JP2013174668A - Production apparatus and production method for fluorine-containing organic silicon compound thin film - Google Patents

Abstract

The present invention provides a manufacturing apparatus and a manufacturing method capable of continuously forming a highly durable fluorine-containing organosilicon compound thin film.
A chamber, a heating container for heating a fluorine-containing organosilicon compound, a plurality of nozzles provided in the chamber, connected to the heating container and supplying the fluorine-containing organosilicon compound, a covering of the nozzle and the substrate A substrate transport mechanism capable of continuously transporting the substrate so as to face the film-forming surface is provided, and the fluorine-containing organosilicon compound thin film is a fluorine-containing organosilicon compound thin film that has undergone solvent removal treatment or is undiluted. A fluorine-containing organosilicon compound is heated from a production apparatus and a solvent-removed or undiluted fluorine-containing organosilicon compound in a heating vessel, and is provided in the chamber and connected to the heating vessel. Method for producing a fluorine-containing organosilicon compound thin film that is supplied and continuously supplies the substrate by the substrate transport mechanism so that the nozzle and the film formation surface of the substrate face each other To provide.
[Selection] Figure 1

Description

  The present invention relates to a fluorine-containing organosilicon compound thin film manufacturing apparatus and manufacturing method.

  Since display glass, optical elements, sanitary equipment, etc. have the opportunity to touch human fingers during use, dirt due to fingerprints, sebum, sweat, etc. is likely to adhere. These stains are difficult to remove when attached, and are conspicuous depending on the amount of light, etc., and thus there is a problem that visibility and aesthetics are impaired.

  In order to solve such a problem, a method of forming an antifouling film made of a fluorine-containing organosilicon compound on the surface of these parts and devices is known.

  For example, Patent Document 1 describes a method of forming a film by vacuum deposition using a porous ceramic pellet impregnated with a raw material and dried as an evaporation source.

  However, when a raw material dried before being introduced into the vapor deposition apparatus is used as a vapor deposition source, the raw material material becomes unstable, and thus the resulting antifouling film performance is not stable and yield is reduced. there were. In addition, the cost for the pelletizing process is high.

  Patent Document 2 describes a method in which a fluorine-substituted alkyl group-containing organosilicon compound-containing solution is heated with an electron beam to form a thin film of the compound on a substrate.

  However, in the invention described in Patent Document 2, when the raw material is heated for a predetermined time or more, the durability of the obtained antifouling film is lowered. For this reason, there are problems that the thickness of the film that can be produced is limited, and that a film having high durability cannot be produced stably.

  Furthermore, in any of the methods described in Patent Documents 1 and 2, it is necessary to set a very small amount of raw material that evaporates within several tens of seconds after heating and to operate in a batch system, resulting in low productivity. Moreover, the apparatus which can be used in order to raise the temperature within a predetermined time is limited, which causes high cost.

  As described above, according to these conventional film forming methods, only a method for producing an antifouling film by a batch method is known, and a durable antifouling film can be produced continuously and stably. It wasn't.

JP 2009-175500 A JP 2008-107836 A

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a manufacturing apparatus and a manufacturing method capable of continuously forming a highly durable fluorine-containing organosilicon compound thin film.

  In order to solve the above problems, the present invention provides a fluorine-containing organosilicon compound thin film manufacturing apparatus for forming a fluorine-containing organosilicon compound thin film on a substrate surface, and a chamber and a heating container for heating the fluorine-containing organosilicon compound A plurality of nozzles that are provided in the chamber and are connected to the heating container by a pipe and supply a fluorine-containing organosilicon compound to the substrate, and the film formation surfaces of the nozzles and the substrate And a substrate transport mechanism capable of continuously transporting the substrate so as to face each other, and the fluorine-containing organosilicon compound has been subjected to solvent removal treatment or diluted with a solvent An apparatus for producing a fluorine-containing organosilicon compound thin film is provided.

  The present invention heats a fluorine-containing organosilicon compound that has been subjected to a removal treatment of a solvent generally added to a fluorine-containing organosilicon compound or that has not been diluted with a solvent (does not contain a solvent). A durable film can be continuously formed by supplying and depositing on a substrate.

  The base material transport mechanism can continuously transport the base material so that the film formation surface of the base material and the plurality of nozzles face each other. A silicon compound thin film can be formed. For this reason, it becomes possible to improve productivity significantly compared with the batch-type film-forming apparatus used conventionally.

Explanatory drawing of the manufacturing apparatus of 1st Embodiment which concerns on this invention 1 is a cross-sectional view of a manufacturing apparatus according to a first embodiment of the present invention. Explanatory drawing of the modification of the manufacturing apparatus of 1st Embodiment which concerns on this invention Explanatory drawing of the modification of the manufacturing apparatus of 1st Embodiment which concerns on this invention Explanatory drawing of the glass substrate carrier of the Example which concerns on this invention Film thickness distribution in a glass substrate carrier after film formation of an example according to the present invention

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not departed from the scope of the present invention. Various modifications and substitutions can be made.

[First Embodiment]
In the present embodiment, an apparatus for producing a fluorine-containing organosilicon compound thin film will be described.

  The apparatus for producing a fluorine-containing organosilicon compound thin film of the present invention is a fluorine-containing organosilicon compound thin film production apparatus for forming a fluorine-containing organosilicon compound thin film on the surface of a substrate.

  A specific configuration will be described with reference to FIGS. In addition, FIGS. 1-4 shows the structural example of the fluorine-containing organosilicon compound thin film manufacturing apparatus of this invention, and is not limited to the form which concerns.

  First, FIG. 1 schematically shows a top view of the fluorine-containing organosilicon compound thin film manufacturing apparatus according to the present embodiment, and FIG. 2 shows a cross-sectional view taken along the line AA ′ of FIG. It is a thing.

  The fluorine-containing organosilicon compound thin film manufacturing apparatus 10 includes a chamber 11 and a heating container 13 for heating the fluorine-containing organosilicon compound 12. And it is provided in the chamber 11, is connected with the heating container 13 and the piping 14, and is provided with a plurality of nozzles (injection ports) 15 for supplying the fluorine-containing organosilicon compound to the substrate. 1 further includes a base material transport mechanism 18 represented by a dotted line in FIG. 1, capable of continuously transporting the base material 17 such that the plurality of nozzles 15 and the film formation surface of the base material 17 face each other. ing.

  In addition, the fluorine-containing organosilicon compound used in this production apparatus is one that has been subjected to solvent removal treatment or one that has not been diluted with a solvent (one that does not contain a solvent).

  In the figure, the substrate 17 is conveyed in the direction of the arrow, and is configured such that a thin film of a fluorine-containing organosilicon compound is formed by vacuum deposition around the area facing the plurality of nozzles 15 (effective film formation area 16). ing.

  Each member will be described.

  The size, shape, material, and the like of the chamber 11 are not limited, and can be selected according to the size of the substrate to be used, film formation conditions in the chamber, and the like.

  The chamber 11 can also be provided with incidental equipment such as gas piping. For example, as shown in FIG. 2, a pipe 21 connected to a vacuum pump and a pipe 22 connected to a gas supply unit so that the inside can be set to a desired degree of vacuum or gas can be supplied in accordance with film forming conditions. Can be provided.

  The size and material of the heating container 13 are not limited. However, since the container may be negatively evacuated after introducing the fluorine-containing organosilicon compound, In addition to these, those having pressure resistance are preferred.

  Moreover, in order to control the atmosphere in the heating container, the heating container can be provided with a pipe connected to a vacuum pump or a gas supply unit. The heating temperature of the heating container at the time of film formation is not limited because it varies depending on the raw material, and it may be heated so as to obtain a sufficient film formation rate.

The shape and material of the pipe 14 connecting the heating container and the plurality of nozzles are not particularly limited. For example, it can also be comprised with a manifold, and can also be comprised from several piping which connects each nozzle and a heating container individually.
Moreover, it is preferable to heat the piping 14 so that the fluorine-containing organosilicon compound which became gaseous in the heating container does not condense between the heating container and each nozzle.

  Further, a variable valve 19 for adjusting the supply amount of the fluorine-containing organosilicon compound is provided in the pipe connecting the heating container and the plurality of nozzles so that the supply amount of the fluorine-containing organosilicon compound from each nozzle can be adjusted. It is preferable that And it is preferable to be comprised so that the opening degree of a variable valve may be controlled according to the detected value from the film thickness meter 20 provided in the chamber.

  This is because, by having such a configuration, it is possible to control the detected value from the film thickness meter 20, that is, the film formation speed, by the opening degree of the variable valve 19, and perform film formation at the target film formation speed. It is. In addition, the film forming speed can be changed depending on the base material, and different types (film thicknesses) of products can be continuously produced without stopping the manufacturing apparatus, thereby improving productivity.

  Furthermore, a substrate sensor (substrate detector) is provided on the upstream side of the substrate supply path from the film formation region so that the supply from the nozzle can be stopped when the substrate is not supplied to the film formation region. It is preferable to be configured so as to be interlocked with a valve or a valve provided on the pipe 14 separately.

  The base material sensor detects whether the base material has passed, and can be constituted by, for example, an infrared sensor. When the substrate does not pass for a certain time by interlocking with the substrate sensor and the valve on the pipe, the supply of the fluorine-containing organosilicon compound to the nozzle is interrupted by closing the valve, and the substrate passes again. In some cases, the valve is opened and configured to start feeding.

  This is because the fluorine-containing organosilicon compound as a raw material is generally expensive, and it is preferable that the raw material not supplied to the substrate is reduced. For this reason, it becomes possible to aim at cost reduction by having such a structure.

  The size and arrangement of the nozzle 15 are not limited, and can be selected depending on the required film forming speed, the size of the substrate, and the like. It is preferable that the opening diameter and the like are adjusted so that the supply amount from each nozzle is uniform so that a uniform fluorine-containing organosilicon compound thin film can be formed by vacuum deposition.

  For example, when forming a film while transporting the base material, the nozzles may be arranged in a line so as to cross the transport direction of the base material, that is, perpendicular to the transport direction of the base material. preferable. In addition, when film formation is performed after the substrate is temporarily stopped in the effective film formation region, nozzles are arranged so that the fluorine-containing organosilicon compound can be supplied uniformly over the entire film formation surface of the substrate. It is preferable.

  Moreover, the nozzle is arrange | positioned so that the nozzle and the film-forming surface of a base material may oppose. In FIG. 1 and FIG. 2, the base material (substrate) is held in the vertical direction with respect to the ground, and since the nozzle is installed so as to face the substrate, the fluorine-containing organosilicon compound is jetted in the horizontal direction from the nozzle. It has become. However, the present invention is not limited to such a configuration, and for example, the base material can be held horizontally with the ground surface and sprayed from the upper surface or the lower surface side. Moreover, a nozzle can be provided so as to face both surfaces of the substrate, and film formation can be performed simultaneously on both the front and back surfaces of the substrate.

  In order to prevent radiant heat from the fluorine-containing organosilicon compound supply path from being transmitted to the base material 17 between the base material 17 and the nozzle 15, a cooling plate 23 can be provided as shown in FIG. 2. The shape and the like of the cooling plate are not limited as long as they are arranged so as not to hinder the supply of the film forming raw material from the nozzle 15.

  The base material 17 is not particularly limited, and various base materials such as glass, plastic, and metal that require antifouling films, water repellent films, and oil repellent films can be employed. Furthermore, it can use also about the shape of a flat form, and the shape | molding process etc. about the shape.

  The base material transport mechanism 18 can also transport the base material 17 so that the plurality of nozzles 15 and the film formation surface of the base material 17 face each other in the chamber. If it can supply continuously, it will not be specifically limited.

  As the substrate transport mechanism, for example, it is general to perform mechanical holding such as holding the substrate tilted obliquely or holding several points around the substrate with a springy jig. It is. If the substrate is relatively small, there is a method in which the substrate is held and fixed by a substrate holding member such as an adsorption pad or an electrostatic chuck, and the substrate holding member is conveyed by a rack and pinion mechanism or the like. Can be mentioned.

  In addition, what is referred to here as “conveying the base material continuously” is only necessary to sequentially transport and supply a plurality of base materials, and there may be an interval between the base materials to be transported.

  In this way, by continuously supplying the substrate to the film formation region by the substrate transport mechanism and forming the film, the amount (number of sheets) of the substrate that can be formed per unit time is increased as compared with the conventional batch type. Therefore, productivity can be increased.

  In addition, when film formation is performed on the film formation surface of the substrate while transporting the substrate without stopping in the film formation region, the substrate transport mechanism is in accordance with the deposition rate of the fluorine-containing organosilicon compound thin film. It is preferable that the substrate conveyance speed can be changed. By configuring the base material transport mechanism so that the base material transport speed can be changed, it becomes possible to form a fluorine-containing organosilicon compound thin film with the desired film thickness, reducing wasteful raw material consumption and improving yield. can do.

  Furthermore, in the manufacturing apparatus of the fluorine-containing organosilicon compound thin film demonstrated so far, in order to supply a base material continuously in a chamber, it can have a base material introduction chamber (front chamber) and a base material take-out chamber.

  As a specific configuration, a base material introduction chamber for introducing a base material into the chamber and a base material take-out chamber for taking out the base material from the chamber are connected to the chamber. The base material introduction chamber and the base material take-out chamber can be independently supplied and exhausted, and the base material transport mechanism is configured between the base material introduction chamber, the chamber, and the base material take-out chamber. It is comprised so that a base material can be conveyed.

  A specific manufacturing apparatus will be described with reference to FIG. The same members as those in FIGS. 1 and 2 are given the same numbers.

  As shown in FIG. 3, a base material introduction chamber (front chamber) 31 for introducing a base material into the chamber and a base material take-out chamber 32 for taking out the base material from the chamber are connected to the chamber 11. The base material introduction chamber 31 and the base material take-out chamber 32 are configured to be able to supply and exhaust air independently. That is, a vacuum pipe connected to the vacuum pump and a gas supply pipe for supplying gas can be provided respectively. Moreover, it is preferable to provide an openable / closable inlet and outlet for introducing and removing the substrate.

  It is preferable to provide walls (gates) 33 and 34 that can be opened and closed between the base material introduction chamber, the chamber, and the base material take-out chamber, and that can keep the airtightness of each room when closed. . Such a gate suffices if at least a range through which the base material can pass is openable and closable.

  And it is preferable to be comprised so that a base material can be conveyed by the base material conveyance mechanism 18 between a base material introduction chamber, a chamber, and a base material take-out chamber. Thereby, a base material can be conveyed with a base material conveyance apparatus from a base material introduction chamber to a chamber and a base material take-out chamber.

  The base material transport mechanism does not have to be an integrated structure from the base material introduction chamber to the chamber base material take-out chamber. For example, each base material introduction chamber, chamber, and base material take-out chamber are configured as individual base material transport mechanisms. It may be configured so that the substrate can be delivered.

  In addition, the arrangement of the base material introduction chamber, the chamber, and the base material take-out room is not particularly limited, and it is sufficient if these three rooms are continuously arranged, and various arrangements can be made according to conditions such as the installation location. can do. For example, it is preferable to arrange three rooms in a straight line as shown in FIG. 3 because the footprint is small and the transport mechanism is simple.

  With this configuration, while the film forming process is being performed in the chamber, the base material for the next film forming process is arranged in the base material introducing chamber, and the base material introducing chamber is the same as the inside of the chamber. The process of setting the atmosphere can be performed in parallel. In addition, after the film formation is completed, the base material can be transported to the base material take-out chamber, and after separating the atmosphere between the chamber and the base material take-out chamber by a wall, the base material can be taken out from the base material take-out chamber. For this reason, even when a substrate is introduced and removed between the chamber and an environment having a different atmosphere, the substrate can be continuously introduced and removed without destroying the atmosphere in the chamber. Thus, productivity can be increased.

  Note that the substrate introduction chamber and the substrate take-out chamber are not limited to one room each, and a plurality of chambers are provided for each, depending on the degree of vacuum and atmosphere, or a plurality of introduction chambers or take-out chambers are arranged in parallel with the chamber Can also be provided.

  Furthermore, it can also have the pre-processing means for processing the base-material surface in the upstream of a base-material conveyance path rather than the some nozzle (film-forming means) which supplies a fluorine-containing organosilicon compound.

  A specific configuration will be described with reference to FIG. In the figure, the same members as those in FIGS.

  As shown in FIG. 4, pretreatment means 35 for treating the substrate surface upstream of the nozzle for supplying the fluorine-containing organosilicon compound is disposed on the upstream side of the substrate conveyance path.

  The content of the pretreatment means is not particularly limited, and can be selected as necessary. Examples thereof include a base film formation treatment on the substrate surface, plasma treatment, and ion gun irradiation.

Here, the method for forming the underlying film and the type of the film are selected depending on the application, etc., but, for example, a silicon oxide film is formed by sputtering to adhere the fluorine-containing organosilicon compound film to the substrate. And a method for increasing the property (bonding strength). In addition, as the plasma treatment, the surface of the base material can be treated with plasma of Ar, O ₂ , H ₂ O, etc. to remove surface contamination and surface modification. In the case of ion gun irradiation, similarly to plasma, Ar, O ₂ , and H ₂ O gas can be used to remove dirt on the surface of the substrate and to modify the surface.

  Note that the preprocessing means is not limited to one, and two or more processes may be performed. For example, both the base film forming process and the plasma process may be performed.

  The place where the pretreatment means is disposed is not particularly limited as long as it is disposed upstream of the effective film formation region in the base material supply path. For example, as shown in FIG. 4, it can be arranged in a chamber provided with a plurality of nozzles (film forming means). In this case, for example, when the atmosphere used in the pretreatment means and the atmosphere of the film formation region are different, an opening (slit) that allows the substrate to pass between the region where the pretreatment means is provided and the film formation region is provided. A partition wall 36 may be provided so that the atmosphere in both regions can be controlled. Furthermore, the opening provided in the partition wall 36 can be configured to be opened and closed by a valve or a movable wall.

  In addition, a chamber for pretreatment means may be provided separately from the chamber having a plurality of nozzles, and the base material may be transported between both chambers by the base material transport mechanism.

  By providing the pretreatment means upstream of the effective film formation region in this way, it becomes possible to improve the adhesion (bonding strength) between the base material and the fluorine-containing organosilicon compound. In addition, by providing the pretreatment means on the base material supply path in this way, workability is improved and productivity is improved as compared with the case where the pretreatment of the base material is separately performed before the base material is supplied to the manufacturing apparatus. It becomes possible to increase.

  Next, the fluorine-containing organosilicon compound used in the present invention will be described. The fluorine-containing organosilicon compound used in the present invention is not particularly limited as long as it imparts antifouling properties, water repellency and oil repellency.

  Specific examples include fluorine-containing organosilicon compounds having one or more groups selected from the group consisting of perfluoropolyether groups, perfluoroalkylene groups, and perfluoroalkyl groups. The perfluoropolyether group is a divalent group having a structure in which perfluoroalkylene groups and etheric oxygen atoms are alternately bonded.

  Specific examples of the fluorine-containing organosilicon compound having one or more groups selected from the group consisting of this perfluoropolyether group, perfluoroalkylene group and perfluoroalkyl group include the following general formulas (I) to (V): The compound etc. which are represented by these are mentioned.

式中、Ｒｆは炭素数１〜１６の直鎖状のパーフルオロアルキル基（アルキル基として、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｘは水素原子又は炭素数１〜５の低級アルキル基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｒ１は加水分解可能な基（例えば、アミノ基、アルコキシ基等）又はハロゲン原子（例えば、フッ素、塩素、臭素、ヨウ素等）、ｍは１〜５０、好ましくは１〜３０の整数、ｎは０〜２、好ましくは１〜２の整数、ｐは１〜１０、好ましくは１〜８の整数である。

In the formula, Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X is hydrogen. An atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), R1 is a hydrolyzable group (for example, amino group, alkoxy group) Etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1 to 50, preferably 1 to 30, n is an integer of 0 to 2, preferably 1 to 2, and p is 1 to 2. It is an integer of 10, preferably 1-8.

_{C q F 2q + 1 CH 2} CH 2 Si (NH 2) 3 (II)
Here, q is 1 or more, preferably an integer of 2 to 20.

Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ), n-heptafluoro. (1,1,2,2-tetrahydro) Penchirushirazan _{(n-C 3 F 7 CH} 2 CH 2 Si (NH 2) 3) or the like can be exemplified.

C _{q ′} F _{2q ′ + 1} CH ₂ CH ₂ Si (OCH ₃ ) ₃ (III)
Here, q ′ is 1 or more, preferably an integer of 1-20.

Examples of the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane _{(n-C 8 F 17 CH} 2 CH 2 Si (OCH 3) 3) or the like can be exemplified.

式（ＩＶ）中、Ｒ^ｆ２は、−（ＯＣ_３Ｆ_６）_ｓ−（ＯＣ_２Ｆ_４）_ｔ−（ＯＣＦ_２）_ｕ−（ｓ、ｔ、ｕはそれぞれ独立に０〜２００の整数）で表わされる２価の直鎖状パーフルオロポリエーテル基であり、Ｒ^２、Ｒ^３は、それぞれ独立に炭素原子数１〜８の一価炭化水素基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）である。Ｘ^２、Ｘ^３は独立に加水分解可能な基（例えば、アミノ基、アルコキシ基、アシロキシ基、アルケニルオキシ基、イソシアネート基等）またはハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等）であり、ｄ、ｅは独立に１〜２の整数であり、ｃ、ｆは独立に１〜５（好ましくは1〜２）の整数であり、ａおよびｂは独立に２または３である。

In formula (IV), R ^f2 is — (OC ₃ F ₆ ) _s — (OC ₂ F ₄ ) _t — (OCF ₂ ) _u — (s, t and u are each independently an integer of 0 to 200). R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-propyl). Group, isopropyl group, n-butyl group and the like. X ² and X ³ are independently hydrolyzable groups (for example, amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) D and e are independently an integer of 1 to 2, c and f are independently an integer of 1 to 5 (preferably 1 to 2), and a and b are independently 2 or 3 is there.

In R ^f2 of the compound (IV), s + t + u is preferably 20 to 300, more preferably 25 to 100. R ² and R ³ are more preferably a methyl group, an ethyl group, or a butyl group. As the hydrolyzable group represented by X ² or X ³ , an alkoxy group having 1 to 6 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable. Further, a and b are each preferably 3.

式（Ｖ）中、ｖは１〜３の整数であり、ｗ、ｙ、ｚはそれぞれ独立に０〜２００の整数であり、ｈは１または２であり、ｉは２〜２０の整数であり、Ｘ^４は加水分解性基であり、Ｒ^４は炭素数１〜２２の直鎖または分岐の炭化水素基であり、ｋは０〜２の整数である。ｗ＋ｙ＋ｚは、２０〜３００であることが好ましく、２５〜１００であることがより好ましい。また、ｉは２〜１０であることがより好ましい。Ｘ^４は、炭素数１〜６のアルコキシ基が好ましく、メトキシ基、エトキシ基がより好ましい。Ｒ^４としては、炭素数１〜１０のアルキル基がより好ましい。

In the formula (V), v is an integer of 1 to 3, w, y and z are each independently an integer of 0 to 200, h is 1 or 2, and i is an integer of 2 to 20. , X ⁴ is a hydrolyzable group, R ⁴ is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w + y + z is preferably 20 to 300, and more preferably 25 to 100. Further, i is more preferably 2 to 10. X ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group. R ⁴ is more preferably an alkyl group having 1 to 10 carbon atoms.

  Further, as a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a commercially available perfluoropolyether group, perfluoroalkylene group and perfluoroalkyl group, KP-801 (trade name, Shin-Etsu Chemical Co., Ltd.) Kogyo Co., Ltd.), KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Optur (registered trademark) DSX and Optool AES (both trade names) , Manufactured by Daikin Industries, Ltd.) can be preferably used.

  In general, fluorine-containing organosilicon compounds are stored in a mixture with a solvent such as a fluorinated solvent in order to suppress deterioration due to reaction with moisture in the atmosphere. If it is subjected to the film forming process as it is, the durability of the obtained thin film may be adversely affected.

  Therefore, in the present invention, a fluorine-containing organosilicon compound that has been subjected to solvent removal treatment before heating in a heating container or a fluorine-containing organosilicon compound that has not been diluted with a solvent (no solvent added) is used. . For example, the concentration of the solvent contained in the fluorine-containing organosilicon compound solution is preferably 1 mol% or less, more preferably 0.2 mol% or less. It is particularly preferable to use a fluorine-containing organosilicon compound that does not contain a solvent.

Examples of the solvent used for storing the fluorine-containing organosilicon compound include perfluorohexane, metaxylene hexafluoride (C ₆ H ₄ (CF ₃ ) ₂ ), hydrofluoropolyether, HFE7200 / 7100 (trade name, manufactured by Sumitomo 3M Limited, HFE7200 is represented by C ₄ F ₉ C ₂ H ₅ , and HFE 7100 is represented by C ₄ F ₉ OCH ₃ ).

  The removal treatment of the solvent (solvent) from the fluorine-containing organosilicon compound solution containing the solvent can be performed, for example, by evacuating a container containing the fluorine-containing organosilicon compound solution.

  The time for performing vacuum evacuation is not limited because it varies depending on the exhaust capacity of the exhaust line, the vacuum pump, etc., the amount of the solution, and the like. For example, it can be performed by evacuating for about 10 hours or more.

Such an operation can also be performed by evacuating the inside of the heating container at room temperature after introducing the fluorine-containing organosilicon compound solution into the heating container and before raising the temperature. In addition, the solvent removal step can be performed in advance with an evaporator or the like before being introduced into the heating container.
However, as described above, the fluorine-containing organosilicon compound having a small or no solvent content is more likely to be deteriorated by contact with the atmosphere, particularly moisture in the atmosphere, as compared with those containing a solvent.

  For this reason, storage containers for fluorine-containing organosilicon compounds with low (or no) solvent content should be replaced with an inert gas such as nitrogen and sealed, and exposed to the atmosphere when handled. It is preferable to shorten the contact time.

  Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into the heating container of the production apparatus immediately after opening the storage container. And after introduction | transduction, it is preferable to remove the air | atmosphere (water | moisture content in air) contained in a heating container by evacuating the inside of a heating container or substituting with inert gas, such as nitrogen and a noble gas. For example, the storage container and the heating container are more preferably connected by a pipe with a valve so that the storage container (storage container) can be introduced into the heating container of the present manufacturing apparatus without coming into contact with the atmosphere.

And after introducing a fluorine-containing organosilicon compound into a heating container and after substituting the inside of a container with a vacuum or an inert gas, it is preferable to start the heating for vacuum deposition immediately.
[Second Embodiment]
In the present embodiment, a method for producing a fluorine-containing organosilicon compound thin film will be described.

  As a method for producing a fluorine-containing organosilicon compound thin film that forms a fluorine-containing organosilicon compound thin film on the substrate surface, a fluorine-containing organic silicon compound that has been previously subjected to solvent removal treatment, or a fluorine-containing organic that has not been diluted with a solvent. The silicon compound is heated in a heating vessel. Then, a fluorine-containing organosilicon compound is supplied from a plurality of nozzles provided in the chamber and connected to the heating container and piping. Fluorine-containing organosilicon, wherein a substrate is continuously supplied by a substrate transport mechanism to a region facing the plurality of nozzles so that the plurality of nozzles and a film formation surface of the substrate are opposed to each other It is a manufacturing method of a compound thin film.

  According to the production method of the present invention, it is possible to continuously supply a fluorine-containing organosilicon compound heated in a heating vessel from a plurality of nozzles. And since the base material is continuously supplied to the effective film formation region by the base material transport mechanism, it is possible to continuously form the fluorine-containing organosilicon compound thin film on the film formation surface of the target base material. It becomes possible. For this reason, it becomes possible to raise productivity remarkably compared with the manufacturing method of the fluorine-containing organosilicon compound thin film performed with the conventional batch type.

  It is preferable that a base material introduction chamber and a base material take-out chamber that can be independently supplied and exhausted are connected to the chamber. The base material introduced into the base material introduction chamber is transported to the chamber by the base material transport mechanism, and after the film forming process, the base material can be transported from the chamber to the base material take-out chamber by the base material transport mechanism. It is preferable.

  With this configuration, while the film forming process is being performed in the chamber, the base material for the next film forming process is arranged in the base material introducing chamber, and the base material introducing chamber is the same as the inside of the chamber. The process of setting the atmosphere can be performed in parallel. Further, the base material after film formation can be transferred to the base material take-out chamber, and the atmosphere between the chamber and the base material take-out chamber can be separated by a wall, and then taken out from the base material take-out chamber. In this way, since it is possible to continuously introduce and remove the substrate without destroying the atmosphere in the chamber, even when equipment is introduced and removed from environments with different atmospheres from the chamber, It is possible to form a film on the material, and productivity can be increased.

  In addition, a variable valve is provided in the piping connecting the heating vessel and the plurality of nozzles so that the supply amount of the fluorine-containing organosilicon compound can be changed, and detection from a film thickness meter provided in the chamber is performed. It is preferable to control the opening of the variable valve according to the value.

  This is because the detection value from the film thickness meter, that is, the film formation speed can be controlled by the opening degree of the variable valve, and film formation can be performed at the target film formation speed. In addition, the film forming speed can be changed depending on the base material, and different types of products can be continuously produced, thereby improving productivity.

  And it is preferable that the base material conveyance mechanism can change the conveyance speed of a base material according to the film-forming speed | rate of a fluorine-containing organosilicon compound thin film.

  This makes it possible to form a fluorine-containing organosilicon compound thin film of a desired film thickness by configuring the substrate conveyance speed of the substrate conveyance mechanism to be changeable, suppressing wasteful raw material consumption, This is because the yield can be improved.

  Before forming the fluorine-containing organosilicon compound thin film, the substrate is preferably subjected to a pretreatment step. As described in the first embodiment, this is because the adhesion between the base material and the fluorine-containing organosilicon compound thin film can be increased by performing a pretreatment step on the base material surface. The content of the pretreatment step is not particularly limited and can be selected as necessary. Examples of the pretreatment step include a base film formation treatment on the substrate surface, plasma treatment, and ion gun irradiation.

Here, the method for forming the underlying film and the type of the film are selected depending on the application, etc., but, for example, a silicon oxide film is formed by sputtering to adhere the fluorine-containing organosilicon compound film to the substrate. And a method for increasing the property (bonding strength). In addition, as the plasma treatment, the surface of the base material can be treated with plasma of Ar, O ₂ , H ₂ O, etc. to remove surface contamination and surface modification. In the case of ion gun irradiation, similarly to plasma, Ar, O ₂ , and H ₂ O gas can be used to remove dirt on the surface of the substrate and to modify the surface.

  The pretreatment process is not limited to one, and two or more processes may be performed. For example, both the base film forming process and the plasma process may be performed.

  The pretreatment step is performed before the film forming step of transporting the base material to the effective film forming region in front of the plurality of nozzles for supplying the fluorine-containing organosilicon compound. For example, it is preferable that the pretreatment means is installed upstream of the region where the nozzle for supplying the fluorine-containing organosilicon compound is installed.

  By performing the pretreatment step before the film formation step in this way, it becomes possible to improve the adhesion (bonding strength) between the base material and the fluorine-containing organosilicon compound. In addition, when the pretreatment process is performed on the same substrate transport path as the film formation process, workability is improved and productivity is increased as compared to the case where the pretreatment of the substrate is separately performed before the substrate is supplied. Is possible.

  In the method for producing a fluorine-containing organosilicon compound thin film described in the present embodiment, for example, the apparatus for producing a fluorine-containing organosilicon compound thin film described in the first embodiment can be preferably used. For this reason, the members other than those described so far, the fluorine-containing organosilicon compound that is a raw material, and the like are the same as those described in the first embodiment, and are therefore omitted here.

  Specific examples will be described below, but the present invention is not limited to these examples.

  In this example, an experiment was performed using a film forming apparatus in which a surface vapor deposition source (linear source vapor deposition source) (manufactured by Hitachi Zosen) was installed in an SDP-850 VT in-line sputtering apparatus (manufactured by ULVAC, Inc.). In the surface evaporation source, the nozzles are arranged in two lines in a straight line so as to cross the substrate transport direction (perpendicular to the substrate transport direction). The thin film obtained at this time is designed so that the film thickness distribution within the range of 550 mm in the height direction of the base material is within 10%.

  The substrate transport mechanism was arranged so that the distance between the substrate and the nozzle of the surface vapor deposition source was kept at 50 mm.

The outline of the apparatus used is the same as that shown in FIG. 1 and FIG. 2, and the substrate is held in the vertical direction and transferred to the effective film formation region provided with the surface vapor deposition source by the substrate transfer mechanism. A film treatment is performed.
(Deposition of antifouling film on glass substrate)
First, 50 g of KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) that is not diluted with a solvent as a fluorine-containing organosilicon compound that is a vapor deposition material (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) is a heating vessel of a film forming apparatus, manufactured by SUS304. Introduced in a crucible.

At this time, the supply of the fluorine-containing organosilicon compound to the crucible was carried out in the air. For this reason, the crucible was evacuated to a pressure of 5 × 10 ⁻² Pa or less with a vacuum pump within 15 minutes after the fluorine-containing organosilicon compound was exposed to the atmosphere.

  The crucible was then heated to 200 ° C. After reaching 200 ° C., a fluorine-containing organic compound was supplied from each nozzle, and the base material was transported by the base material transport mechanism so that each nozzle and the film formation surface of the base material face each other.

  A glass substrate (trade name: Dragon Trail substrate manufactured by Asahi Glass Co., Ltd.) having a 100 mm square and a thickness of 1.1 mm was used as the base material. As shown in FIG. 5, the glass substrate has a width of 850 mm in the height direction (arrow direction indicated by Y in FIG. 5), and a width of 1200 mm in the direction parallel to the conveyance direction 53 (arrow direction indicated by X in FIG. 5). A plurality of 100 mm □ glass substrates 52 arranged in a carrier 51 were transported to and passed through a surface vapor deposition source by a base material transport mechanism while being held in a vertical direction, thereby performing a film forming process.

  Then, when the glass substrate passes through the effective film formation region at a speed of 900 mm / min, the deposition amount is adjusted so that the film thickness formed on the glass substrate surface is about 12 nm. It was.

  The amount of vapor deposition can be adjusted by measuring the amount of vapor deposition using a crystal oscillator monitor provided in the vacuum chamber where the surface vapor deposition source is installed, and changing the opening of the valve provided on the pipe connecting the heating vessel and the nozzle. Done by controlling. In addition, when a desired vapor deposition amount could not be obtained even when the valve opening was opened to 80%, the crucible temperature was increased by 10 ° C.

  The substrate was conveyed at a constant speed of 900 mm / min while adjusting the deposition amount, and the glass substrate was continuously supplied to produce a glass substrate on which an antifouling film was formed. As a result, after 53 hours from the start of film formation, the crucible temperature rose to 290 ° C., and a desired vapor deposition amount could not be obtained even when the valve opening reached 80%.

  In addition, the glass substrate used what performed the surface washing process beforehand. As a specific procedure, the surface of each substrate was cleaned in the order of [1] ultrasonic cleaning with alkaline detergent Sunwash TL-75 (2%) solution [2] ultrasonic cleaning with ultrapure water. .

The glass substrates subjected to the film forming process were each taken out from the vacuum chamber, and then placed in a high-temperature bath PR-1SP (manufactured by Espec Co., Ltd.) with the film surface standing vertically to the ground. After heat treatment for 60 minutes, the film was subjected to a durability test.
(Durability test of membrane)
1 μL of pure water was dropped on the glass substrate subjected to film formation by the above method, and the contact angle was measured to obtain the initial water contact angle.

Next, the surface of each substrate on which the thin film was formed was applied with a pressure of 1000 g / cm ² using a surface abrasion tester PA300A manufactured by Daiei Kagaku Seiki Seisakusho using a gold cloth (attached white cloth for dyeing fastness test) as a rubbing material. Rubbed 50,000 reciprocations, that is, 100,000 times at a speed of 107 mm / sec. Thereafter, the contact angle was measured as in the case of the initial water contact angle. And the rate of change from the initial water contact angle was calculated. The results are shown in Table 1. In the table, the elapsed time after reaching the film formation start temperature is the time when the crucible temperature reached the initial vapor deposition temperature of 200 ° C. and the film formation was started. Show the time until.

  For example, in the table, the elapsed time of 2 hours after reaching the film formation start temperature indicates that the glass substrate has started film formation 2 hours after the crucible temperature reached 200 ° C.

これによれば、成膜開始から５０時間程度経過しても、１０万回擦った後の膜の接触角低下率が５％以下と、高い耐久性能を示している。また、蒸着時の温度に関しても、膜の耐久性に影響がないことがわかる。つまり、本発明の製造方法によれば、長時間の間、安定的に耐久性の高い膜が製造可能であることが分かる。
（膜厚分布の測定結果）
膜厚分布は、エリプソメーター（株式会社堀場製作所製）による分光エリプソメトリー法にて確認した。

According to this, even when about 50 hours have elapsed from the start of film formation, the contact angle reduction rate of the film after rubbing 100,000 times is 5% or less, indicating high durability performance. It can also be seen that the film durability is not affected by the temperature at the time of vapor deposition. That is, according to the manufacturing method of the present invention, it can be seen that a highly durable film can be manufactured stably for a long time.
(Measurement result of film thickness distribution)
The film thickness distribution was confirmed by spectroscopic ellipsometry using an ellipsometer (manufactured by Horiba, Ltd.).

  The film thickness distribution measurement was performed on a sample formed when 3 hours had elapsed after the crucible temperature reached 200 ° C.

  The measurement results are shown in FIGS. 6 (A) and 6 (B).

  First, FIG. 6 (A) shows the film thickness distribution in the height direction in the carrier of the fluorine-containing organosilicon compound thin film formed on the glass substrate placed on the carrier.

  The position in the height direction in FIG. 6A means the length in the arrow direction indicated by Y in FIG. 5, and the center portion 54 in the vertical direction of the carrier is 0, and the upper side ( The arrow direction (indicated by Y) is positive, and the lower side is negative. The film thickness distribution in the height direction is obtained by measuring the film thickness distribution in the height direction when the position in the transport direction described later is 600 mm.

  FIG. 6B shows the thickness distribution in the transport direction (horizontal direction) in the carrier of the fluorine-containing organosilicon compound thin film formed on the glass substrate placed in the carrier.

  The position in the transport direction in FIG. 6B means the length in the direction of the arrow indicated by X in FIG. 5, that is, the horizontal direction (represented by X from the front end portion 54 of the carrier transport direction 53). Distance). The film thickness distribution in the transport direction is obtained by measuring the film thickness distribution at a position in each transport direction when the position in the height direction is 0 mm (carrier center portion).

  First, according to the result of FIG. 6A, the value was around 120 mm at all the measurement points, and the film thickness distribution was about ± 10.5%. Further, according to FIG. 6B, a value of about 120 mm was obtained at all measurement points in the transport direction, and the film thickness distribution was about ± 9.4%.

  From the above results, it was confirmed that a film thickness distribution of about ± 10% can be obtained in the linear source deposition source used this time in both the height direction and the conveyance direction.

DESCRIPTION OF SYMBOLS 11 Chamber 12 Fluorine-containing organosilicon compound 13 Heating container 14 Piping 15 Nozzle 17 Base material 18 Base material conveyance mechanism 19 Variable valve 20 Film thickness meter 31 Base material introduction chamber 32 Base material extraction chamber 33 Pretreatment means

Claims (10)

An apparatus for producing a fluorine-containing organosilicon compound thin film that forms a fluorine-containing organosilicon compound thin film on a substrate surface,
A chamber;
A heating vessel for heating the fluorine-containing organosilicon compound;
A plurality of nozzles provided in the chamber, connected to the heating vessel by piping, and supplying a fluorine-containing organosilicon compound to the substrate;
A substrate transport mechanism capable of continuously transporting the substrate such that the plurality of nozzles and the film formation surface of the substrate face each other, and
The fluorine-containing organosilicon compound thin film production apparatus according to claim 1, wherein the fluorine-containing organosilicon compound has been subjected to solvent removal treatment or not diluted with a solvent. A base material introduction chamber for introducing a base material into the chamber and a base material take-out chamber for taking out the base material from the chamber are connected to the chamber,
The base material introduction chamber and the base material take-out chamber are configured to be able to supply and exhaust air independently,
2. The fluorine-containing organosilicon according to claim 1, wherein the base material transport mechanism is configured to transport a base material between the base material introduction chamber, the chamber, and the base material take-out chamber. Compound thin film manufacturing equipment.   3. The fluorine-containing material according to claim 1, wherein the base material transport mechanism is capable of changing a transport speed of the base material according to a film forming speed of the fluorine-containing organosilicon compound thin film. Equipment for producing organosilicon compound thin films. The pipe connecting the heating container and the plurality of nozzles is provided with a variable valve for adjusting the supply amount of the fluorine-containing organosilicon compound,
The fluorine-containing organosilicon compound thin film according to any one of claims 1 to 3, wherein the opening degree of the variable valve is controlled in accordance with a detection value from a film thickness meter provided in the chamber. manufacturing device.   5. The fluorine-containing organosilicon compound thin film according to claim 1, further comprising pretreatment means for treating a substrate surface upstream of the plurality of nozzles in the substrate conveyance path. Manufacturing equipment. A method for producing a fluorine-containing organosilicon compound thin film comprising forming a fluorine-containing organosilicon compound thin film on a substrate surface,
The fluorine-containing organosilicon compound that has been subjected to the solvent removal treatment or the fluorine-containing organosilicon compound that has not been diluted with the solvent is heated in a heating vessel,
A fluorine-containing organosilicon compound is supplied from a plurality of nozzles provided in the chamber and connected by the heating container and piping,
Fluorine-containing organosilicon, wherein a substrate is continuously supplied by a substrate transport mechanism to a region facing the plurality of nozzles so that the plurality of nozzles and a film formation surface of the substrate are opposed to each other A method for producing a compound thin film. The chamber is connected to a base material introduction chamber capable of supplying and exhausting air independently, and a base material take-out chamber,
The base material introduced into the base material introduction chamber is transported to the chamber by the base material transport mechanism,
The method for producing a fluorine-containing organosilicon compound thin film according to claim 6, wherein after the film formation process, the base material is transported from the chamber to the base material take-out chamber by the base material transport mechanism.   The said base material conveyance mechanism changes the conveyance speed of a base material according to the film-forming speed | rate of a fluorine-containing organosilicon compound thin film, The manufacturing method of the fluorine-containing organosilicon compound thin film of Claim 6 or 7 characterized by the above-mentioned. . The piping connecting the heating container and the plurality of nozzles is provided with a variable valve so that the supply amount of the fluorine-containing organosilicon compound can be changed,
The fluorine-containing organosilicon compound thin film according to any one of claims 6 to 8, wherein the opening degree of the variable valve is controlled based on a detection value from a film thickness meter provided in the chamber. Manufacturing method.   The method for producing a fluorine-containing organosilicon compound thin film according to any one of claims 6 to 9, wherein the substrate is subjected to a pretreatment step before forming the fluorine-containing organosilicon compound.

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