JPWO2006092927A1 - Antifouling film and antifouling film manufacturing apparatus - Google Patents

Abstract

An object of the present invention is to obtain an antifouling film excellent in antifouling performance, such as high uniformity and excellent water repellency, oil repellency, sebum and ink wiping property and repeated durability, without variation. For this purpose, the antifouling film is formed on a base material using an organometallic compound having an organic group having a fluorine atom as a thin film forming gas raw material, and a negative secondary ion measurement is performed using a Tof-SIMS measuring device. The detected intensity ratio of NO 3− ions to the total detected ion intensity is 1.0 × 10 −3 or less, and the detected intensity ratio of NH 4+ ions to the total detected ion intensity is 1.0. × 10-4 or more.

Description

  The present invention is formed by using an organometallic compound having an organic group having a fluorine atom as a thin film forming raw material, has little adhesion of dirt, dust, etc., and can easily remove attached dirt, dust, etc. Related to antifouling film.

  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.

In view of the above problems, a method of easily forming an antifouling film using an atmospheric pressure plasma method 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, it has been found that the above method does not have sufficient durability and causes some variation in antifouling performance.

  Therefore, an object of the present invention is to obtain a highly uniform and reproducible antifouling film excellent in antifouling performance, such as excellent water repellency, oil repellency, sebum and ink wiping properties and repeated durability. It is in.

  The above object of the present invention is achieved by the following means.

[1] When an antifouling film formed on a substrate from a raw material mainly composed of an organometallic compound having an organic group having a fluorine atom is subjected to negative secondary ion measurement using a Tof-SIMS measurement device The detected intensity ratio of NO ₃ ⁻ ions to the total detected ion intensity is 1.0 × 10 ⁻³ or less, and the detected intensity ratio of NH ₄ ⁺ ions to the total detected ion intensity when a positive secondary ion is measured is 1. An antifouling film characterized by being 0 × 10 ⁻⁴ or more.

    [2] The antifouling film according to [1], which is formed by a dry thin film forming method.

  [3] A gas in which the dry thin film forming method uses an organometallic compound having an organic group having a discharge gas and a fluorine atom between opposing electrodes (discharge space) at or near atmospheric pressure. Characterized in that the gas is excited by applying a high-frequency voltage between the electrodes and the thin film is obtained on the substrate by exposing the substrate to the excited gas. The antifouling film according to [2].

  [4] In the dry thin film forming method, a discharge gas is introduced into a discharge space and excited under atmospheric pressure or a pressure in the vicinity thereof, and the excitation gas and an organometallic compound having an organic group having a fluorine atom are obtained. It is an atmospheric pressure plasma method in which a thin film is obtained on the substrate by contacting the substrate with the indirect excitation gas as an indirect excitation gas by contacting the contained thin film forming gas outside the discharge space. The antifouling film according to [2].

  [5] The antifouling film according to any one of [1] to [4], wherein the organometallic compound having an organic group having a fluorine atom is 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. ]
[6] The antifouling film according to [5], 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. ]
[7] The antifouling film according to [6], 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, and Rf represents an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Alternatively, it represents an alkenyl group, and X represents a simple bond or a divalent group. R ₁₂ represents an alkyl group, an alkenyl group, or an aryl group, and k represents an integer of 0 to 50. ]
[8] The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (4), [1] to [4] Antifouling membrane.

[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. ]
[9] The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (5), [1] to [4] Antifouling membrane.

General formula (5)
During _{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p [Formula, M represents In, Al, Sb, Y or La, Rf is at least hydrogen atoms One represents an alkyl group or an alkenyl group 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. ]
[10] The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (6), [1] to [4] Antifouling membrane.

General formula (6)
_{Rf 1 (OC 3 F 6)} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3 wherein, Rf ₁ is 1 to the number of carbon atoms 16 linear or branched perfluoroalkyl groups, R ₂ represents a hydrolyzable group, Z represents —OCONH— or —O—, m1 represents an integer of 1 to 50, n1 represents an integer of 0 to 3, p1 Represents an integer of 0 to 3, q1 represents an integer of 1 to 6, and 6 ≧ n1 + p1> 0. ]
[11] The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (7), [1] to [4] Antifouling membrane.

[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. ]
[12] The antifouling film according to any one of [3] to [11], wherein the atmospheric pressure plasma method is performed in an atmosphere containing 15 vol% or more of nitrogen gas as a discharge gas.

  [13] Before the antifouling film is formed on the base material by the dry thin film forming method, the base material is exposed to a discharge space or an excited discharge gas to perform pretreatment [2] to [12] The antifouling film according to any one of [12].

  [14] The antifouling film according to any one of [1] to [13], wherein the substrate surface contains an inorganic compound.

  [15] The antifouling film according to any one of [1] to [14], wherein a main component of the substrate surface is a metal oxide.

  [16] An antifouling film production apparatus for producing the antifouling film according to any one of [1] to [15].

  According to the present invention, an antifouling film having high uniformity, excellent water repellency and oil repellency, excellent antifouling performance such as wiping of sebum and ink and repeated durability thereof can be obtained with good reproducibility.

It is a figure which shows an example of the plasma discharge processing apparatus under atmospheric pressure or the pressure of the vicinity. It is a perspective view which shows an example of a roll rotation electrode. It is a perspective view which shows an example of a prismatic fixed electrode. It is the figure which showed an example from which the positional relationship of the electrode of a plasma discharge treatment apparatus and a base material differs. It is the figure which showed another example from which the positional relationship of the electrode of a plasma discharge treatment apparatus and a base material differs. 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 sectional drawing which shows an example of the atmospheric pressure plasma discharge processing apparatus which can be used for this invention. It is sectional drawing which shows another example of the atmospheric pressure plasma discharge processing apparatus from which arrangement | positioning of the electrode which can be used for this invention differs.

Explanation of symbols

1, 30, 100 Plasma discharge treatment apparatus 101, 102 Electrode 5, 41 High frequency power supply 25 Roll rotating electrode 25A, 36A, 101A, 102A Metal base material 25B, 36B, 101B, 102B Dielectric 31, 131 Plasma discharge treatment vessel 32, 132 Discharge treatment chamber 36, 136 Prismatic fixed electrode 40, 140 Voltage application means 50, 150 Gas filling means 51, 151 Gas generator 52, 152 Air supply port 53, 153 Exhaust port 60, 160 Electrode temperature adjustment means 64, 67 164, 167 Guide rolls 65, 66, 165, 166 Nip rolls 68, 69, 168, 169 Partition plate 103 Processing position F, 8 Base material G Reactive gas G 'Processing exhaust gas G ° Reactive gas P causing plasma discharge P Liquid pump A Discharge space 2, 2 'First electrode 3, 3' Second power Electrode 4 Voltage application means 6 Insulator 9 Ground G ₁ Discharge gas G ₁ ′ Excited discharge gas M Thin film forming gas A Discharge space B Discharge space outside

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

  As a result of intensive studies, the present inventors have found that nitrogen atmospheric pressure plasma, particularly nitrogen atmospheric pressure plasma in a reducing atmosphere, has little durability, antifouling performance, and variation. Further, the present inventors examined the composition of the film in detail, and found that an antifouling film having excellent antifouling property, durability and less variation can be formed when satisfying a certain composition, not limited to nitrogen atmospheric pressure plasma. I found it.

  First, the organometallic compound having an organic group having a fluorine atom used as a thin film forming raw material in the formation of the antifouling film according to the present invention will be described in detail.

  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, An organometallic compound directly bonded to a metal such as lanthanum, iron, neodymium, copper, gallium, hafnium. 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. To express. 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)
^{_{Rf 1 (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), Rf ¹ 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.

Number of carbon atoms of the linear or branched perfluoroalkyl group may be introduced into Rf ¹ is more preferably 1 to 16, 1 to 3 is most preferred. Therefore, the _{^{Rf 1, -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: An organic titanium compound having fluorine such as (CF ₃ C ₂ H ₄ ) (CH ₃ ) ₂ Ti—O—Ti (CH ₃ ) ₃ , and the following fluorine-containing organometallic compounds are given as examples. Can do.

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 mentioned 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. It is marketed by Solvay Solexis Co., Ltd. (for example, Fluorolink S10), etc., and 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.

  In the present invention, a thin film is formed on a substrate using an organometallic compound having an organic group having a fluorine atom. The use of a raw material mainly composed of these organometallic compounds means that these components are contained in an amount of 50% by mass or more, preferably 70% by mass or more, in the raw material for film formation.

  The substrate used is not particularly limited, and examples thereof include metal oxide, plastic (film), metal, ceramics, paper, wood, nonwoven fabric, glass plate, ceramic, and building material. From the viewpoint of exerting the object effect of the present invention, it is preferable that the surface is composed of a surface containing an inorganic compound or a surface containing an organic compound. Among them, a metal oxide such as silica or titania is more preferable as a main component. It is the base material of the surface. 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. Further, for example, an antireflection film having a metal oxide film layer is a preferable substrate, and the antifouling layer according to the present invention is preferably formed on the outermost surface thereof.

  The method for forming the antifouling film is not limited, but for example, the following sol-gel method or the like as a method by coating, or atmospheric pressure plasma, vacuum plasma, sputter deposition or the like as a dry thin film forming method.

  In order to form a thin film mainly composed of a metal oxide using the organometallic compound having an organic group having fluorine according to the present invention by the sol-gel method, for example, an organic metal having an organic group having fluorine according to the present invention. In addition to using a compound, a metal oxide sol obtained from a metal alkoxide or alkoxysilane or a metal salt is coated on a base material to form a three-dimensional crosslink and gel, thereby forming a uniform film of metal oxide or silica. This is basically the same as the method of forming. The sol is in a state of low viscosity and fluidity. For example, a state in which a certain amount of three-dimensional cross-linking is applied after applying this to a substrate is considered to be a gel state. Although it may contain, such a state is also expressed here for convenience such as gel or gel thin film.

  Similar to metal alkoxide and alkoxysilane, a sol solution is prepared from an organic metal compound having an organic group having fluorine, and a condensation reaction catalyst (curing accelerator) such as an acid is added to form a sol.

  A metal oxide film is formed by mixing these sol-gel curing accelerator solutions immediately before coating or adding and coating them by any method.

  By using the metal compound having an organic group having a fluorine atom according to the present invention, a film or a thin film mainly composed of a metal oxide can be obtained.

  A multimer partially hydrolyzed and polymerized can also be used.

  Examples of the catalyst as a curing accelerator for promoting the crosslinking by the condensation reaction of these organometallic compounds include the following.

  First, lower alcohols such as water and methanol. These promote the crosslinking reaction by condensation of the metal alkoxide by substituting the alkoxy group of the metal compound (having an alkoxy group) or metal alkoxide having an organic group having a fluorine atom with a hydroxyl group or a methoxy group, respectively. Of these, water is preferred.

  Acids. The acid has a catalytic action that promotes hydrolysis of the above metal alkoxide, or hydrolysis or solvolysis with methanol or the like, and promotes a condensation reaction such as dehydration or demethanol. Therefore, this is an inorganic or organic acid. Any of them may be used, and examples include hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, phthalic acid, benzoic acid, p-toluenesulfonic acid and the like.

  Metal catalysts such as Al chelate and Zr chelate. Examples of chelating ligands include picolinic acid, salicylic acid, 1,3-diketones, and the like.

  Further, as a catalyst, instead of the above acids, monocyclic amines, diethanolamines, triethanolamines, diethylamines, triethylamines, bicyclic ring amines such as DBU (diazabicycloundecene-1), DBN (diazabicyclononene), etc. Bases such as ammonia and phosphine can also be used.

  Components such as metal alkoxide are dissolved or dispersed in a solvent. As the solvent, the above metal alkoxide, in addition to this, a catalyst, other necessary components, etc. are coated on a plastic film, a glass substrate or the like. A thin film is formed. Since it is necessary to evaporate the solvent after coating, a volatile solvent is preferable as the solvent, and any solvent can be used as long as it does not react with an organometallic compound or a catalyst and does not dissolve a substrate such as a plastic film. A solvent that is usually used can be used. For example, water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, methoxymethyl alcohol, acetates such as ethyl acetate and methyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol mono Examples thereof include ethylene glycol monoalkyl ethers such as ethyl ether, dimethylformamide, dimethyl sulfoxide, and acetylacetone.

  Drying after coating is possible even at room temperature, but it is preferable to heat, and this promotes hydrolysis and polycondensation reactions as the solvent evaporates, making it possible to create a stronger three-dimensionally crosslinked gel film It becomes. Therefore, the heat treatment can be performed at a heating temperature suitable for these purposes or the heat resistance of the plastic film or the like, and is usually 40 ° C. or higher, preferably 50 ° C. to 280 ° C. It is performed within the range and the substrate has heat resistance.

  As described above, in the sol-gel method, after applying the sol solution to the substrate, generally, a heat treatment (firing) step at a high temperature is required. Instead of heating, the wavelength is 360 nm or less. It is also useful to use a method of crystallizing a metal oxide forming a thin film by irradiating with ultraviolet light.

  These sol solutions are applied using known coating machines such as dipping, spin coater, knife coater, bar coater, blade coater, squeeze coater, reverse roll coater, gravure roll coater, slide coater, curtain coater, spray coater, die coater, etc. Can be applied. Of these, a method capable of continuous application is preferably used. In the case of simultaneous multi-layering, a solution containing a metal alkoxide or metal salt such as alkoxysilane and a solution having a curing accelerator are simultaneously multi-layered by the above-mentioned coating machine. You can use the machine. Moreover, in this invention, the antifouling film | membrane concerning this invention can be obtained by adding ammonia in a coating liquid.

  Moreover, the thin film concerning this invention can be formed with the dry-type thin film formation method. Some typical examples of these dry thin film forming methods include vapor deposition, sputtering, and CVD.

  For example, in the vacuum deposition method, the inside of the vapor deposition apparatus provided with an exhaust port connected to a vacuum pump for keeping the inside of the vapor deposition apparatus is kept in vacuum, and the metal compound having the organic group having fluorine atoms is used as a raw material compound. As an evaporation source, for example, a sintered filter impregnated with these raw material compounds is used, and the entire filter is heated with an electron gun under vacuum conditions to generate a vapor flow of the organometallic compound raw material. By introducing an additive gas such as ammonia or ammonia, the antifouling film according to the present invention can be formed on the substrate introduced into the apparatus.

  A vacuum plasma CVD process can be similarly used to form a thin film according to the present invention.

In the vacuum plasma CVD process, it is necessary to introduce a reactive gas so as to keep the atmosphere in the range of 6.67 × 10 ⁻¹ Pa to 2.67 × 10 ³ Pa, in order to increase the processing speed. In this case, it is preferable to adopt a high output condition on the high voltage side as much as possible for the counter electrode. In the msts and vacuum plasma CVD processing, the frequency of the pulse electric field is preferably 1 kHz to 100 kHz.

  The magnitude of the voltage applied to the counter electrode is appropriately determined, but it is preferable that the electric field strength be in the range of 1 to 100 kV / cm when applied to the electrode. If it is less than 1 kV / cm, the process takes too much time, and if it exceeds 100 kV / cm, arc discharge tends to occur. In addition, the larger the treatment speed is, the higher the processing speed is. Further, a pulse electric field on which direct current is superimposed may be applied.

  Also in these vacuum apparatuses, it is preferable that the sheet-like base material subjected to the surface treatment is introduced into the processing container and discharged so as to continuously travel through the space between the counter electrodes.

  Moreover, in this invention, the antifouling film | membrane concerning this invention can be obtained by introduce | transducing nitrogen and ammonia as additive gas at the time of thin film formation.

  Similarly, the sputtering method can be used for forming the antifouling film according to the present invention, and the antifouling film according to the present invention can be obtained by introducing an additive gas such as nitrogen or ammonia into the sputtering apparatus.

  In the present invention, a gas containing a discharge gas and an organometallic compound having an organic group having a fluorine atom as a thin film forming gas raw material component is supplied between opposing electrodes (discharge space) at atmospheric pressure or in the vicinity thereof. Then, a so-called atmospheric pressure plasma method (described later) is used in which the gas is excited by applying a high-frequency voltage between the electrodes, and a thin film is obtained on the substrate by exposing the substrate to the excited gas. be able to.

  In the present invention, the antifouling film of the present invention is a vapor deposition method, a sputtering method and a vacuum plasma among these film formation methods, rather than a wet film formation method such as a sol-gel method. It has been found that a dry thin film forming method such as a CVD process or an atmospheric pressure plasma method is a preferable film forming method, and a particularly preferable thin film forming method is an atmospheric pressure plasma method. The atmospheric pressure plasma method will be described in detail later.

  The antifouling film of the present invention will be described.

  The present inventors examined a thin film mainly composed of a metal oxide formed using the organometallic compound having an organic group having a fluorine atom. The formed thin film was subjected to surface analysis by Tof-SIMS. It has been found that the antifouling property of the formed film becomes good when a specific relationship is satisfied with respect to the specific ion species to be detected and their amount.

That is, when surface analysis by Tof-SIMS is performed, the ratio of the detected intensity of NO ₃ ⁻ ions to the total detected ion intensity when negative secondary ions are measured is 1.0 × 10 ⁻³ or less, and positive secondary The ratio of the detected intensity of NH ₄ ⁺ ions to the total detected ion intensity when ions are measured is 1.0 × 10 ⁻⁴ or more, preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ^−2. When the relationship between the intensity of negative secondary ions and positive secondary ions is better, one is less than a certain value and the other is larger than a certain value, these are mainly metal oxides. It has been found that the thin film is particularly excellent in water repellency and oil repellency.

In order to obtain these ion detection intensities according to the present invention, for example, in the atmospheric pressure plasma method, operation factors such as applied voltage, applied output, applied frequency, gas type and amount, and concentration are appropriately set. For example, if the applied voltage is lowered too much, the intensity ratio of NH ₄ ⁺ ions becomes small, and if the voltage is raised too much, the intensity ratio of NH ₄ ⁺ ions becomes too large and the antifouling film according to the present invention cannot be obtained. .

  In the thin film formed from an organometallic compound having an organic group having a fluorine atom, for example, a compound such as fluorine-containing alkoxysilane by the above-described method, basically, fluorine atoms are somehow formed in the film (for example, fluorine In the case of a film having excellent antifouling properties, the present inventors have added in addition to fluorine atoms from the results of the above-mentioned Tof-SIMS. Furthermore, it is considered that nitrogen atoms are incorporated into the film structure in some form (for example, as some ions, or a bond between nitrogen and alkyl or metal).

  The measuring method by Tof-SIMS is shown below.

<Measuring method>
NO ₃ ⁻ and NH ₄ ⁺ in the thin film can be measured using a time-of-flight secondary ion mass spectrometer. The apparatus and measurement conditions are not limited to the following.

In the present invention, a time-of-flight secondary ion measurement device (Tof-SIMS) used was TRIFT-II (US) manufactured by PHI. Considering the possibility of sample deterioration due to vacuum before setting to the measurement position from sample evacuation, it must be performed within 10 minutes. In was used as a primary ion, the acceleration voltage was 15 kV, and an area of 60 μm × 60 μm was measured. The measured mass range is 0.5a. For positive secondary ions. m. u. -2000a. m. u. For negative secondary ions, 0.5 a. m. u. -1000a. m. u. As measured. The integration time needs to be adjusted so that the amount of In ions to be irradiated is 1.0 × 10 ¹² ions / cm ² or less. This time, it was 3 minutes for the positive secondary ion measurement and 1 minute for the negative secondary ion measurement. If a phenomenon (charge up) occurs in which the sample is charged during measurement and secondary ions cannot be obtained, it is necessary to take charge correction measures. This time, a metal mesh for charge correction and an electron gun for charge correction were used. Furthermore, the mass resolution (M / ΔM) is 3000 or more (in C ₃ H ₇ ⁺ ) for positive ion detection and 2000 or more (for negative secondary ion detection) so that detection peaks are sufficiently separated ( OH ^- to be), the need to adjust the sample voltage, lens voltages and the like. The measurement spectrum needs to be calibrated in order to obtain the mass number accurately.

  When peak separation is insufficient and peak intensity is difficult to obtain, it is necessary to perform a peak separation operation so that only a target peak can be obtained by a peak separation routine or the like.

Calculation method:
The detected intensity ratio of NH ₄ ⁺ ions to the total detected ion intensity is 0.5 a. m. u. -2000a. m. u. Calculated as the ratio (NH ₄ ⁺ ion intensity / total ion intensity) of the detected NH ₄ ⁺ ion intensity (number of detected ions) to all positive ion intensity (number of detected ions) did.

Further, the detected intensity ratio of NO ₃ ⁻ ions is 0.5 a. m. u. -1000a. m. u. Calculated as ^- (ionic strength / total ionic strength NO ₃₎ ^- for all the detected negative ionic strength (number of detected ions), NO ₃ is detected in the ionic strength ratio of (the number of detected ions) did.

  About these ions, when it is in such a range, it is not clear why a film having high water repellency, oil repellency and excellent antifouling property is obtained, but the generation of the negative secondary ions is first, It is considered that ions adsorbed or weakly bound to the film surface are released by collision of temporary ions, and even on the film surface formed from the fluorine atom-containing organometallic compound of the present invention, the generation of negative secondary ions is It is thought that it originates from the residue of the compound used for manufacture, such as a catalyst and an additive causing these, and when these organic matter and inorganic matter increase, the water repellency or oil repellency etc. of the surface of these substances will be impaired. thinking. On the other hand, positive secondary ions are often generated from atoms that constitute the surface (or the inside of the pole surface), such as metals, and for example, a relatively large amount of ammonium ions or the like can be seen here. Nitrogen is considered to be incorporated into, for example, by bonding with metal atoms, and the presence of such nitrogen atoms to some extent is necessary and preferable for the film having the above properties.

  In order to obtain such a thin film, the manufacturing method is basically not limited, and it is sufficient that some form of nitrogen is incorporated into the film in a similar form even if a small amount of nitrogen is used.

In the present invention, as described above, an organic metal compound having an organic group having a discharge gas and a fluorine atom between opposing electrodes (discharge space) under atmospheric pressure or a pressure in the vicinity thereof is used as a thin film forming gas raw material component. A gas is supplied, a high frequency voltage is applied between the electrodes to excite the gas, and a thin film is obtained on the substrate by exposing the substrate to the excited gas, or a discharge gas is introduced into the discharge space. An indirect excitation gas that is excited by introduction and brought into contact with the excited discharge gas and a thin film forming gas containing an organic metal compound having an organic group having a fluorine atom outside the discharge space. The antifouling film is formed using a so-called atmospheric pressure plasma method to obtain a thin film on the base material by exposing the base material to the base material when measured by the Tof-SIMS. ₃ ^- equal negative Forming a film in which the ON is 1.0 × 10 ⁻³ or less and the ratio of the detected intensity of NH ₄ ⁺ ions to the total detected ion intensity when measuring positive secondary ions is 1.0 × 10 ⁻⁴ or more Is preferable.

  In order to fix nitrogen atoms in the film in this way, in addition to an organic metal compound having an organic group having a fluorine atom containing nitrogen in a thin film forming gas (raw material gas), a nitrogen-containing component (for example, ammonia) In particular, an organometallic compound having an organic group having a fluorine atom is preferably used as a thin film forming gas raw material in an atmosphere containing 15 vol% or more of nitrogen gas as a discharge gas. The atmospheric pressure plasma treatment is performed by supplying the gas to be used. In this way, it is presumed that nitrogen atoms are fixed in the thin film without mixing, particularly with a nitrogen-containing component as an additive gas.

  A thin film formed by an atmospheric pressure plasma method using an organometallic compound having an organic group having a fluorine atom at these atmospheric pressures or near atmospheric pressure as a thin film forming gas raw material component is mainly composed of metal oxide as described above. For example, in the case of an organic silicon compound (fluorine-containing alkoxysilane or the like), it is considered that the film is mainly composed of silicon oxide, and in the case of an organic titanium compound (fluorine-containing titanium alkoxide or the like), for example, the film is mainly composed of titanium oxide. Basically, however, it is considered that components or organic groups derived from organic groups having fluorine atoms as raw materials are also bonded to these metal oxides. The meaning of the main component is considered to be that an organic group, a fluorine-containing organic group, a fluorine atom or the like is incorporated into the structure at a certain ratio, rather than having a silicon oxide or titanium oxide structure completely.

  Next, an atmospheric pressure plasma method, which is the most preferable method for producing an antifouling film using an organometallic compound having an organic group having a fluorine atom according to the present invention as a raw material for forming a thin film, will be described.

  With the atmospheric pressure plasma method, a discharge gas and a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom are introduced into the discharge space and excited under atmospheric pressure or a pressure near atmospheric pressure, The substrate is exposed to excited gas (plasma gas) to form a thin film on the substrate.

  Further, the discharge gas is introduced into the discharge space and excited, and the thin film forming gas containing the organometallic compound having an organic group having a fluorine atom is brought into contact with the outside of the discharge space to form an indirect excitation gas. A thin film may be formed on the base material by exposing the base material to a gas, and several such variations can be considered, but a material more suitable for the material, apparatus, etc. used can be used.

  When the discharge gas directly exposed to the discharge space is brought into contact with the thin film forming gas outside the discharge space, it is estimated that the thin film forming gas receives energy from the discharge gas excited in the discharge space and is indirectly excited. . In this invention, what processed the thin film formation gas in this way is called indirect excitation plasma gas.

  Using indirect excitation plasma gas in this way can form an antifouling film at a very high speed and at a higher speed than when using a thin film forming gas directly exposed to the discharge space. There is.

  Further, in the present invention, the discharge space is sandwiched between electrode pairs arranged to face each other at a predetermined distance, and a voltage is applied by introducing a discharge gas or a thin film forming gas between the electrode pairs. It is a space where discharge occurs. The term “outside the discharge space” means a space that is not the discharge space.

  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.

  In the present invention, the discharge gas supplied to the discharge space is a gas capable of causing discharge. Examples of the discharge gas include nitrogen, rare gas, air, hydrogen, oxygen, and the like. These may be used alone as a discharge gas or may be mixed. It is preferable to contain 50-100 volume% of discharge gas with respect to the total gas supplied to discharge space.

  In the present invention, the thin film forming gas refers to a gas that is chemically deposited on a substrate to form a thin film. In the present invention, the content of the organometallic compound having an organic group having a fluorine atom according to the present invention relative to the thin film forming gas is preferably in the range of 0.001 to 30.0% by volume.

  The thin film forming gas of the present invention can contain nitrogen, a rare gas, or the like described as the discharge gas. The thin film forming gas of the present invention may be used by mixing 0.001% to 30% by volume of auxiliary gas such as hydrogen gas, oxygen gas, nitrogen gas, air.

  In particular, when a rare gas such as helium or argon is used as the discharge gas, it is preferable to mix a gas containing nitrogen, for example, nitrogen gas, hydrogen gas, ammonia gas or the like as an auxiliary gas.

  By using the above-mentioned atmospheric pressure plasma method as these discharge gas and thin film forming gas, a thin film mainly composed of metal oxide can be obtained as an antifouling film on the substrate.

  Next, some specific examples of the atmospheric pressure plasma discharge treatment apparatus suitable for the production of the antifouling film of the present invention will be described below with reference to the drawings.

  FIG. 1 is a view showing another example of a plasma discharge processing apparatus under atmospheric pressure or a pressure in the vicinity thereof according to the present invention. FIG. 1 includes a plasma discharge processing apparatus 30, a gas filling means 50, a voltage applying means 40, and an electrode temperature adjusting means 60. FIG. 1 shows a plasma discharge treatment of the substrate F between the roll rotating electrode 25 and the plurality of prismatic fixed electrodes 36. The substrate F is unwound from the original winding (not shown) and conveyed, or the substrate F is conveyed from the previous process, passes through the guide roll 64 and passes through the nip roll 65 to block the air and the like. , While being wound while being in contact with the roll rotating electrode 25, it is transferred between the plurality of prismatic fixed electrodes 36, passed through the nip roll 66 and the guide roll 67, and taken up by a winder (not shown), or Transfer to process. The gas filling means 50 controls the flow rate of the reaction gas G containing the thin film forming gas and the discharge gas generated by the gas generator 51 and puts it into the plasma discharge treatment vessel 31 of the discharge treatment chamber 32 from the air supply port 52. The inside of the plasma discharge treatment vessel 31 is filled with a reaction gas G containing a discharge gas and a thin film forming gas, and the treatment exhaust gas G ′ is discharged from the exhaust port 53. Next, the voltage applying means 40 applies a voltage to the prismatic fixed electrode 36 by the high frequency power supply 41, and the roll rotating electrode 25 is grounded to generate discharge plasma. The roll rotating electrode 25 and the prismatic fixed electrode 36 are heated or cooled using the electrode temperature adjusting means 60 and fed to the electrode. The temperature of the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is adjusted from the inside of the roll rotating electrode 25 and the prismatic fixed electrode 36 via the pipe 61 by the liquid feed pump P. The return piping from the electrode is omitted. 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 rotating electrode using a roll 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 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

  The plasma discharge treatment vessel 31 may be a metallic vessel insulated with Pyrex (registered trademark) glass or plastic. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to achieve insulation.

  The electrode according to the present invention is composed of a metal base material and a dielectric material coated thereon. FIG. 2 is a perspective view showing an example of the roll rotating electrode in the present invention. In FIG. 2, the structure of the roll rotating electrode 25 is a combination in which a metal base material 25A having metallic conductivity is coated with a dielectric 25B sealed with an inorganic substance after ceramic spraying. The dielectric may be a lining.

  FIG. 3 is a perspective view showing an example of a prismatic fixed electrode. In FIG. 3, the prismatic fixed electrode 36 is the same as the above-mentioned roll rotating electrode, or a combination in which a dielectric 36B covered with an inorganic substance after ceramic spraying is applied to a metal base material 36A having metallic conductivity. It has become. The dielectric may be a lining. The fixed electrode may be a columnar (cylindrical) type. As the fixed electrode, the prismatic fixed electrode 36 is preferable because it has the effect of expanding the discharge range as compared with the cylindrical type.

  In these electrodes, metals such as silver, platinum, stainless steel, aluminum, iron, titanium, copper, and gold 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 it is preferable to perform a sealing treatment with silicon oxide or the like. As the sealing treatment, the alkoxysilane sealing material can be made inorganic by a sol-gel reaction.

  FIG. 4 is a diagram showing an example in which the positional relationship between the electrode and the substrate of the plasma discharge treatment apparatus is different. A reactive gas G containing a discharge gas and a thin film forming gas is introduced between the electrodes 101 and 102 of the plasma discharge processing apparatus 100 to cause plasma discharge. Thereby, the plasma-excited reactive gas G ° (represented by a dotted line) flows downward to form a thin film on the surface of the substrate F that is transferred under the electrode. G ′ is the treated exhaust gas. 101A and 102A are metal base materials of the electrodes 101 and 102, and 101B and 102B are dielectrics. There is also a method of forming a thin film on a substrate having projections and depressions such as a lens at the processing position 103 by generating a reactive gas G ° causing plasma discharge, instead of the substrate F that transfers the gap in this way.

  FIG. 5 is a view showing another example of the plasma discharge processing apparatus under the atmospheric pressure or the pressure in the vicinity thereof according to the present invention.

  The plasma discharge treatment apparatus 100 is not shown in addition to a high-frequency power source that applies a high-frequency electric field between the opposing electrodes 101 and 102, which are composed of a metal base material and dielectrics 101B and 102B, and the opposing electrodes. Means, electrode temperature adjusting means, and the like.

  A base material F is disposed in a region where the counter electrodes 101 and 102 are opposed to each other, a reaction gas G including a discharge gas and a thin film forming gas is introduced, and the base material F is exposed to the discharge space A to thereby form the base material. A thin film is formed on F.

  The voltage applying means applies a voltage from the high frequency power sources 5 and 41 to the metal base material having the metal conductivity of each electrode. 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.

  As a high frequency power source, a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (15 kHz), a high frequency power source manufactured by Shinko Electric (50 kHz), a high frequency power source manufactured by HEIDEN Laboratory (continuous mode) Use, 100 kHz), a high-frequency power source (200 kHz) manufactured by Pearl Industry, etc. can be used.

  A method or conditions for performing plasma discharge treatment in a thin film forming gas atmosphere under these atmospheric pressures or pressures in the vicinity thereof will be described.

There is no particular limitation on the frequency of the high-frequency electric field applied between the counter electrodes when the antifouling film according to the present invention is formed using these apparatuses, but the high-frequency power source is preferably 0.5 kHz or more and 200 kHz or less. More preferably, it is 0.5 kHz or more and 80 kHz or less. The power supplied between the counter electrodes is preferably low power, and the power 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 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.

  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.

  When forming a thin film according to the present invention, it is effective to perform a pretreatment when forming a thin film by exposing the substrate to a discharge space. An atmospheric pressure plasma discharge apparatus used for the pretreatment is shown in FIG. An atmospheric pressure plasma discharge device or the like can be used.

  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.

  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.

  As the atmospheric pressure plasma discharge apparatus that can be used in the above method, for example, when the discharge gas is mainly helium or argon, the same apparatus as each atmospheric pressure plasma discharge apparatus described in the above-mentioned figure is used. However, when nitrogen gas is the main component of the discharge gas, it is preferable to use the atmospheric pressure plasma discharge apparatus shown in FIG.

  FIG. 6 is a schematic view showing an example of an atmospheric pressure plasma discharge apparatus used for the surface treatment of the substrate according to the present invention.

The outline of the apparatus is substantially the same as the configuration shown in FIG. 1, but the discharge space (between the counter electrodes) between the roll rotating electrode (first electrode) 135 and the square tube type fixed electrode group (second electrode) 136. to) 132, a roll rotating electrode (first electrode) 135 a frequency omega ₁ from the first power source 141 a high-frequency voltage V _1, also prismatic fixed electrode group (the second electrode) 136 second power supply A high frequency voltage V ₂ is applied from 142 at a frequency ω ₂ .

  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.

Note that the roll rotating electrode 135 may be the second electrode, and the square tube 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 source has the capability of applying a higher frequency voltage (V ₁ > V ₂ ) than the second power source, and the frequency has the capability of ω ₁ <ω ₂ .

  Further, in these two-frequency type plasma CVD apparatuses, as the high frequency power source, a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (15 kHz), and a high frequency power source manufactured by Shinko Electric (50 kHz), Heiden Laboratory high frequency power supply (continuous mode use, 100 kHz), Pearl Industrial high frequency power supply (200 kHz), Pearl Industrial high frequency power supply (800 kHz), Pearl Industrial high frequency power supply (2 MHz), JEOL high frequency power supply (13.56 MHz), Pearl Industry high frequency power supply (27 MHz), Pearl Industry high frequency power supply (150 MHz), and 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.

  Moreover, the plasma discharge processing apparatus shown in FIG. 7 below is a cross-sectional view showing another example of the processing apparatus useful for the present invention.

  In FIG. 7, a discharge gas is introduced into the discharge space and excited, and the thin film forming gas containing the organometallic compound having an organic group having a fluorine atom is brought into contact with the excited discharge gas outside the discharge space. An apparatus for forming a thin film mainly composed of metal oxide on a substrate by exposing the substrate to the indirectly excited plasma gas and exposing the substrate to the indirectly excited plasma gas is shown.

  In FIG. 7, the plasma discharge processing apparatus 1 mainly includes a counter electrode in which a first electrode 2 and a second electrode 3 and a first electrode 2 ′ and a second electrode 3 ′ are arranged to face each other, In addition to the high-frequency power source 5 for applying a high-frequency electric field between the counter electrodes as the voltage applying means 4, although not shown, a gas supply means for introducing a discharge gas into the discharge space and a thin film forming gas outside the discharge space, It comprises electrode temperature adjusting means for controlling the electrode temperature.

A discharge space is a region A sandwiched between the first electrode 2 and the second electrode 3 or between the first electrode 2 'and the second electrode 3' and having a dielectric shown by hatching on the first electrode. The discharge gas G ₁ is introduced into the discharge space and excited. Further, no discharge occurs in a region sandwiched between the second electrodes 3 and 3 ', and a thin film forming gas M containing an organometallic compound having an organic group having a fluorine atom is introduced here. Next, in the region B outside the discharge space where there is no counter electrode, the excited discharge gas G1 ′ and the thin film forming gas M are brought into contact with each other as an indirect excitation gas and exposed to the surface of the substrate 8 to the indirect excitation gas. To form a thin film. In addition, the base material 8 here can process not only a sheet-like base material like a support body but various sizes and shapes. For example, a thin film can be formed on a base material having a thickness such as a lens shape or a spherical shape.

  In the thin film forming method of the present invention, an organometallic compound having an organic group having a fluorine atom is used as a thin film forming raw material, and the excited discharge gas and the thin film forming gas are brought into contact with each other in a region outside the discharge space. By using an excitation gas, it is possible to obtain a thin film having excellent water repellency, oil repellency, sebum and ink wiping properties, repeated durability thereof, and good abrasion resistance.

  A pair of counter electrodes (the first electrode 2 and the second electrode 3 or the first electrode 2 'and the second electrode 3') are composed of a metal base material and a dielectric, and the inorganic material is formed by lining the metal base material. It may be constituted by a combination in which a dielectric material having a natural property is coated, or a combination in which a dielectric material subjected to sealing treatment with a substance having an inorganic property after ceramic spraying is applied to a metal base material. The metal base material, the dielectric lining material, the ceramics used for the thermal spraying of the dielectric material are the same as described above, and the sealing treatment is the same as described above, for example, by making the alkoxylane-based sealing material sol-gel reacted to make it inorganic. Applicable.

  In FIG. 7, the counter electrode is a plate electrode such as the first electrode 2 and the second electrode 3 and the first electrode 2 ′ and the second electrode 3 ′, but one or both electrodes are hollow. It may be a cylindrical electrode or a prismatic electrode. The high-frequency power source 5 is connected to one of the counter electrodes (second electrode 3, 3 '), and the other electrode (first electrode 2, 2') is grounded by the ground 9, and a voltage is applied between the counter electrodes. It is comprised so that can be applied. Further, in contrast to the configuration shown in FIG. 1, a configuration may be adopted in which voltage application is made to the first electrodes 2 and 2 ′ and the other second electrodes 3 and 3 ′ are grounded.

  The voltage applying means 4 applies a voltage from the high frequency power source 5 to each electrode pair. As a high frequency power source, a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (15 kHz), a high frequency power source manufactured by Shinko Electric (50 kHz), a high frequency power source manufactured by HEIDEN Laboratory (continuous mode) Use, 100 kHz), Pearl Industrial High Frequency Power Supply (200 kHz), Pearl Industrial High Frequency Power Supply (800 kHz), Pearl Industrial High Frequency Power Supply (2 MHz), JEOL High Frequency Power Supply (13.56 MHz), Pearl Industrial High Frequency Power Supply (27 MHz) ), A high frequency power source (150 MHz) manufactured by Pearl Industries, Ltd. 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.

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 is preferably 0.5 kHz or more and 2.45 GHz or less as the high-frequency power source. The power supplied between the counter electrodes is preferably 0.1 W / cm ² or more and 50 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 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.

FIG. 8 shows another embodiment of an electrode system and an atmospheric pressure plasma discharge apparatus that perform plasma treatment as an indirect excitation gas by bringing an excited discharge gas and a thin film forming gas into contact with each other outside the discharge space. Although the configuration is basically the same as that of the atmospheric pressure plasma discharge apparatus shown in 7 above, the direction of the flow of the excited discharge gas G ₁ and the thin film forming gas M is devised to generate indirect excitation gas because mixing is good. Efficiency is good.

  In addition, when forming a thin film by using an organometallic compound having an organic group having a fluorine atom according to the present invention, particularly by an atmospheric pressure plasma method, as a pretreatment, as a substrate surface, for example, an antireflection layer or the like, a metal oxide It is preferable that a film having an object surface is treated with an excited discharge gas excluding the thin film forming gas. By exposing the base material such as metal oxide, plastic (film), metal, etc., which is the base material for forming the antifouling film according to the present invention, to the excited discharge gas in this manner, metal oxide, plastic stock, etc. Desirable modification of the film surface occurs, and the antifouling layer according to the present invention is preferably improved in adhesion to the substrate. These plasma treatments can also be performed under the same conditions by the atmospheric pressure plasma treatment apparatus.

  The base material used in the present invention is preferably a base material such as a plastic film or a plastic sheet, preferably a plastic film as a support, and a base material mainly composed of a metal oxide such as silica or titania on the surface thereof. For example, an antireflection film having a metal oxide film layer is a preferable substrate. The antifouling layer according to the present invention is preferably formed on these outermost surfaces.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<< Preparation of thin film (antifouling film) formed body >>
[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 80 μm-thick cellulose triacetate film (trade name: Konica Katak KC80UVSF, manufactured by Konica) 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)
Four atmospheric pressure plasma discharge treatment apparatuses shown in FIG. 6 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. The roll electrode was rotated in synchronization with the transport 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
Additive gas: 2.0% by volume of hydrogen
<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 were sequentially provided, and a base material having an antistatic layer, a hard coat layer, and an antireflection layer was produced. 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]
An antifouling film was formed on the film base material having the hard coat layer and the antireflection layer produced as described above, using the atmospheric pressure plasma discharge treatment apparatus shown in FIG.

Discharge gas: Nitrogen 99.0% by volume
Raw material: Exemplified compound 15 0.01 vol% (included in discharge gas)
(Example compound 15 is vaporized in nitrogen gas by a vaporizer manufactured by STEC Co.)
Additive gas: 1.0% by volume of hydrogen
A discharge power of 0.5 W / cm ² was applied to the high frequency power source with a high frequency power source (frequency: 5 kHz) manufactured by Shinko Electric.

[Preparation of Sample 2]
In the preparation of Sample 1, Sample 2 was prepared in the same manner except that the following pretreatment A was applied to the substrate before film formation.

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

[Preparation of Sample 3]
Sample 2 was prepared in the same manner as Sample 1 except that the substrate was subjected to the following pretreatment B before film formation.

Pretreatment B: Before forming an antifouling film on the substrate, nitrogen: oxygen = 99: 1 (volume ratio) is introduced as a discharge gas using the apparatus shown in FIG. Exposed to gas for 3 seconds. The high frequency power source was a high frequency power source (frequency: 50 kHz) manufactured by Shinko Electric, and the discharge output was set to 5 W / cm ² .

[Preparation of Sample 4]
In the preparation of Sample 1, Sample 4 was prepared in the same manner except that a glass plate (product name: 0.5 t 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 5]
Sample 5 was prepared in the same manner as in the preparation of Sample 1, except that the discharge gas was changed as follows.

Discharge gas: Nitrogen 70.0 vol%
Discharge gas: Argon 29.0% by volume
[Preparation of Sample 6]
Sample 6 was prepared in the same manner as in the preparation of Sample 1, except that the additive gas was changed as follows.

Additive gas: 1.0% by volume
[Preparation of Sample 7]
An antifouling film was formed using an atmospheric pressure plasma discharge treatment apparatus shown in FIG. 7 instead of the film forming apparatus shown in FIG.

The following gas type A was introduced as the discharge gas G _{1 and} gas type B was introduced as the thin film forming gas M from the introduction port.

  The supplied thin film forming gas (gas species B) and discharge gas (gas species A) exit from each gas discharge port, that is, are brought into contact with each other outside the discharge space to form an indirect excitation gas. To obtain a sample 7 by forming a thin film on the surface of the substrate. At this time, the substrate was moved in a direction perpendicular to the film forming gas release angle. This movement was performed by scanning in the horizontal direction in the figure.

<Gas type A: Discharge gas>
Nitrogen gas 99.0% by volume
Hydrogen gas 1.0% by volume
<Gas type B: Thin film forming gas>
Nitrogen gas 100% by volume
Organometallic compound (Exemplary Compound 15) 0.01% by volume (included in nitrogen gas)
The amount of gas species B and gas species A used was used in a volume ratio of 1: 3.

The high frequency power source 5 was applied with a discharge power of 5 W / cm ² by a high frequency power source (frequency: 13.56 MHz) manufactured by Pearl Industry.

[Production of Samples 8 to 10]
Samples 8 to 10 were prepared in the same manner except that each of the organometallic compounds described below was used in place of the exemplified compound 15 used as a raw material in the preparation of the sample 7.

Sample 8: Exemplary compound 128
Sample 9: Exemplary compound 129
Sample 10: Fluorolink S10 manufactured by Solvay Solexis Co., Ltd.
(Perfluoropolyether having both ends of triethoxysilane)
[Preparation of Sample 11]
Sample 11 was prepared in the same manner as in the preparation of Sample 7 except that the gas type A was changed as follows.

<Gas type A: Discharge gas>
Nitrogen gas 100.0% by volume
[Preparation of Sample 12: Comparative Example]
A coating solution in which Exemplified Compound 15 is diluted with isopropyl alcohol so that the average dry film thickness is 10 nm on the substrate having the prepared antistatic layer, hard coat layer and antireflection layer (addition of acetic acid as a catalyst) Was coated with a bar coating so that the wet film thickness was 15 μm, dried, and then heat-treated at 90 ° C. for 5 hours to prepare a comparative sample 12.

[Production of Sample 13: Comparative Example]
Sample 13 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 14]
Sample 14 was prepared in the same manner as in the preparation of Sample 1 except that the discharge gas was changed as follows.

Discharge gas: Argon 94.0% by volume
Discharge gas: Nitrogen 5.0% by volume
[Production of Sample 15: Comparative Example]
Sample 15 was produced in the same manner as in the production of Sample 1 except that the discharge gas and additive gas were changed as follows.

Discharge gas: Nitrogen 99.9% by volume
Addition gas: Oxygen 0.1% by volume
[Production of Sample 16: Comparative Example]
Sample 16 was prepared in the same manner as in the preparation of Sample 12, except that acetic acid was used instead of ammonia.

[Preparation of Sample 17: Comparative Example]
Sample 17 was prepared in the same manner as in the preparation of Sample 12, except that nitric acid was used instead of the catalyst.

<< Measurement and evaluation of characteristic values of each sample >>
About each obtained sample, the following items were measured and evaluated.

[Tof-SIMS measurement]
Measuring method:
NO ₃ in the thin film ^- ₄ ⁺ is equal negative ions and NH, measured using a time-of-flight secondary ion mass spectrometer.

As a time-of-flight secondary ion measurement apparatus (Tof-SIMS), TRIFT-II (US) manufactured by PHI was used. Considering the possibility of sample deterioration due to vacuum before setting to the measurement position from sample evacuation, it was performed within 10 minutes. In was used as a primary ion, the acceleration voltage was 15 kV, and an area of 60 μm × 60 μm was measured. The measured mass range is 0.5a. For positive secondary ions. m. u. -2000a. m. u. For negative secondary ions, 0.5 a. m. u. -1000a. m. u. As measured. The integration time needs to be adjusted so that the amount of In ions to be irradiated is 1.0 × 10 ¹² ions / cm ² or less. This time, 3 minutes in the measurement of positive secondary ions, negative secondary ion measurement 1 minute. Charge correction measures were taken so that a phenomenon (charge-up) in which the sample is charged during measurement and secondary ions cannot be obtained (charge-up) does not occur. This time, a metal mesh for charge correction and an electron gun for charge correction were used. Furthermore, the mass resolution (M / ΔM) is 3000 or more (in C ₃ H ₇ ⁺ ) for positive ion detection and 2000 or more (for negative secondary ion detection) so that detection peaks are sufficiently separated ( The sample voltage, lens voltage, and the like were adjusted so as to be (in OH ⁻ ). The measurement spectrum was also calibrated to obtain the mass number accurately.

Calculation method:
The detected intensity ratio of NH ₄ ⁺ ions to the total detected ion intensity is 0.5 a. m. u. -2000a. m. u. Calculated as the ratio (NH ₄ ⁺ ion intensity / total ion intensity) of the detected NH ₄ ⁺ ion intensity (number of detected ions) to all positive ion intensity (number of detected ions) did.

Further, the detected intensity ratio of NO ₃ ⁻ ions is 0.5 a. m. u. -1000a. m. u. Calculated as ^- (ionic strength / total ionic strength NO ₃₎ ^- for all the detected negative ionic strength (number of detected ions), NO ₃ is detected in the ionic strength ratio of (the number of detected ions) did.

(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 thin film uniformity]
According to the above method, the contact angle to water was measured at 50 locations, and the difference between the maximum and minimum contact angles was determined. If the difference was within 3 degrees, it was ◯, if it was within 5 degrees, △ exceeded 5 degrees. In some cases, it was determined as x, and this was used as a measure of thin film uniformity.

[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 at the same position to test how many times it can be wiped, and the wiping property of the oil-based ink was evaluated according to the following criteria.

  (Double-circle): It wiped off even if it repeated 100 times or more.

  ○: Wipe off 50 to 99 times.

  Δ: Wipe off 20 to 49 times.

  X: It became impossible to wipe off less than 20 times.

  The results are shown in Table 1.

  As shown in Table 1, it can be seen that the Tof-SIMS measurement results according to the present invention have excellent antifouling properties, wiping properties and repeated durability.

Claims (16)

All detections when negative secondary ions are measured using a Tof-SIMS measuring device in an antifouling film formed on a substrate from a raw material mainly composed of an organometallic compound having an organic group having a fluorine atom The detected intensity ratio of NO ₃ ⁻ ions to the ion intensity is 1.0 × 10 ⁻³ or less, and the detected intensity ratio of NH ₄ ⁺ ions to the total detected ion intensity when measuring positive secondary ions is 1.0 × 10 Antifouling film characterized by being ^-4 or more. The antifouling film according to claim 1, wherein the antifouling film is formed by a dry thin film forming method. The dry thin film forming method supplies a gas that uses a discharge gas and an organometallic compound having an organic group having a fluorine atom as a thin film forming gas raw material between opposing electrodes (discharge space) under atmospheric pressure or a pressure in the vicinity thereof. The atmospheric pressure plasma method of obtaining a thin film on the substrate by exciting the gas by applying a high-frequency voltage between the electrodes and exposing the substrate to the excited gas. The antifouling film according to the second item of the range. The dry thin film forming method is a thin film containing an excitation gas and an organometallic compound having an organic group having a fluorine atom by introducing and exciting a discharge gas into a discharge space under atmospheric pressure or a pressure in the vicinity thereof. It is an atmospheric pressure plasma method for obtaining a thin film on a base material by exposing the base material to the indirect excitation gas as an indirect excitation gas by contacting the forming gas outside the discharge space. The antifouling film according to item 2 of the above. The antifouling film according to any one of claims 1 to 4, wherein the organometallic compound having an organic group having a fluorine atom is 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 antifouling film according to claim 5, 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 antifouling film according to claim 6, 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, and Rf represents an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Alternatively, it represents an alkenyl group, and X represents a simple bond or a divalent group. R ₁₂ represents an alkyl group, an alkenyl group, or an aryl group, and k represents an integer of 0 to 50. ] The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (4), according to any one of claims 1 to 4. Antifouling membrane.

[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. ] 5. The organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (5), according to any one of claims 1 to 4. Antifouling membrane.
General formula (5)
During _{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p [Formula, M represents In, Al, Sb, Y or La, Rf is at least hydrogen atoms One represents an alkyl group or an alkenyl group 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 organic metal compound having an organic group having a fluorine atom is a compound represented by the following general formula (6), according to any one of claims 1 to 4. Antifouling membrane.
General formula (6)
_{Rf 1 (OC 3 F 6)} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3 wherein, Rf ₁ is 1 to the number of carbon atoms 16 linear or branched perfluoroalkyl groups, R ₂ represents a hydrolyzable group, Z represents —OCONH— or —O—, m1 represents an integer of 1 to 50, n1 represents an integer of 0 to 3, p1 Represents an integer of 0 to 3, q1 represents an integer of 1 to 6, and 6 ≧ n1 + p1> 0. ] The organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (7), according to any one of claims 1 to 4. Antifouling membrane.

[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 antifouling film according to any one of claims 3 to 11, wherein the atmospheric pressure plasma method is performed in an atmosphere containing 15 vol% or more of nitrogen gas as a discharge gas. 3. The method according to claim 2, wherein a pretreatment is performed by exposing the substrate to a discharge space or an excited discharge gas before forming an antifouling film on the substrate by the dry thin film forming method. 13. The antifouling film according to any one of items 12. The antifouling film according to any one of claims 1 to 13, wherein the substrate surface contains an inorganic compound. The antifouling film according to any one of claims 1 to 14, wherein a main component of the substrate surface is a metal oxide. An antifouling film production apparatus for producing the antifouling film according to any one of claims 1 to 15.