume or more of a rare gas and / or nitrogen as a discharge gas capable of causing discharge together with the above-described organometallic compound having an organic group having a fluorine atom. Is preferred. The additive gas preferably contains a reducing gas or an oxidizing gas in the range of 0.01 to 10% by volume, more preferably hydrogen gas is used as the reducing gas, or oxygen is used as the oxidizing gas. Use gas. Furthermore, as a discharge gas, for example, air or the like may be mixed and used as necessary.

  Moreover, in the thin film formation gas which concerns on this invention, it is preferable that it is the range of 0.001-30.0 volume% as content of the organometallic compound which has the organic group which has the above-mentioned fluorine atom.

  The material of the base material processed by the thin film forming method according to the present invention is not particularly limited, and examples thereof include metal oxides, plastics, metals, ceramics, paper, wood, nonwoven fabrics, glass plates, ceramics, building materials, and the like. In particular, it is preferable that the surface of the base material is composed of a surface containing an inorganic compound or a surface containing an organic compound, from the viewpoint of exhibiting the object effect of the present invention. It is a surface substrate mainly composed of a metal oxide such as titania. The substrate may be in the form of a sheet or a molded product. Examples of glass include plate glass and lenses, and examples of plastic include plastic lenses, plastic films, plastic sheets, and plastic molded products. When the base material uses such a plastic as a support, one having a metal oxide film formed on the surface thereof is preferable.

  Next, a thin film forming apparatus used in the thin film forming method of the present invention will be described.

  The thin film forming method of the present invention, as described above, is composed of electrode pairs facing each other under atmospheric pressure or near atmospheric pressure, and prevents the electrode pairs from being directly exposed to the excited thin film forming gas. Having a cleaning film, heated stepwise or continuously until the cleaning film reaches the discharge surface upstream of the discharge surface of the electrode pair in the transport direction of the cleaning film, and A thin film forming method for transporting a cleaning film in close contact with the discharge surface and at least a part of the surface of the electrode pair other than the discharge surface that is continuous with the discharge surface, wherein the discharge space includes the electrode pair. A thin film forming gas containing an organometallic compound having an organic group having a fluorine atom is introduced, the thin film forming gas is excited, and the substrate is exposed to the excited thin film forming gas. More and forms a thin film on the substrate.

  In the present invention, the discharge space is a space which is sandwiched between electrode pairs arranged to face each other at a predetermined distance, and causes discharge by introducing a thin film forming gas between the electrode pairs and applying a voltage. .

  The form of the discharge space is not particularly limited, and may be, for example, a slit formed by opposing plate electrode pairs or a space formed in a circumferential shape between two cylindrical electrodes.

  In the present invention, the atmospheric pressure or the pressure in the vicinity of the atmospheric pressure refers to a pressure of 20 kPa to 200 kPa. In this invention, the more preferable pressure between the electrodes which apply a voltage is 70 kPa-140 kPa.

  FIG. 1 is a cross-sectional view showing an example of a discharge space composed of opposed electrode pairs used in a conventional thin film forming method.

  The plasma discharge treatment apparatus 99 includes electrodes 101 and 102 that face each other and form a discharge space A of the thin film forming gas G, a support member 104 that supports the base material F so as to face this flow path, and a thin film forming gas. A gas nozzle (not shown) that is introduced into the discharge space A and supplies the base material F is provided. That is, in this plasma discharge processing apparatus 99 for forming a thin film, an electric field is applied to both electrodes 101 and 102 from the high frequency power source 5 while jetting a thin film forming gas G from a gas nozzle to the base material F supported by the support 104. This is applied to form a discharge space A, and the excited thin film forming gas G ′ generated in the discharge space A is ejected toward the substrate F, and the substrate F is exposed to the excited thin film forming gas G ′. A thin film can be formed on the substrate F.

  However, in the plasma discharge processing apparatus 99 described above, discharge plasma is generated in the discharge space A and the thin film forming gas is excited, so that the discharge surface of the electrodes 101 and 102 forming the discharge space A is excited. Contamination is likely to occur due to the thin film forming gas G ′, particularly the excited thin film forming gas G ′ containing an organometallic compound having an organic group having a fluorine atom. If the discharge surface is contaminated, stable discharge cannot be performed, which leads to a deterioration in quality.

  In the thin film forming method of the present invention, in order to solve the above problems, a cleaning film is provided at the electrode pair, and the cleaning film discharges upstream of the discharge surface of the electrode pair in the transport direction of the cleaning film. By heating stepwise or continuously until reaching the surface, and transporting the cleaning film in close contact with the discharge surface and at least a part of the surface of the electrode pair other than the discharge surface continuous to the discharge surface, Effectively prevent contamination by excited thin film forming gas at the electrode part of the discharge surface, especially excited thin film forming gas containing an organometallic compound having an organic group having fluorine atoms, and can continuously form a long-term thin film. The antifouling film is highly uniform and has excellent water repellency, oil repellency, sebum and ink wiping properties and repeated durability. Thin film forming method capable to form realizes the.

  The thin film forming method of the present invention includes a cleaning film transport mechanism that transports a cleaning film that prevents dirt from adhering to the electrode in close contact with the surface of the electrode.

  Since the cleaning film transport mechanism according to the present invention transports the cleaning film in close contact with the surface of the electrode, the surface of the electrode is covered with the cleaning film, and as a result, the electrode surface is contaminated by the excited thin film forming gas. Can be prevented.

  Also, since the cleaning film is transported by the cleaning film transport mechanism, the cleaning film in close contact with the surface of the electrode can be continuously replaced with a new one, and the electrode surface can be made maintenance-free for a long time. it can.

  The thin film forming method of the present invention is characterized in that the cleaning film is conveyed in close contact with the discharge surface of the electrode and at least a part of the electrode surface other than the discharge surface continuous with the discharge surface. If wrinkles or slippage occurs in the cleaning film located on the discharge surface of the electrode, the uniformity of the airflow in the discharge space is disturbed, resulting in non-uniform film formation. The cause of the wrinkles and creases is that they enter the discharge space in an unsupported state and contract under the influence of heat or the like. However, in the configuration according to the present invention, since the cleaning film is in close contact with the discharge surface of the electrode and the electrode surface other than the discharge surface continuous to the discharge surface, the cleaning film is supported by the surface other than the discharge surface. Enter the discharge space. As a result, even if the cleaning film is affected by heat, the surface of the cleaning film can be kept uniform, and wrinkles and slippage can be prevented. Therefore, uniformity in the plasma space can be maintained, and a high-quality thin film can be formed.

  The thin film forming method of the present invention has a heating mechanism stepwise or continuously until the cleaning film reaches the discharge surface upstream of the discharge surface of the electrode in the transport direction of the cleaning film. Is one of the features.

  By providing the heating mechanism defined above, the heating mechanism heats the cleaning film on the upstream side of the discharge surface of the electrode, so that the cleaning film can be heated before coming into contact with the discharge surface of the electrode. For this reason, even if the cleaning film enters the discharge space, it can be prevented from being suddenly and excessively influenced by heat, and shrinkage of the discharge plasma due to heat can be suppressed. Therefore, it is possible to further prevent the cleaning film from wrinkling and slipping.

  In the thin film forming method of the present invention, the entire width of the cleaning film is preferably set to be larger than the discharge surface of the electrode. By setting the entire width of the cleaning film so as to be larger than the discharge surface of the electrode, the electrode is covered by the cleaning film in a range beyond the discharge surface. For this reason, exposure to the excited thin film forming gas can be further suppressed, and contamination of the electrode can be prevented. Furthermore, since the cleaning film edge does not enter the discharge space, arc discharge due to concentration of discharge can be prevented.

  In the thin film forming method of the present invention, the film transport mechanism preferably transports the cleaning film to at least a part of the thin film forming gas supply unit and then transports the cleaning film to the surface of the electrode forming the gas flow path. That is, the cleaning film is brought into contact with at least a part of the thin film forming gas supply unit and then transported to the surface of the electrode forming the flow path, whereby the space from the thin film forming gas supply unit to the flow path is cleaned. By being partitioned by the film, the thin film forming gas can be prevented from flowing out of the flow path.

  Hereinafter, although the thin film forming apparatus provided with the cleaning film used in the thin film forming method of the present invention will be described with reference to the drawings, the embodiment of the present invention is not limited to these drawings.

  FIG. 2 is a cross-sectional view showing an example of a discharge space composed of opposing electrode pairs provided with a cleaning film used in the thin film forming method of the present invention.

  In FIG. 2, the plasma discharge processing apparatus 99 has a pair of electrodes 101 and 102 facing each other with a gap a on the peripheral surface of the support 104 on which the substrate F is placed. The pair of electrodes 101 and 102 are disposed with a gap b therebetween. The gap b is the discharge space A, and the opposing surfaces of the electrodes 101 and 102 constituting the discharge space A are discharge surfaces 101a and 102a, respectively.

  The electrodes 101 and 102 are square columnar electrodes in which a dielectric is coated on the surface of a conductive metal base material. The corners 215 of the electrodes 101 and 102 are formed in an arc shape. That is, since the four surfaces of the electrodes 101 and 102 are continuous via the corner portion 215, the surfaces other than the discharge surfaces 101a and 102a and the discharge surfaces 101a and 102a are also continuous.

  In the plasma discharge treatment apparatus 99, as shown in FIG. 2, a gas supply unit (mixed gas supply unit) 124 that introduces gas toward the gap b between the pair of electrodes 101 and 102 is opposed to the gap b. Has been placed. That is, the gap b functions as a flow path that guides the gas supplied from the gas supply unit 124 to the base material F on the support 104. The gas supply unit 124 includes a nozzle main body part 125 having a gas flow path formed therein, a gas ejection part 126 that projects from the nozzle main body part 125 toward the flow path, and communicates with the gas flow path to eject gas. Is provided.

  In the plasma discharge treatment apparatus 99, a film transport mechanism 130 that transports a cleaning film 127 that prevents the electrodes 101 and 102 from being soiled to the electrodes 101 and 102 in a continuous or intermittent manner is provided on each of the electrodes 101 and 102. It is provided according to. The film transport mechanism 130 is provided with a first film guide roller 131 that guides the cleaning film 127 in the vicinity of the gas supply unit 124. An unillustrated unwinding roller for the cleaning film 127 or an original roll for the cleaning film 127 is provided on the upstream side of the first film guide roller 131.

  Further, a winding unit (not shown) for winding the cleaning film 127 through the second film guide roller 132 is provided farther than the gas supply unit 124 than the first film guide roller 131. Yes.

  Further, the plasma discharge treatment apparatus 99 has a cleaning film against the discharge surfaces 101a and 102a of the electrodes 101 and 102 in order to prevent creases and wrinkles that occur when the cleaning film 127 contacts the discharge surfaces 101a and 102a. A heating member 128 for heating the cleaning film 127 is provided on the upstream side in the transport direction of 127.

  That is, in the plasma discharge processing apparatus 99, the cleaning film 127 is pulled out from the unwinding roller by the film transport mechanism 130, and then guided to the first film guide roller 131, so that the nozzle body of the gas supply unit 124. After contacting the peripheral edge of the portion 125, the surface of the heating member 128 is contacted and heated, and then contacts the discharge surfaces 101 a and 102 a via the corner portions 215 of the electrodes 101 and 102, and then the second film guide. It is guided by the roller 132 and is wound up by the winding unit. At this time, since the corner portion 215 is formed in an arc shape, the cleaning film 127 can be prevented from being caught when moving from the surface (surface of the corner portion 215) other than the discharge surfaces 101a and 102a to the discharge surfaces 101a and 102a. Can be transported smoothly. In this description, the discharge surfaces 101a and 102a of the electrodes 101 and 102 are flat surfaces. However, the discharge surfaces 101a and 102a may be formed into curved surfaces that protrude toward the other discharge surfaces 101a and 102a. . In such a case, the adhesion between the discharge surfaces 101a and 102a of the electrodes 101 and 102 and the cleaning film 127 can be further enhanced.

  As described above, since the cleaning film 127 and the nozzle main body 125 are in contact with each other, the space from the gas supply unit 124 to the discharge space A is partitioned by the cleaning film 127 so that the gas flows. It can prevent flowing out of the road.

  Here, when the cleaning film 127 is not in close contact with the electrodes 101 and 102, the surfaces of the electrodes 101 and 102 become the discharge surfaces 101a and 102a as described above, but the cleaning film 127 is in close contact with the electrodes 101 and 102. In this case, the surface of the cleaning film 127 that is in close contact with the discharge surfaces 101a and 102a becomes the discharge surface. Therefore, when the cleaning film 127 is in close contact with the electrodes 101 and 102, the discharge space A is formed from the surface of the cleaning film 127.

  The electrodes 101 and 102 are composed of a metal base material and a dielectric, and a combination of coating the metal base material with a dielectric having an inorganic property, and after spraying ceramics on the metal base material, It may be configured by a combination in which a dielectric material sealed with a material having a specific property is coated. Metals such as titanium, silver, platinum, stainless steel, aluminum, and iron can be used as the metal base material. Dielectric lining materials include silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Of these, borate glass is preferable because it is easy to process. As the ceramic used for the thermal spraying of the dielectric, alumina is preferable, and a sealing material such as silicon oxide is preferable. Further, the alkoxysilane-based sealing material can be made inorganic by a sol-gel reaction.

  The cleaning film 127 according to the present invention is formed of, for example, a resin film, paper, cloth, nonwoven fabric, or the like. Examples of the resin include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, and polychlorinated salts. Vinylidene, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl alcohol copolymer, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfone, polyetherimide, polyamide, fluororesin, Polymethyl acrylate, acrylate copolymer, etc. are mentioned, preferably Polyesters excellent inexpensive and productivity, a resin film, particularly as a main component polyethylene terephthalate (PET) and PET. The cleaning film 127 used in the present invention is a film having a thickness of 10 to 1000 μm, more preferably 20 to 100 μm. Further, the property required of the material is preferably excellent in heat resistance, that is, thermal dimensional stability, because the temperature becomes very high during the atmospheric pressure plasma treatment. Furthermore, in order to improve thermal dimensional stability, what gave annealing treatment etc. is more preferable.

  Next, embodiments of an atmospheric pressure plasma discharge treatment apparatus, an atmospheric pressure plasma discharge treatment method, and an electrode system for an atmospheric pressure plasma discharge treatment apparatus used in the thin film forming method of the present invention will be described below with reference to the drawings. However, the present invention is not limited to this.

  FIG. 3 is a view showing an example of a plasma discharge processing apparatus under atmospheric pressure or a pressure in the vicinity thereof according to the present invention.

  This atmospheric pressure plasma discharge treatment apparatus excites a thin film forming gas by generating a discharge plasma under atmospheric pressure or a pressure near atmospheric pressure, and exposes the substrate to the excited thin film forming gas, This is a thin film forming apparatus for forming a thin film. As shown in FIG. 3, the thin film forming apparatus is rotatably provided with a roll-shaped support member 10 that conveys a sheet-like base material F in close contact with the peripheral surface thereof.

  In order to adjust the surface temperature inside the support member 10, for example, a temperature adjusting medium such as water or silicone oil can be circulated, and in this circulating portion, as shown in FIG. A temperature control device 4 is connected via a pipe 3. Further, on the periphery of the support member 10, a thin film is formed on the base material transport mechanism 13 and the base material F as shown in FIG. 2 in order to transport the base material F in close contact with the peripheral surface of the support member 10. A plurality of thin film discharge treatment apparatuses 100 equipped with a cleaning film 127 for forming are provided.

  In the base material transport mechanism 13, the first guide roller 14 and the nip roller 15 that guide the base material F to the peripheral surface of the support member 10 and the base material F that is in close contact with the peripheral surface are peeled off and guided to the next step. A second guide roller 16 and a drive source (not shown) that rotates the first guide roller 14, the second guide roller 16, and the support member 10 in an interlocking manner are provided.

  Further, as shown in FIG. 4, in the thin film discharge processing apparatus 100, a gas supply unit (mixed gas supply unit) 124 that ejects a thin film forming gas toward the gap between the pair of electrodes 101 and 102 faces the gap. Are arranged as follows. That is, the gap functions as a flow path for guiding the thin film forming gas supplied from the gas supply unit 124 to the base material F on the support member 10. The gas supply unit 124 includes a nozzle main body 125 having a gas flow path formed therein, and a gas jet that protrudes from the nozzle main body (not shown) toward the flow path, and communicates with the gas flow path to eject gas. Part (not shown).

  In addition, the thin film discharge processing apparatus 100 includes a film transport mechanism 130 that continuously or intermittently transports a cleaning film 127 that prevents the electrodes 101 and 102 from being soiled, in close contact with the electrodes 101 and 102. 102 is provided. The film transport mechanism 130 is provided with a first film guide roller for guiding the cleaning film 127 in the vicinity of the gas supply unit 124. An unillustrated unwinding roller for the cleaning film 127 or an original roll for the cleaning film 127 is provided on the upstream side of the first film guide roller.

  FIG. 4 is a perspective view showing the electrode pair 101, 102. The electrode pair 101, 102 is a square columnar electrode in which a dielectric 212 is coated on the surface of a conductive metallic base material 211. The corners 215 of the electrode pairs 101 and 102 are formed in an arc shape. That is, since the four surfaces of the electrode pairs 101 and 102 are continuous via the corner portion 215, the surfaces other than the discharge surfaces 101a and 102a and the discharge surfaces 101a and 102a are also continuous. The electrode pair 101, 102 has a hollow inside, and the temperature adjusting device 4 is connected to the hollow portion 213 through the pipe 3 as shown in FIG. 3. By flowing a temperature adjusting medium through the hollow portion 213, the temperature of the electrode surface can be adjusted. A high frequency electric field can be applied between the electrode pairs 101 and 102 of the thin film discharge processing apparatus 100 by the high frequency power source 5.

  In the plasma discharge processing apparatus according to the present invention, the voltage applying means applies a voltage to the metal base material having metal conductivity of each electrode by a high frequency power source. The high frequency power source for applying a voltage to the counter electrode for forming the antifouling film according to the present invention is not particularly limited, but is preferably a relatively low power source. Two or more power supplies may be applied simultaneously.

  Examples of the high frequency power source used in the present invention include a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source (5 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (15 kHz), a high frequency power source manufactured by Shinko Electric (50 kHz), and the HEIDEN Laboratory. High frequency power supply (continuous mode use, 100 kHz), high frequency power supply from Pearl Industries (200 kHz), high frequency power supply from Pearl Industries (800 kHz), high frequency power supply from Pearl Industries (2 MHz), high frequency power supply from JEOL (13.56 MHz), Pearl An industrial high frequency power supply (27 MHz), a pearl industrial high frequency power supply (150 MHz), or the like can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.

  A method or conditions for plasma discharge treatment in a thin film forming gas atmosphere under atmospheric pressure or a pressure in the vicinity thereof according to the present invention will be described.

The frequency of the high frequency electric field applied between the counter electrodes when forming the antifouling film according to the present invention is not particularly limited, but the high frequency power source is preferably 0.5 kHz or more and 200 kHz or less, more preferably 0. 5 kHz or more and 80 kHz or less. The power supplied between the counter electrodes is preferably 0.05 W / cm ² or more and 10 W / cm ² or less. Note that the voltage application area (cm ² ) in the counter electrode refers to the area where discharge occurs. The high-frequency voltage applied between the counter electrodes may be an intermittent pulse wave or a continuous sine wave.

  In the present invention, the distance between the counter electrodes (b in FIG. 2) is determined in consideration of the thickness of the dielectric on the metal base material of the electrodes, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the dielectric when the dielectric is placed on one of the electrodes and the distance between the dielectrics when the dielectric is placed on both of the electrodes is the distance between the electrodes. From the viewpoint of discharging, 0.1 mm to 20 mm is preferable, and 0.2 to 10 mm is more preferable.

  In the present invention, the atmospheric pressure or the pressure in the vicinity thereof represents a pressure of 20 to 200 kPa, and 90 to 110 kPa, particularly 93 to 104 kPa is preferable in order to obtain the effects described in the present invention.

  Before forming the thin film according to the present invention, the thin film may be formed by exposing the base material to a separately provided discharge space. In addition, before the thin film is formed, the surface of the base material may be previously subjected to charge removal, and dust may be further removed. As the charge removal means and the dust removal means after the charge removal process, in addition to the normal blower type and contact type, a charge removal device in which a plurality of positive and negative ion generation charge removal electrodes and an ion attracting electrode are opposed to each other so as to sandwich the substrate, and thereafter Alternatively, a high-density static elimination system (Japanese Patent Laid-Open No. 7-263173) provided with positive and negative DC type static elimination devices may be used. Further, examples of the dust removal means after the static elimination treatment include a non-contact type jet-type depressurization type dust removal device (Japanese Patent Laid-Open No. 7-60211) and can be preferably used, but are not limited thereto.

  In the thin film forming method of the present invention, the substrate can be exposed to the excited thin film forming gas after performing the pretreatment by exposing the substrate to the discharge space or the excited discharge gas.

  As the atmospheric pressure plasma discharge device used for the pretreatment for forming a thin film by exposing the substrate to an excitation discharge gas before forming the thin film according to the present invention, the atmospheric pressure plasma discharge device shown in FIG. 1 can be used. .

  Further, as the atmospheric pressure plasma discharge device used for the pretreatment for forming the thin film by exposing the substrate to the discharge space before forming the thin film, the atmospheric pressure plasma discharge device shown in FIG. 5 can be used.

  The plasma discharge treatment apparatus 200 includes a pair of second electrodes 101 ′ and 102 ′ with a gap therebetween so as to form a thin film forming gas flow path, and a support for the substrate F at a position facing the electrode pair. The first electrode 104 ′ is disposed, and an electric field is applied between the first electrode and the second electrode to form a discharge space A. In addition, a gas nozzle (not shown) for introducing a thin film forming gas into the discharge space A and supplying it to the substrate F is provided.

  That is, in the plasma discharge processing apparatus 200 for forming a thin film, the second electrode 101 ′ is applied from the high frequency power source 5 to the base material F supported by the first electrode 104 ′ from a gas nozzle, for example, while discharging discharge gas. , 102 ′ and the first electrode 104 ′ to form a discharge space A, and after exposing the substrate to the discharge space A, the substrate is exposed to the excited thin film forming gas according to the present invention. be able to.

  Moreover, in the thin film formation method of this invention, it is preferable that the base-material surface which forms a thin film contains an inorganic compound, or the main component of a base-material surface is a metal oxide.

  The base material surface in the present invention contains an inorganic compound, and the main component of the base material surface is a metal oxide. The base material before forming the antifouling layer according to the present invention is an inorganic compound or a metal oxide. For example, it means that a functional thin film such as an antireflection film or an antiglare film has already been formed.

  Examples of the inorganic compound or metal oxide include titanium dioxide (for example, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, silicon oxide, and the like.

  In the present invention, an atmospheric pressure plasma discharge apparatus can be used as one method for providing a layer containing the above-described constituent on the surface of the substrate.

FIG. 6 includes a plasma discharge processing apparatus 300, a gas supply unit 150, a voltage application unit 140, and an electrode temperature adjustment unit 160. The substrate F is subjected to plasma discharge treatment as the roll rotating electrode 135 and the rectangular tube type fixed electrode group 136. In the discharge space (between the counter electrodes) A between the roll rotating electrode (first electrode) 135 and the square tube fixed electrode group (second electrode) 136, the roll rotating electrode (first electrode) 135 has a first power source. a frequency omega ₁ of the high-frequency voltages V ₁ from 141, also prismatic fixed electrode group (second electrode) 136 adapted to apply a high frequency voltage V ₂ to a frequency omega ₂ of the second power supply 142 Yes.

  A first filter 143 is installed between the roll rotation electrode (first electrode) 135 and the first power supply 141 so that the current from the first power supply 141 flows toward the roll rotation electrode (first electrode) 135. ing. The first filter is designed to make it difficult for the current from the first power supply 141 to pass to the ground side and to easily pass the current from the second power supply 142 to the ground side. Further, a second filter 144 is installed between the square tube type fixed electrode group (second electrode) 136 and the second power source 142 so that the current from the second power source flows toward the second electrode. . The second filter 144 is designed to make it difficult for the current from the second power source 142 to pass to the ground side and to easily pass the current from the first power source 141 to the ground side.

The roll rotating electrode 135 may be the second electrode, and the square tube type fixed electrode group 136 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply has the ability to apply a higher frequency voltage (V ₁ > V ₂ ) than the second power supply, and the frequency has the ability to satisfy ω ₁ <ω ₂ . Moreover, it is not always necessary to use both the first power source and the second power source, and either one can be used. When the discharge gas is nitrogen gas, both the first power source and the second power source are used. Preferably, when the discharge gas is a rare gas such as helium or argon, only one of the power supplies may be used.

  Substrate F passes between guide tube 164 and nip roll 165 to block air or the like accompanying the substrate, and transfers between square tube fixed electrode group 136 while being wound while being in contact with roll rotating electrode 135. Then, it passes through the nip roll 166 and the guide roll 167 and is transferred to the thin film forming process according to the present invention which is the next process. The process gas H is generated in the gas generator 151 which is the gas supply means 150 and the flow rate is controlled so that the process gas is in the plasma discharge processing container 170 between the counter electrodes (this is the discharge space) A from the air supply port 152. Then, the inside of the plasma discharge treatment container 170 is filled with the treatment gas, and the treatment exhaust gas H ′ subjected to the discharge treatment is discharged from the exhaust port 153.

  The roll rotating electrode 135 and the rectangular tube type fixed electrode group 136 are heated or cooled using the electrode temperature adjusting means 160 and fed to the electrodes. The temperature of the medium whose temperature is adjusted by the electrode temperature adjusting means 160 is adjusted by the liquid feed pump P from the inside of the roll rotating electrode 135 and the rectangular tube type fixed electrode group 136 through the pipe 161. During the plasma discharge treatment, the properties and composition of the thin film obtained may vary depending on the temperature of the substrate, and it is preferable to appropriately control this. As the medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to control the temperature inside the roll rotating electrode 135 so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur as much as possible. Reference numerals 168 and 169 denote partition plates that partition the plasma discharge processing vessel 131 from the outside.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

《Preparation of thin film sample》
[Preparation of substrate]
(Formation of antistatic layer)
The coating composition of the antistatic layer 1 having the following composition was die-coated on one surface of a cellulose triacetate film (manufactured by Konica, trade name: Konicatak KC80UVSF) having a thickness of 80 μm so that the dry film thickness was 0.2 μm. And dried at 80 ° C. for 5 minutes to provide an antistatic layer.

<Coating composition for antistatic layer>
Dianal (BR-88 manufactured by Mitsubishi Rayon Co., Ltd.) 0.5 parts by mass Propylene glycol monomethyl ether 60 parts by mass Methyl ethyl ketone 15 parts by mass Ethyl lactate 6 parts by mass Methanol 8 parts by mass Conductive polymer resin IP-16 (Japanese Patent Laid-Open No. 9-203810) Publication) 0.5 parts by mass (formation of hard coat layer)
The following hard coat layer composition was applied to the film on which the antistatic layer was formed so that the dry film thickness was 3.5 μm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high-pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured, and a hard coat film having a hard coat layer was produced. The refractive index of the hard coat layer was 1.50.

<Hard coat layer composition>
Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Diethoxybenzophenone (UV photoinitiator) 2 parts by weight Methyl ethyl ketone 50 Part by mass Ethyl acetate 50 parts by mass Isopropyl alcohol 50 parts by mass The above composition was dissolved with stirring.

(Coating back coat layer)
The backcoat layer coating composition described below was applied to the opposite side of the surface coated with the hard coat layer with a gravure coater to a wet film thickness of 14 μm and dried at a drying temperature of 85 ° C. Was applied.

<Backcoat layer coating composition>
Acetone 30 parts by weight Ethyl acetate 45 parts by weight Isopropyl alcohol 10 parts by weight Cellulose diacetate 0.5 parts by weight Aerosil 200V 0.1 parts by weight (formation of an antireflection layer)
The four atmospheric pressure plasma discharge treatment apparatuses shown in FIG. 8 are connected, the electrode gap between the two electrodes of each apparatus is set to 1 mm, the following gas is supplied to the discharge space of each apparatus, and the hard coat produced above A thin film was sequentially formed on the layer. A high frequency power source manufactured by Shinko Electric Co., Ltd. (50 kHz) is used as the first high frequency power source for the first electrode of each device, the high frequency voltage is 10 kV / mm and the output density is 1 W / cm ² , and the second electrode is the second high frequency power source. As a high-frequency power source, a high-frequency power source manufactured by Pearl Industrial Co., Ltd. (13.56 MHz) is used. A high-frequency voltage of 0.8 kV / mm and an output density of 5.0 W / cm ² are applied, and plasma discharge is performed to mainly produce titanium oxide. A thin film as a component and an antireflection layer mainly composed of silicon oxide were formed. The discharge start voltage of nitrogen gas in the discharge space of each device at this time was 3.7 kV / mm. The following thin film forming gas was vaporized by a vaporizer in nitrogen gas and supplied to the discharge space while heating. Moreover, the roll electrode was rotated in synchronization with the conveyance of the cellulose ester film using a drive. Both electrodes were adjusted and kept at 80 ° C.

<Gas composition for titanium oxide layer formation>
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Addition gas: Hydrogen 2.0% by volume
<Gas composition for forming silicon oxide layer>
Discharge gas: Nitrogen 98.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Addition gas: Oxygen 1.0% by volume
On the hard coat layer, a titanium oxide layer, a silicon oxide layer, a titanium oxide layer, and a silicon oxide layer are provided in this order, and a substrate having an antistatic layer, a hard coat layer, and an antireflection layer (this is shown in Table 1). (Referred to as TAC). Each of the layers constituting the antireflection layer has a refractive index of 2.1 (film thickness of 15 nm), a refractive index of 1.46 (film thickness of 33 nm), a refractive index of 2.1 (film thickness of 120 nm), and a refractive index of 1. .46 (film thickness 76 nm).

[Preparation of Sample 1]
A high frequency power source (frequency: 5 kHz) manufactured by Shinko Electric Co., Ltd. was used on the base material having the hard coat layer and the antireflection layer prepared above, using an atmospheric pressure plasma discharge treatment apparatus provided with the cleaning film shown in FIGS. ), A thin film forming gas having the following composition was introduced into a discharge space to which a discharge power of 1.0 W / cm ² was applied, and an antifouling film as a thin film was formed to obtain Sample 1.

<Thin film forming gas composition>
Discharge gas: Nitrogen 98.3% by volume
Organometallic compound: Exemplified compound 15 0.2% by volume
(Example compound 15 is vaporized in nitrogen gas by a vaporizer manufactured by STEC Co.)
Additive gas: 1.5% by volume of hydrogen
[Preparation of Samples 2 to 11]
Samples 2 to 11 were produced in the same manner as in the production of Sample 1 except that Exemplified Compound 15 which was an organometallic compound was changed to each Exemplified Compound shown in Table 1.

[Preparation of Sample 12]
In the preparation of Sample 1, Sample 12 was prepared in the same manner except that the following pretreatment A was applied to the surface of the base material before forming the antifouling film.

Pretreatment A: Before forming the antifouling film on the substrate, the apparatus shown in FIG. 1 is used to inject and excite discharge gas of nitrogen: oxygen = 99: 1 (volume%) to Exposed to the excited discharge gas for 3 seconds. The high frequency power source was a high frequency power source (frequency: 50 kHz) manufactured by Shinko Electric Co., Ltd., and the discharge output was set to 5 W / cm ² .

[Preparation of Sample 13]
Sample 13 was prepared in the same manner as Sample 1 except that the following pretreatment B was applied to the surface of the base material before forming the antifouling film.

Pretreatment B: Before forming the antifouling film on the substrate, the apparatus shown in FIG. 5 was used to inject and excite discharge gas of nitrogen: oxygen = 99: 1 (volume%) to Exposed to the excited discharge gas for 3 seconds. The high frequency power source was a high frequency power source (frequency: 50 kHz) manufactured by Shinko Electric Co., Ltd., and the discharge output was set to 5 W / cm ² .

[Preparation of Sample 14]
Sample 14 was prepared in the same manner as in the preparation of Sample 1, except that a glass plate (product name: 0.5t soda lime glass single-side polished product manufactured by Nippon Sheet Glass Co., Ltd.) was used instead of the cellulose ester film as the base material. did.

[Preparation of Sample 15]
Sample 15 was prepared in the same manner as in the preparation of Sample 1, except that argon was used instead of the discharge gas.

[Preparation of Sample 16]
Sample 16 was prepared in the same manner as the sample 1 except that the apparatus used for forming the antifouling film was replaced with the apparatus shown in FIG. 3 and the apparatus shown in FIG. 1 without a cleaning film was used. Was made.

[Preparation of Samples 17 to 20]
Samples 17 to 20 were prepared in the same manner as in the preparation of Sample 16, except that Exemplified Compound 15 that was an organometallic compound was changed to each Exemplified Compound shown in Table 1.

[Preparation of Sample 21]
Sample 21 was prepared in the same manner as in the preparation of Sample 1, except that Exemplified Compound 15 which was an organometallic compound was changed to Fluorolink S10 manufactured by Solvay Solexis Co., Ltd.

[Preparation of Sample 22]
Sample 22 was prepared in the same manner as Sample 1 except that oxygen was used instead of hydrogen as the additive gas.

[Preparation of Sample 23]
In the production of Sample 1, the discharge gas was changed to nitrogen (98.3% by volume), except that the gas composition was changed to 50.0% by volume of nitrogen and 48.3% by volume of argon. Sample 23 was produced.

<< Measurement and evaluation of characteristic values of each sample >>
Samples 1 to 23 produced by each of the thin film forming methods described above were sampled immediately after the thin film formation and samples after 3 hours of continuous thin film formation, and the following measurements and evaluations were performed on each sample. went.

(Measurement of contact angle)
About each sample, the contact angle with respect to the water of the antifouling film surface and the contact angle with hexadecane were measured using a contact angle meter CA-W manufactured by Kyowa Interface Science Co., Ltd. in an environment of 23 ° C. and 55%. In addition, the measurement was performed at 10 locations at random and the average value was obtained.

[Evaluation of oil-based ink wiping performance]
Using oil-based ink (Zebra Co., Ltd. Mackey extra fine black MO-120-MC-BK), the sample surface was painted 3 mmφ, and then the oil-based ink image was wiped off with a soft cloth (BEMCOT M-3 250 mm × 250 mm manufactured by Asahi Kasei Co., Ltd.) This operation was repeated 20 times at the same position, the remaining state of the oil-based ink after wiping 20 times was visually observed, and the wiping property of the oil-based ink was evaluated according to the following criteria.

◎: Oil-based ink was completely wiped off ○: Oil-based ink was almost wiped off ×: Oil-based ink was not wiped off in part [Measurement of surface resistivity]
As a result of measuring the surface specific resistance values of the samples of the present invention according to the following method, they were all 1 × 10 ¹² Ω / □ or less.

(Measurement method of surface resistivity)
The sample was conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and then measured using a Teraohm Meter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd. The electrodes used for the measurement were measured by placing two electrodes (1 cm x 5 cm in contact with the sample) at an interval of 1 cm, contacting the sample with the electrode, and multiplying the measured value by 5 times. The specific resistance value (Ω / □) was used.

  The results excluding the surface specific resistance obtained as described above are shown in Table 1.

  As can be seen from Table 1, an antifouling film was formed using a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom using an atmospheric pressure plasma discharge treatment apparatus equipped with a cleaning film. The sample of the invention is superior to the comparative example in the water repellency of the formed antifouling film, the wiping property of the oil-based ink, and the sample after the continuous thin film formation is maintained without reducing its effect. I understand that

It is sectional drawing which shows an example of the discharge space comprised from the electrode pair which opposes used with the conventional thin film formation method. It is sectional drawing which shows an example of the discharge space comprised from the opposing electrode pair provided with the cleaning film used for the thin film formation method of this invention. It is a figure which shows an example of the plasma discharge processing apparatus under the atmospheric pressure which concerns on this invention, or the pressure of the vicinity. It is a perspective view showing the electrode pair used with the plasma discharge processing apparatus which concerns on this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge apparatus used for the surface treatment of the base material which concerns on this invention. It is the schematic which shows another example of the atmospheric pressure plasma discharge apparatus used for thin film formation of the base-material surface based on this invention.

Explanation of symbols

3 Piping 4 Temperature control device 5 High frequency power source 6 Ground 10 Support member 13 Substrate transport mechanism 14 First guide roller 15 Nip roller 16 Second guide roller 99, 100, 200, 300 Plasma discharge treatment device 101, 102 Electrode 101 ', 102 'second electrode 104 support 104' first electrode 101a, 102a discharge surface 124 gas supply part 125 nozzle body part 126 gas ejection part 127 cleaning film 128 heating member 130 film transport mechanism 131 first film guide roller 132 first film 2 Film guide roller 135 Roll rotating electrode 136 Square column type fixed electrode group 140 Voltage applying means 141 First power supply 142 Second power supply 150 Gas supplying means 151 Gas generator 160 Electrode temperature adjusting means 164, 167 Guide roll 16 5, 166 Nip roll 170 Plasma discharge treatment vessel 211 Metal base material 212 Dielectric 213 Hollow portion 215 Corner portion F Substrate G Thin film forming gas G ′ Excited thin film forming gas A Discharge space

Claims (19)

A thin film forming gas is introduced into a discharge space composed of electrode pairs facing each other at atmospheric pressure or near atmospheric pressure, the thin film forming gas is excited, and the substrate is exposed to the excited thin film forming gas. In the thin film formation method of forming a thin film on the substrate,
The thin film forming gas contains an organometallic compound having an organic group having a fluorine atom,
The electrode pair has a cleaning film that prevents direct exposure to the excited thin film forming gas, and the cleaning film is heated stepwise or continuously upstream in the transport direction until reaching the discharge surface. And a method of forming a thin film, wherein the thin film is transported in close contact with the discharge surface and at least a part of the surface of the electrode pair other than the discharge surface continuous with the discharge surface. The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (1).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. j represents an integer of 0 to 150. ] The thin film forming method according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group or an aryl group. K represents an integer of 0 to 50, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be linked to form a ring. ] The thin film forming method according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₂ represents an alkyl group, an alkenyl group, or an aryl group, and k represents an integer of 0 to 50. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (4).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. j represents an integer of 0 to 150. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (5).
General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
[Wherein, M represents In, Al, Sb, Y or La, and Rf represents an alkyl group or an alkenyl group in which at least one hydrogen atom is substituted with a fluorine atom. X represents a simple bond or a divalent group, and Y represents a simple bond or an oxygen atom. R ₈ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R ₉ represents a substituted or unsubstituted alkyl group or alkenyl group. k represents an integer of 0 to 50, m + n + p = 3, m is at least 1, and n and p each represent an integer of 0 to 2. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (6).
General formula (6)
^{_{R f1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3
[Wherein, R ^f1 represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1 to 50 An integer, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (7).

[Wherein, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1, m and n Represents an integer of 0 to 2, and p represents an integer of 1 to 10. ] The thin film forming method according to claim 1, wherein the discharge space is formed by applying a high-frequency electric field between the pair of electrodes. The thin film forming method according to claim 1, wherein the thin film forming gas contains 50% by volume or more of a rare gas and / or nitrogen. The thin film forming method according to claim 1, wherein the thin film forming gas contains 0.01 to 10% by volume of a reducing gas. The thin film forming method according to claim 11, wherein at least one of the reducing gases is hydrogen gas. The thin film forming method according to claim 1, wherein the thin film forming gas contains 0.01 to 10% by volume of an oxidizing gas. The thin film forming method according to claim 13, wherein at least one of the oxidizing gases is oxygen gas. The thin film is formed on the substrate by exposing the substrate to a discharge space or an excited discharge gas and performing a pretreatment, and then exposing the substrate to the excited thin film forming gas. The thin film formation method of any one of 1-14. The method of forming a thin film according to claim 1, wherein the surface of the base material on which the thin film is formed contains an inorganic compound. The thin film forming method according to any one of claims 1 to 15, wherein a main component of a base material surface forming the thin film is a metal oxide. A thin film forming body obtained by the thin film forming method according to claim 1. It is a thin film formation body obtained by the thin film formation method of any one of Claims 1-17, Comprising: The surface specific resistance value of the thin film surface formed on the base material is 23 degreeC, 55% RH conditions A thin film forming body characterized in that it is 1 × 10 ¹² Ω / □ or less below.

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