JP2000328230A - Method for deposition of organic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for deposition of an organic film which controls a film thickness, sufficiently satisfies its function and stably embodies the reproducibility thereof without a failure when the film is deposited on the surface of an article to provide the article with a slippery function, water repellent function, stainproofing function, etc. SOLUTION: This method for deposition of the organic film consists in substantially uniformly and constantly depositing the film containing an organic material on the base material for deposition by heating and evaporating a finite amount of the organic material 9 containing an organic polysiloxane compound or perfluoroalkyl group-containing compound, measuring an evaporation rate and controlling the output of a heating source in such a manner that the evaporation rate is made substantially constant in accordance with the result of the measurement. At this time, the output is provided with an upper limit and/or a lower limit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an organic film by heating and evaporating a finite amount of an organic material containing an organic polysiloxane compound or a compound containing a perfluoroalkyl group, thereby forming a film on an article. It is.

[0002] The present invention also relates mainly to the use of a slip function on an article,
The present invention relates to a film-forming method for imparting a water-repellent function, a stain-preventing function, etc., and in particular for imparting a thin film to an article without impairing the appearance of the article.

The present invention also relates to a film used on the outermost surface of various display screens, the outermost surface of an optical filter used in front of various display screens, the outermost surface of an eyeglass lens or the like,
In particular, the present invention relates to a method for forming a film to be provided on the outermost surface of the antireflection function film.

[0004]

2. Description of the Related Art Hitherto, as a method of applying a film containing an organic polysiloxane compound or a compound containing a perfluoroalkyl group to a substrate to be formed on a film, dip coating, spin coating, curtain coating, roll transfer coating, gravure, and the like are known. A solution coating method such as a printing method represented by printing, a dry method such as a vacuum deposition, an ion plating, and a sputtering method have been used.

[0005] The above dip coating is disclosed in
Although described in 148902, it is difficult to strictly control the thickness of the film containing the compound depending on the viscosity of the solution. If the film is too thin, the slippery function, water repellent function, stain prevention function, etc. will not be sufficiently exhibited.On the other hand, if the film is too thick, there will be a problem with the durability of the film, or if the surface of the film is rubbed, the film will be damaged. There was also the problem of being taken off.

[0006] Regarding the dry method, see Japanese Unexamined Patent Publication No.
No. 72055, etc., an organic film-forming substance is formed very thinly by a vacuum evaporation method, and as a result, the thickness of the formed film is 0.0
It was not possible to control the thickness of the thin film to be 3 micrometers. Therefore, to determine whether or not the film actually satisfies the functions of water repellency and antifouling property, it was necessary to take out the resulting film from the vacuum vessel and evaluate it. In practice, when the organic matter evaporates, the pressure in the vacuum chamber rises due to its boiling or sublimation.However, by observing the degree of this pressure increase, a finite amount is determined, or the shutter plate above the heating source is opened and closed. I went. In this case, there has been a problem that the film is too thin to perform its intended function, or the film is too thick to rub the surface, causing the film to peel off, become whitish, and become dirty.

When a finite amount of an organic substance containing an organic polysiloxane compound or a perfluoroalkyl group-containing compound is formed as a very thin film having a thickness of 100 nm or less at most, it is difficult to control the evaporation itself. Had not been done.

On the other hand, although it is not an organic substance containing an organic polysiloxane compound or a compound containing a perfluoroalkyl group, a method for controlling evaporation of an organic film in a dry method is disclosed in JP-A-63-270456. Temperature control has been performed to keep the temperature of the Knudsen cell constant, as described in US Pat. However, this is a control for controlling the evaporation phenomenon of the organic matter by the temperature, and does not control the amount of evaporation or the thickness of the evaporated film. Therefore, the function is not controlled with respect to the function that is performed by the formed film thickness as in the case of the slipperiness function, the water repellency function film, the stain prevention function film, and the like.

[0009]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention described below.

An object of the present invention is to form a film on the surface of an article by heating and evaporating a finite amount of an organic substance containing an organic polysiloxane compound or a compound containing a perfluoroalkyl group in a dry process such as a vacuum evaporation method. In addition, when providing a slip function, water repellency function, dirt prevention function, etc., properly control the film thickness, stably realize the reproducibility without failure, and make the function necessary and sufficient It is an object of the present invention to provide a method for forming an organic film satisfying the following conditions.

[0011]

Means for Solving the Problems A method for forming an organic film according to the present invention has the following constitution to solve the above-mentioned object.

That is, the method for forming an organic film according to the present invention is a method for forming a film containing an organic substance containing an organic polysiloxane compound or a perfluoroalkyl group-containing compound on a substrate to be formed. Heating and evaporating an organic substance, controlling an output of a heating source so as to keep the evaporation amount substantially constant based on a measurement result of the evaporation amount, and providing an upper limit and / or a lower limit to the output. This is a method for forming an organic film.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a finite amount of an organic substance containing an organic polysiloxane compound or a perfluoroalkyl group-containing compound is heated and evaporated, the amount of evaporation is measured, and the measurement result is also obtained. The upper limit and / or the lower limit are provided to the output of the heating source so as to make the evaporation amount substantially constant, and the film containing the organic substance is formed on the film formation target substrate. .

In the practice of the present invention, the heating means has an output capable of controlling the amount of evaporation.
Examples include an electron gun heating method, an induction heating method, and a light irradiation method, and the resistance heating method is most preferable. In the resistance heating method, rapid bumping or the like of the organic substance is less likely to occur, which is convenient. Further, a heat radiation heating method using a resistance heating boat is most preferable. In this case, the problem of bumping and rapid decomposition of the compound do not occur, and the characteristics of the film actually formed can be predicted by the organic substance to be heated, which is very advantageous. Here, the thermal radiation heating method using a resistance heating boat means that the organic material and the resistance heating boat do not have a contact point (do not contact), and the heat of the resistance heating boat is transmitted through a certain space by radiant heat transfer. This is the method used.
Here, molybdenum or tungsten is preferably used as the material of the boat used in the resistance heating method in terms of high melting point and durability.

Means for measuring the evaporation amount of the organic substance include an optical film thickness meter, a quadrupole mass spectrometer, and a quartz crystal film thickness meter. Since it is necessary to measure a very small amount of mass in order to control the thickness, a quartz-type film thickness meter is advantageous. The quartz-type film thickness meter referred to here is a film thickness meter that deposits a film on a crystal called a crystal oscillator and calculates a change in mass from a change in a natural frequency. In general, metal films and metal oxide films are generally used, but among organic films, application examples of a finite amount of organic materials including organic polysiloxane compounds or perfluoroalkyl group-containing compounds have not been seen. I can't.

When an organic substance is heated and evaporated in this way, endothermic behavior occurs once due to latent heat of evaporation, or behavior such as heat of decomposition or heat of dissociation occurs. In some cases, it was not possible to control well just by adjusting the parameters in the integral and derivative controls. In the organic evaporation phenomenon, the relationship between the temperature and the vapor pressure cannot be linearly determined, and the behavior cannot often be predicted due to the fact that various kinds of organic substances are mixed and thus have many boiling points.

In the case of vacuum deposition, it is very difficult to keep the vacuum pressure near the evaporation source constant, and reproducibility is often not obtained due to the relationship with the vapor pressure. Furthermore, if the heating of organic materials is not really uniform,
Due to the heat capacity problem due to the size of the material, it was sometimes difficult to stably evaporate for a certain period of time.

Further, after controlling the evaporation phenomenon, a time delay occurs in the deposition rate captured by the film thickness monitor,
There is often a mismatch between the evaporation phenomenon occurring at the moment and the control signal derived from the deposition rate actually measured by the film thickness monitor.

Therefore, in addition to performing the PID control on the output, an upper limit and / or a lower limit is used for the output.
Then, very stable and reproducible control became possible.

That is, first, the case where an upper limit is set for the output to the heating source in the present invention will be described.

After the deposition speed starts to increase on the monitor at a constant output, it approaches the target speed. As the evaporation phenomenon progresses, the deposition rate gradually increases. The rising curve becomes steep, and even if the control is performed with the normal PID control parameters, the output to the heating source may become zero, but the deposition rate will increase rapidly and may be far away from the target speed. If an upper limit is set for the output to the heating source, the time required to reach the target deposition rate becomes slightly longer, but the control can be performed without abruptly increasing the deposition rate rise curve. The method of determining the upper limit depends on the evaporation phenomenon of the organic substance, but the output to the heating limit is tested several times at a constant output from below. The film thickness at the time of evaporation is monitored by a monitor, and when the deposition rate reaches the target, the output is set to zero and the target deposition rate × 5
Preferably, the output does not exceed the double deposition rate.

Next, a case where a lower limit is set for the output to the heating limit will be described.

After the deposition speed starts to increase on the monitor at a constant output, it approaches the target speed. As the evaporation phenomenon progresses, the deposition rate gradually increases. Then, the normal P
When controlled by the ID control parameter, the output to the heating source is gradually reduced beyond the target deposition rate. However, the deposition rate may decrease rapidly due to the disturbance of the evaporation phenomenon described above, and even if the output to the heating source is rapidly increased, the deposition rate may be less than 10% of the target deposition rate.
In this case, if a lower limit is set for the output to the heating source, it is possible to prevent a rapid decrease in the deposition rate during control. The method of determining the lower limit depends on the evaporation phenomenon of the organic substance, but the output to the heating limit is tested several times at a constant output from below. Preferably, the output is monitored by the above film thickness monitor, and the output is reduced when the deposition rate reaches the target, and after a certain time (for example, 10 seconds), the deposition rate becomes 10% of the target deposition rate. The time is preferably determined in consideration of the response of the deposition rate.

It is also preferable to combine an upper limit and a lower limit with the output to the heating source.

In the present invention, the thickness of the film formed on the target substrate plate is very preferably 1 nm to 30 nm. More preferably, it is very preferably from 2 nm to 10 nm. This is because, when it has a desired slip function, water repellency function, and antifouling function, its effect becomes difficult to be sufficiently exhibited when the thickness is 1 nm or less, for example, a contact angle with water as a measure for the water repellency function. You can tell by measuring. When the film thickness exceeds 30 nm, the characteristics are sufficiently satisfied when evaluated by a contact angle, but a phenomenon occurs in which the film is too thick and the film is peeled off when the surface is rubbed.
For this reason, it is whitened and looks dirty. When the film thickness is 2 nm to 10 nm, target characteristics can be stably obtained.

The organic substance used in the present invention is preferably held on a porous material. This means that organic substances can be uniformly dispersed and retained as a substance.
This is because, if the state of dispersion is good, heating is performed evenly and uniform evaporation is possible. If the liquid is put in a container in a liquid state, the vaporization phenomenon varies near the heater and on the evaporation surface, and the phenomenon such as bumping cannot be avoided.

Further, in the present invention, it is preferable to use an organic substance by attaching it to a fibrous conductive substance. Because organic substances are attached to the fibrous conductive material surface,
When heated, heating can be performed through the conductive fibers, and uniform heating of the organic material can be performed. Here, as the conductive material, iron, aluminum, copper, or carbon having high heat resistance is preferably used. Particularly, commercially available steel wool is suitable because it is inexpensive and easy to handle. The shape and the wire diameter are not particularly limited, but the wire diameter is preferably 0.01 mm to 1 mm, and more preferably 0.025 mm to 0.05 mm, from the viewpoint of workability, heat conductivity, and adhesion of organic substances. is there.

In the present invention, it is more preferable that the conductive substance is placed in a holding frame that is open in at least one direction. This can prevent the organic substance from flowing downward when the organic substance is melted by heating by being put in the holding frame, and also prevent contamination of the lower surface of the vacuum chamber. Further, if there is a direction in which evaporation occurs in any direction, it may cause the wall of the vacuum chamber to be contaminated. Therefore, it is preferable to open the evaporation direction only to the substrate to be film-formed.

In the present invention, as the organic polysiloxane compound, a polydimethylsiloxane polymer is particularly preferably used because it can increase the characteristic contact angle. Specific examples of such siloxanes include polyalkylsiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polymethylvinylsiloxane having a terminal silanol group, polyalkenyl, or polyarylsiloxane, and various crosslinking agents such as tetraacetoxysilane and tetraacetoxysilane. Add tetrafunctional silane such as alkoxyoxysilane, tetraethylmethylketoxime silane, tetraisopropenyl silane, and trifunctional silane such as alkyl or alkenyltriacetoxysilane, triketoxime silane, or triisopropenyl silane trialkoxy silane. Examples of the mixture include those mixed and, in some cases, reacted in advance.

Examples of other polysiloxanes include Si-
Compounds obtained by reacting a polysiloxane having an H bond with a compound having an unsaturated group in the presence of a catalyst such as a platinized compound and curing the compound can also be used.

The perfluoroalkyl group-containing compound is not particularly limited, but a polymer containing a perfluoro group-containing (meth) acrylate and a copolymer with another monomer are particularly preferable. Among these polymers, those into which various functional groups are introduced for the purpose of crosslinking and curing are used. Specific examples thereof include hydroxyl group-containing monomers such as hydroxy (meth) acrylate, and (meth)
Copolymers with a carboxyl group-containing monomer such as acrylic acid are exemplified. Further, a copolymer with a monomer having a double bond having different reactivity such as allyl (meth) acrylate is also mentioned as an example capable of crosslinking and curing. The polymerization form of such a copolymer is not particularly limited, and random copolymers, block copolymers, and the like can be applied, but from the viewpoint of improving water repellency, adhesion of the surface of the substrate on which a film is to be formed, and the like. Block copolymers are particularly preferably used.

The molecular weight of the above-mentioned organopolysiloxane having a terminal silanol is not particularly limited, but is preferably 1 in terms of number average molecular weight in terms of stability, ease of handling, and the like.
000 to 1,000,000, more preferably 2000 to 500,000 terminal silanol organopolysiloxanes are used.

Further, it is also possible to hydrolyze monomers such as dimethyldichlorosilane, dimethyldialkoxysilane and dimethylacetoxysilane to obtain an organic polysiloxane having a terminal silanol group. Further, it is possible to further advance the condensation reaction to obtain the above-mentioned organopolysiloxane having a terminal silanol group.

Various curing agents and three-dimensional crosslinking agents can be added to the composition containing the above-mentioned organic substance for the purpose of accelerating curing or making the composition curable. Examples of these are silicone resin curing agents,
Examples include silane coupling agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds, melamine resins, polyfunctional acrylic resins, and urea resins.

As a more specific example, it is simple and preferable that the organic substance used in the present invention contains a compound represented by the following formula (I).

N—C _p F _{p + 1} CH ₂ CH ₂ Si (NH ₂ ) ₃ ... (I) (where p is a natural number) For example, 3,3,3-trifluoropropyltriaminosilane, 2- Compounds such as (perfluoropropyl) ethyltriaminosilane, 2- (perfluorobutyl) ethyltriaminosilane, (perfluorohexyl) ethyltriaminosilane, and 2- (perfluorooctyl) ethyltriaminosilane may be used alone or in combination of two or more. Can also be used as a mixture.

The organic substance is represented by the following formula (II) and has a number average molecular weight of 500 to 10 to further improve the slipping property and the wiping property of a fingerprint or the like as a function of preventing contamination.
It is preferably used that it contains a silicon-containing organic-containing fluorine compound of 000.

[0038]

Embedded image (In the formula, Rf represents a perfluoroalkyl group. Z
Represents a fluorine or trifluoromethyl group. a, b, c,
d and e each independently represent 0 or an integer of 1 or more, and a + b + c + d + e is at least 1 or more, and a, b, c, d, e
The order of the recurring units is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R
¹ represents a hydroxyl group or a hydrolyzable substituent. R ² is
Represents hydrogen or a monovalent hydrocarbon group. l is 0, 1 or 2
Represents m represents 1, 2 or 3. According to the present invention, the organic substance having an alkoxysilane structure via a carbamate bond at a terminal represented by the following formula (III) is used as a material for improving the wiping property of fingerprints and the like as a slipping property and a stain-preventing function. It is preferably a fluorine compound.

Rf {(CH ₂ ) _n OCONH—R ¹ —Si (OR ² ) ₃ } _m Formula (III) (wherein, Rf is an organic group containing a fluorine-containing oxaalkyl group or a fluorine-containing alkyl group) , N is an integer of 1 to 4, R ¹
Is a divalent organic group, R ² is a monovalent organic group, and m is an integer of 1 to 4. In the present invention, when the surface of the substrate to be formed is a film containing silicon dioxide as a main component, the slipping function, the water repellent function, and the dirt prevention function are required for the adhesion of the film formed of the organic substance. It is advantageous in terms of adhesion and its durability to exert.

Further, when the substrate to be formed is a substrate with an antireflection film, the stain is very conspicuous, and the effect of the present invention is most exerted. That is, if the target film is not uniform and the desired film thickness is not obtained, that is, if the film is too thin, the antifouling function is insufficient. Or

In the use of a filter substrate for a display screen as a substrate on which a film is to be formed, it is widely used because it is effective for asthenopia. However, it is often said that the surface is stained by fingerprints. Such a problem can be solved by using a film obtained by forming a film.

In the present invention, the effect is particularly large when a film forming method is used in which the substrate to be formed passes through the film forming region.

In the case of the conventional vacuum evaporation method, when a finite amount of organic substance is used as an evaporation material, a bell jar type vacuum evaporation machine, that is, an evaporation source is heated in a lower part of the evaporation chamber, and a film is formed on the upper part. It is common to use a method of fixing or rotating the target substrate, but in this case, if the amount of the organic substance to be included as a finite amount is determined, a certain film thickness can be obtained by using up the organic substance. Guaranteed. However, in the case of the substrate-passing type film formation as shown in FIG. 1, a necessary amount for evaporation, which is converted from the film thickness corresponding to the length of the substrate to be passed, is included as a finite amount as an organic substance. However, there are often problems that the chemical runs out before reaching the target passage length of the substrate or that the thickness of only the first half is increased.

On the other hand, when the present invention is applied, both the film thickness formed on the passing substrate and the target passing substrate length can be formed sufficiently and sufficiently.

In the present invention, in order to accurately control the thickness of the film made of an organic substance to a desired thickness, it is preferable that the passing speed is substantially constant.

In particular, the film forming chamber has first and second stockers which can store a substrate to be formed in multiple stages before and after the film forming region. The method is preferably applied to a method of manufacturing a substrate with a thin film in which the substrate to be film-formed is sequentially taken out, sequentially passed through a film-forming region, and sequentially taken into a second stocker.

Hereinafter, an example of a method for forming an organic film according to the present invention will be described with reference to the drawings. However, the present invention is not limited to this.

FIG. 1 is a schematic view showing an example of a vapor deposition apparatus used in the method of forming an organic film according to the present invention.

In FIG. 1, the vacuum chamber 1 is basically composed of substrate holding chambers 2 and 2 ′, a substrate transfer chamber 3 and a vapor deposition chamber 4. Sealing mechanisms 8 and 8 ′ are provided in this, and are sealed under reduced pressure by a vacuum pump (not shown). Substrate 6
Are held by a substrate holding mechanism (hereinafter referred to as a stocker) 5 or 5 ′, and are transported one by one through the upper part of the vapor deposition chamber one by one by a transport roller 7 to form a film.
Alternatively, it is held at 5. An organic substance 9 is attached to the conductive substance 10 in advance, and the holding frame 1
1 and put it inside the vapor deposition chamber 4.
A current is output to the resistance heating boat 12 and the resistance heating boat 1
The organic material 9 is heated by the radiant heat of Step 2. An evaporation phenomenon occurs due to the relationship between the pressure inside the evaporation chamber 4 and the melting point boiling point sublimation point of the heated organic substance 9. The vaporized organic substance flies as a vaporized molecule with partial dissociation and decomposition. When the flying molecules reach the crystal unit 13, the mass of the crystal unit 13 changes, and the film thickness can be identified from the change in the natural frequency. With respect to this film thickness, the film thickness per unit time, that is, the deposition rate is calculated, and a control signal is sent to the output controller 16 using the arithmetic unit 15 so that the measurement result becomes constant. The output controller 16 outputs a current to the resistance heating boat 12. At this time, an upper limit or (and) a lower limit is set for the output. In this way, after confirming that the evaporation amount, that is, the deposition rate, is substantially constant with respect to the target evaporation amount, the inside of the substrate transfer chamber 3 above the evaporation chamber 4 is operated in cooperation with the stocker 5 and the transfer roller 7. Through the substrate 6 to form a film. After confirming that all the substrates 6 in one stocker have passed through the upper part of the vapor deposition chamber 4, the output to the resistance heating boat is stopped. The relationship between the film formed on the substrate and the deposition rate of the quartz film thickness gauge 14 can be determined strictly by experiments.

The organic film of the present invention can be formed, for example, on a car window glass (windshield, rear window, side window), motorcycle shield, helmet shield,
Mirrors, hand mirrors, textiles, cloths, clothes (for example, skirts, pants, cutters, suits and other spices that can be wiped off quickly), leather goods (car handles, bicycle handles,
Handbag, bag, shoes), mouse (for PC),
It is suitably used for applications such as cups, vases, carrying cases, telephone receivers, mobile phones, seals, door handles, show windows, tickets, various tickets, cards such as banks, and the front of watches.

[0051]

EXAMPLES (Example 1) (1) Preparation of base material (substrate) for film formation A commercially available polymethyl methacrylate plate (trade name "Acrylite" LN- manufactured by Mitsubishi Rayon Co., Ltd.) was used as a base material for film formation.
084, about 70% transmittance of gray color original, about 2m thick
m) was used. Examples of the hard coat paint include those obtained by hydrolyzing vinyltriethoxysilane with glacial acetic acid and those obtained by hydrolyzing methyltriethoxysilane with glacial acetic acid described in Example 1 of JP-A-59-114501. Used as a mixture. Sodium acetate as a curing agent was added to the mixed solution to obtain a paint. This coating material was applied to the film formation target substrate by an immersion method, cured at 90 ° C. for 3 hours, and a hard coat having a thickness of about 2 μm was applied. A ZrO2 / SiO2 layer is formed on this hard-coated substrate by vacuum evaporation.
A metal oxide was deposited in the order of / TiO2 / SiO2 to obtain a substrate with an antireflection film having a relative luminous reflectance of about 0.5%.
The substrate size is 700mm × 1200mm × 2mm,
Sixteen sheets were made.

(2) Preparation of Organic Substance and Deposition Material Steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 1;
Wire diameter about 0.035mm), outer diameter 18mm, height 7mm
It was packed in a copper container having a wall thickness of 1 mm and having an open top. Into this, 10 g of 2- (perfluorooctyl) ethyltriaminosilane diluted to 3% with m-xylene hexafluoride was poured, attached to the steel wool, and dried at room temperature for about 24 hours to obtain a vapor deposition material.

(3) Preparation of Antifouling Film A molybdenum material having a height (width) of 7 mm and a thickness of 0.5 mm was formed into an annular shape having a diameter of 22 mm to obtain a resistance heating boat. The deposition material obtained in the above (2) was put in the center of the ring. Thus, it is set in the vapor deposition device shown in FIG.
Further, 16 substrates for film formation obtained in the above (1) were put into a stocker, and the pressure in the vapor deposition chamber 4 was set to 1 × 10 ⁻³ Pa. The distance between the evaporation source and the substrate transfer surface is 1000 m.
m, the film thickness monitor is 600 mm high from the evaporation source,
It was arranged at a horizontal distance of 500 mm from the evaporation source.

First, a current of 650 A was supplied to the resistance heating boat, and the organic substance was heated and evaporated. The deposition rate was measured with a film thickness monitor. Gradually the rate began to rise. The target rate was set at 6 Å / s. The current value output to the resistance heating boat was controlled by PID control based on the signal of the film thickness meter. When the rate falls below the target of 6 angstroms / s, control is performed in the direction of increasing the current, and when the rate exceeds 6 Å / s, control is performed in the direction of decreasing the current. The current value of the output is 680 A as the upper limit and 400 A as the lower limit. Set. The current value was controlled between 400A and 680A. After confirming that control could be performed within a range of 6 Å / s ± 10% for 20 seconds, the substrate in the stocker was transported horizontally at a speed of 5 m / min. The time when 16 substrates were conveyed and completely passed over the upper part of the vapor deposition chamber was 4 minutes.

The antifouling film was prepared in the same manner as described above.
The test was performed six times. The deposition rate on the film thickness monitor could be controlled within the range of 6 Å / s ± 20% while the substrate to be film-formed was transported over the upper part of the vapor deposition chamber for all 36 times.

(4) Evaluation of Antifouling Film (1) Film Thickness The film thickness of the antifouling film on 16 substrates was set at 16 points (1 point / 1 sheet) in the transport direction, and a sample was prepared by an ultra-thin section method. 40000 with transmission electron microscope (H-600 manufactured by Hitachi)
It was measured on a photograph of 0 times. As a result, the thickness of all 16 points was from 4 nm to 8 nm.

(2) Water repellency Sixteen substrates were taken at 16 points (1 point / 1 sheet), and a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type) was used. A 5 mm water droplet was formed at the tip of the needle, and this was brought into contact with the sample surface to form a droplet. The angle between the liquid droplet and the surface generated at this time was measured and defined as a static contact angle. All 16 points ranged from 110 ° to 111 °.

(3) Reflection interference color The reflection interference color by the antireflection film was a pale bluish purple color, but hardly changed before and after the formation of the antifouling film.

(4) Appearance When the transmitted color was confirmed, no change was observed before and after the formation of the antifouling film. Of course, there was no problem such as whitening.

(5) Wiping stains The glass was wiped many times with a glass wiper (trade name "Toraysee") manufactured by Toray Industries, Ltd., but no wiping stains were generated.

(6) Durability Ethanol was impregnated into a glass wipe (trade name “Toraysee”) manufactured by Toray Industries, Inc. and rubbed 100 times at a pressure of ² kg / cm ² . The change in the contact angle was measured, and the change was 2 ° or less.

(7) Wiping of Fingerprints Nose oil was applied and wiped off with Toray Co., Ltd.'s eyeglass wiping (trade name "Tresea"). The oil was easily wiped off by about 5 wiping operations.

The above evaluation was performed 36 times, and almost the same results were obtained.

(Example 2) (1) Preparation of substrate for film formation A film was formed in exactly the same manner as in Example 1.

(2) Preparation of Organic Substance and Deposition Material Steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 1;
(A wire diameter of about 0.035 mm) was packed in a copper container having an outer diameter of 18 mm, a height of 7 mm, and a thickness of 1 mm and having an open top. In this, the following formula (I) diluted to 3% with perfluorohexane was used.
V)

[0066]

Embedded image Is attached to the steel wool and dried at room temperature for about 24 hours.
It was used as an evaporation material.

(3) Preparation of Antifouling Film A material of molybdenum having a height (width) of 7 mm and a thickness of 0.5 mm was formed into an annular shape having a diameter of 22 mm to obtain a resistance heating boat. The deposition material obtained in the above (2) was put in the center of the ring. Thus, it is set in the vapor deposition device shown in FIG.
Further, 16 substrates for film formation obtained in the above (1) were put into a stocker, and the pressure in the vapor deposition chamber 4 was set to 1 × 10 ⁻³ Pa. The distance between the evaporation source and the substrate transfer surface is 1000 m.
m, the film thickness monitor is 600 mm high from the evaporation source,
It was arranged at a horizontal distance of 500 mm from the evaporation source.

First, an electric current of 600 A was applied to the resistance heating boat to heat and evaporate the organic substance. The deposition rate was measured with a film thickness monitor. Gradually the rate began to rise. The target rate was set at 6 Å / s. The current value output to the resistance heating boat was controlled by PID control based on the signal of the film thickness meter. When the rate falls below the target of 6 Å / s, control is performed in the direction of increasing the current, and when the rate exceeds the target, the direction of decreasing the current is controlled. The upper limit of the output current value is 620 A and the lower limit is 450 A. Set. The current value was controlled between 450A and 620A. After confirming that control could be performed within a range of 6 Å / s ± 10% for 20 seconds, the substrate in the stocker was transported horizontally at a speed of 5 m / min. The time when 16 substrates were conveyed and completely passed over the upper part of the vapor deposition chamber was 4 minutes.

The antifouling film was prepared in exactly the same manner as described above.
The test was performed four times. In all cases, the deposition rate on the film thickness monitor could be controlled within the range of 6 Å / s ± 20% while the substrate to be film-formed was being transported above the vapor deposition chamber 24 times.

(4) Evaluation of Antifouling Film (1) Film Thickness The film thickness of the antifouling film on 16 substrates was set at 16 points (1 point / 1 sheet) in the transport direction, and a sample was prepared by an ultra-thin section method. 40000 with transmission electron microscope (H-600 manufactured by Hitachi)
It was measured on a photograph of 0 times. As a result, the thickness of all 16 points was from 4 nm to 8 nm.

(2) Water repellency 16 substrates (16 points (1 point / 1 sheet)) were taken and a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type) was used. A 5 mm water droplet was formed at the tip of the needle, and this was brought into contact with the sample surface to form a droplet. The angle between the liquid droplet and the surface generated at this time was measured and defined as a static contact angle. All 16 points are 1
It was between 10 ° and 111 °.

(3) Reflection interference color The reflection interference color by the antireflection film was a pale bluish purple color, but hardly changed before and after the formation of the antifouling film.

(4) Appearance When the transmitted color was confirmed, no change was observed before and after the formation of the antifouling film. Of course, there was no problem such as whitening.

(5) Wiping dirt The glass was wiped many times with Toray Co., Ltd. (trade name "Toraysee"), but no wiping dirt was generated.

(6) Durability Ethanol was impregnated into a glass wipe (trade name “Toraysee”) manufactured by Toray Industries, Inc. and rubbed 100 times at a pressure of ² kg / cm ² . The change in the contact angle was measured, and the change was 2 ° or less.

(7) Wipeability of Fingerprint The nose oil was applied and wiped off with Toray Co., Ltd. eyeglass wiping (trademark "Tresea"). The oil was easily wiped off by three wiping operations.

The above evaluation was performed 24 times, and almost the same results were obtained.

(Example 3) (1) Preparation of substrate for film formation A substrate was formed in exactly the same manner as in Example 1. (2) Preparation of organic substances and evaporation materials Steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 1;
(A wire diameter of about 0.035 mm) was packed in a copper container having an outer diameter of 18 mm, a height of 7 mm, and a thickness of 1 mm and having an open top. 1 g of the liquid shown in the following synthesis example was adhered to the steel wool and dried at room temperature for about 24 hours to obtain a vapor deposition material. (Synthesis example) HO-CH ₂ CF ₂ (CF ₂ CF ₂ O) n-CF ₂ CH ₂ —OH (Perfluoropolyethylene glycol-based compound Number average molecular weight 1
500) Isocyanate propyl pyrotriethoxysilane (OCN-CH ₂ CH ₂ CH ₂ -Si
(OCH ₂ CH ₃ ) ₃ ) 30 mmol and 0.01 g of DBTDL (dibutyltin dilaurate: catalyst) were added to 20 g of diethyl ether.
After dissolving and dropping in the mixture, the mixture was refluxed and stirred for 8 hours, and reacted, and then the solvent was distilled off to obtain a white viscous liquid.

(3) Preparation of Antifouling Film A molybdenum material having a height (width) of 7 mm and a thickness of 0.5 mm was formed into an annular shape having a diameter of 22 mm to obtain a resistance heating boat. The deposition material obtained in the above (2) was put in the center of the ring. Thus, it is set in the vapor deposition device shown in FIG.
Further, 16 substrates for film formation obtained in the above (1) were put into a stocker, and the pressure in the vapor deposition chamber 4 was set to 1 × 10 ⁻³ Pa. The distance between the evaporation source and the substrate transfer surface is 1000 m.
m, the film thickness monitor is 600 mm high from the evaporation source,
It was arranged at a horizontal distance of 500 mm from the evaporation source.

First, an electric current of 600 A was applied to the resistance heating boat to heat and evaporate the organic substance. The deposition rate was measured with a film thickness monitor. Gradually the rate began to rise. The target rate was set at 6 Å / s. The current value output to the resistance heating boat was controlled by PID control based on the signal of the film thickness meter. When the rate falls below the target of 6 angstroms / s, control is performed in the direction of increasing the current, and when the rate exceeds the target, the current is decreased. The upper limit of the output current value is 600 A and the lower limit is 200 A. Set. The current value was controlled between 200A and 600A. After confirming that control could be performed within a range of 6 Å / s ± 10% for 20 seconds, the substrate in the stocker was transported horizontally at a speed of 5 m / min. The time when 16 substrates were conveyed and completely passed over the upper part of the vapor deposition chamber was 4 minutes.

The antifouling film was prepared in the same manner as described above.
The test was performed six times. The deposition rate on the film thickness monitor could be controlled within the range of 6 Å / s ± 20% while the substrate to be film-formed was transported over the upper part of the vapor deposition chamber for all 36 times.

(4) Evaluation of Antifouling Film (1) Film Thickness The film thickness of the antifouling film on 16 substrates was set at 16 points (1 point / 1 sheet) in the transport direction, and a sample was prepared by an ultra-thin section method. 400,000 with a transmission electron microscope (H-600 manufactured by Hitachi)
Measurements were taken at × magnification. As a result, all 16 points were from 4 nm to 8
It had a thickness of nm.

(2) Water repellency 16 substrates (16 points (1 point / 1 sheet)) were taken and a contact angle meter (type CA-D, manufactured by Kyowa Interface Science Co., Ltd.) was used. A 5 mm water droplet was formed at the tip of the needle, and this was brought into contact with the sample surface to form a droplet. The angle between the droplet and the surface generated at this time was measured and defined as the static contact angle. All 16 points are 1
It was between 10 ° and 111 °.

(3) Reflection interference color The reflection interference color by the antireflection film was a pale blue-violet color, but almost no change was observed before and after the formation of the antifouling film.

(4) Appearance When the transmitted color was confirmed, no change was observed before and after the formation of the antifouling film. Of course, there was no problem such as whitening.

(5) Wiping dirt The glass was wiped many times with Toray Co., Ltd.'s eyeglass wiping (trade name "Toraysee"), but no wiping dirt was generated.

(6) Durability Ethanol was soaked in a glass wipe (trade name “Toraysee”) manufactured by Toray Industries, Inc. and rubbed 100 times at a pressure of ² kg / cm ² . The change in the contact angle was measured, and the change was 2 ° or less.

(7) Wiping ability of fingerprints The oil of the nose was applied and wiped off with a glass wiper (trade name "Toraysee", manufactured by Toray Industries, Inc.). The oil was easily wiped off by a single wiping operation.

The above evaluation was performed 36 times, and almost the same results were obtained.

(Example 4) (1) Preparation of substrate for film formation A substrate was formed in exactly the same manner as in Example 1.

(2) Preparation of Organic Substance and Vapor Deposition Material In a copper container having an outer diameter of 18 mm, a height of 7 mm, and a thickness of 1 mm and an open upper side, 1 g of the liquid shown in the following synthesis example was left as it was. And

(Synthesis example) HO-CH ₂ CF ₂ (CF ₂ CF ₂ O) n-CF ₂ CH ₂ -O
H (perfluoropolyethylene glycol-based compound, number average molecular weight 1500) and isocyanate propyl pyrotriethoxysilane (OCN-
After 30 mmol of CH ₂ CH ₂ CH ₂ —Si (OCH ₂ CH ₃ ) ₃ ) and 0.01 g of DBTDL (dibutyltin dilaurate: catalyst) are dissolved in 20 g of diethyl ether and added dropwise, the mixture is refluxed with stirring for 8 hours, and reacted. When the solvent was distilled off, a white viscous liquid was obtained.

(3) Preparation of Antifouling Film A material of molybdenum having a height (width) of 7 mm and a thickness of 0.5 mm was formed into an annular shape having a diameter of 22 mm to obtain a resistance heating boat. The deposition material obtained in the above (2) was put in the center of the ring. Thus, it is set in the vapor deposition device shown in FIG.
Further, 16 substrates for film formation obtained in the above (1) were put into a stocker, and the pressure in the vapor deposition chamber 4 was set to 1 × 10 ⁻³ Pa. The distance between the evaporation source and the substrate transfer surface is 1000 m.
m, the film thickness monitor is 600 mm high from the evaporation source,
It was arranged at a horizontal distance of 500 mm from the evaporation source.

First, a current of 600 A was applied to the resistance heating boat to heat and evaporate the organic substance. The deposition rate was measured with a film thickness monitor. The rate began to rise sharply. The target deposition rate was set to 6 angstroms / s, and when it reached 2 angstroms / s, the current value control to the resistance heating boat was started. PID based on signal from film thickness meter
In addition to controlling the current value output to the resistance heating boat with the control, upper and lower limits are set for the output current value. The upper limit of the current value was set to 500A, and the lower limit was set to 450A. The current value was controlled between 450A and 500A. When the evaporation rate reached 6 Å / s, the substrate in the stocker was transported horizontally at a speed of 5 m / min. The time when the 16 substrates were conveyed and passed through the upper part of the vapor deposition chamber was 4 minutes. Although the phenomenon of bumping of the material was slightly observed, it could be controlled between 2 angstroms / s and 40 angstroms / s.

(4) Evaluation of Antifouling Film (1) Film Thickness The film thickness of the antifouling film on 16 substrates was taken at 16 points (1 point / 1 sheet) in the transport direction, and a sample was prepared by an ultra-thin section method. 40000 with transmission electron microscope (H-600 manufactured by Hitachi)
It was measured on a photograph of 0 times. As a result, the thickness of all 16 points was from 2 nm to 35 nm.

(2) Water repellency Sixteen substrates were taken at 16 points (1 point / 1 sheet), and a contact angle meter (CA-D type, manufactured by Kyowa Interface Science Co., Ltd.) was used. A 5 mm water droplet was formed at the tip of the needle, and this was brought into contact with the sample surface to form a droplet. The angle between the droplet and the surface generated at this time was measured and defined as the static contact angle. All 16 points are 1
It was between 08 ° and 111 °.

(3) Reflection interference color The reflection interference color by the antireflection film was a pale bluish purple color, but hardly changed before and after the formation of the antifouling film.

(4) Appearance When the transmitted color was confirmed, no change was observed before and after the formation of the antifouling film. Of course, there was no problem such as whitening.

(5) Wiping dirt The glass was wiped many times with Toray Co., Ltd. (trade name "Toraysee"), but no wiping dirt was generated.

(6) Durability Ethanol was impregnated into a glass wipe (trade name “Toraysee”) manufactured by Toray Industries, Inc., and rubbed 100 times at a pressure of ² kg / cm ² . The change in the contact angle was measured, and the change was 2 ° or less.

(7) Wipeability of Fingerprint The oil of the nose was applied and wiped off with a glass wiper (trade name “Toraysee”, manufactured by Toray Industries, Inc.). The oil was easily wiped off by a single wiping operation.

(Comparative Example 1) (1) Preparation of a substrate to be formed A film was prepared in exactly the same manner as in Example 1.

(2) Preparation of Organic Substance and Deposition Material Steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 1;
(A wire diameter of about 0.035 mm) was packed in a copper container having an outer diameter of 18 mm, a height of 7 mm, and a thickness of 1 mm and having an open top. Into this, 10 g of 2- (perfluorooctyl) ethyltriaminosilane diluted to 3% with m-xylene hexafluoride was poured, attached to the steel wool, and dried at room temperature for about 24 hours to obtain a vapor deposition material.

(3) Preparation of antifouling film A molybdenum material having a height (width) of 7 mm and a thickness of 0.5 mm was formed into an annular shape having a diameter of 22 mm to obtain a resistance heating boat. The deposition material obtained in the above (2) was put in the center of the ring. In this manner, the substrate 1 is set in the vapor deposition apparatus shown in FIG. 1 which does not have the crystal monitor and the evaporation source control system based on the crystal monitor.
Six sheets are put into a stocker, and the pressure of the vapor deposition chamber 4 is set to 1 × 1
0 ^-3 Pa. The distance between the evaporation source and the substrate transfer surface is 1000 mm, and the film thickness monitor is set at a height of 6 mm from the evaporation source.
00 mm and a horizontal distance of 500 mm from the evaporation source.

First, a current of 650 A was supplied to the resistance heating boat, and the organic substance was heated and evaporated. With the evaporation, the pressure in the deposition chamber rose and eventually fell. Pressure is 3 × 10
^{When the} pressure rose to ^-3 Pa, the substrate in the stocker was transported horizontally at a speed of 5 m / min. Thereafter, the pressure gradually increases, and when the sixth substrate just reaches the upper part of the vapor deposition chamber, the pressure reaches a local maximum of 2 × 10 ^-2 Pa, and then the pressure starts to decrease, and the sixteenth substrate holder starts to move. When the passage was completed, the pressure was 4 × 10 ⁻³ Pa.
The deposition rate on the film thickness monitor is 4 angstroms / degree when the third substrate to be deposited passes through the upper part of the deposition chamber.
s when the 5th sheet has passed 18 angstrom /
s, 80 angstroms /
s, 50 angstroms /
s, 2 angstrom / s when the 8th sheet is passing
Met. The first to second sheets and the ninth to sixteenth sheets were less than 2 Å / s.

(4) Evaluation of Antifouling Film (1) Film Thickness The film thickness of the antifouling film on 16 substrates was set at 16 points (1 point / 1 sheet) in the transport direction, and a sample was prepared by an ultra-thin section method. 40000 with transmission electron microscope (H-600 manufactured by Hitachi)
It was measured on a photograph of 0 times. In the first and second sheets, almost no film thickness was observed. The third sheet had a thickness of 4 nm, the fourth sheet had a thickness of 6 nm, the fifth sheet had a thickness of 30 nm, the sixth sheet had a thickness of 110 nm, and the seventh sheet had a thickness of 80 nm. The 8th sheet had a thickness of 2 nm, and the ninth and subsequent sheets showed almost no film thickness.

(2) Water repellency 16 substrates (16 points (1 point / 1 sheet)) were taken and a contact angle meter (type CA-D, manufactured by Kyowa Interface Science Co., Ltd.) was used. A 5 mm water droplet was formed at the tip of the needle, and this was brought into contact with the sample surface to form a droplet. The angle between the droplet and the surface generated at this time was measured and defined as the static contact angle. The first one is 30
゜ The second sheet is 40 ゜, the third and fourth sheets are 110 ゜, the fifth sheet is 111 ゜, the sixth sheet is 112 ゜, the seventh sheet is 111 ゜, the eighth sheet is 109 ゜, and the ninth sheet is The angle was 60 ° to 20 ° to 30 ° after the 10th sheet.

(3) Reflection interference color The reflection interference color by the antireflection film was a pale bluish purple color. From the first sheet to the fourth sheet and after the eighth sheet, little change was observed before and after the formation of the antifouling film, the fifth sheet changed to a slightly bluish color, and the sixth and seventh sheets showed a very large color. The change resulted in a blue reflective interference color.

(4) Appearance When the transmitted color was confirmed, no change was observed before and after the formation of the antifouling film. Only the sixth and seventh sheets appeared slightly whitened.

(5) Wiping dirt The sixth and seventh sheets were rubbed many times with Toray Co., Ltd.'s eyeglass wiping (trademark "Toraysee"). The more the wiper was wiped, the more the wiped portion was whitened, but wiping stains occurred. The fifth sheet also appeared to have a slight tendency to wipe.

(6) Durability Ethanol was impregnated into a glass wipe (trade name “Toraysee”) manufactured by Toray Industries, Inc. and rubbed 100 times at a pressure of ² kg / cm ² . The change in the contact angle was measured, and the change was 2 ° or less.

(7) Fingerprint wiping property Nose oil was applied and wiped off with Toray Co., Ltd. eyeglass wiping (trademark "Tresee"). When the wiping was performed about 5 times, the oil was easily wiped off. It was only the third, fourth, fifth and eighth substrates.

(Comparative Example 2) Based on the results of Comparative Example 1, when manufacturing is performed using the vapor deposition apparatus shown in FIG. 1, the deposition rate on the film thickness monitor is in the range of 2 Å / s to 18 Å / s. When it was within, the antifouling film formed on the film formation target substrate was judged to be good. Therefore, when it was out of the range, it was regarded as abnormal.

The procedure was performed in exactly the same manner as in Example 1 except that the upper and lower limits were set for the output current value to the resistance heating boat. 1
The operation was performed 00 times and an abnormality occurred 21 times. Of these, 14 times exceeded the upper limit of 18 Å / s, and 7 times exceeded the lower limit of 2 Å / s. The abnormality occurrence rate was 21%.

[0115]

According to the present invention, in a dry process such as a vacuum deposition method, a finite amount of an organic substance containing an organic polysiloxane compound or a perfluoroalkyl group-containing compound is heated and evaporated to form a film-forming object. In the case of forming a film on the surface of the base material and having a slippery function, a water repellent function, a stain prevention function, etc., the film thickness is controlled, and furthermore, the reproducibility is realized stably without failure, and It is possible to form an organic film that satisfies the function as required.

Further, according to the present invention, a thin film can be formed without impairing the appearance of the substrate on which the film is to be formed. Further, the organic film-forming substrate (substrate) obtained by the present invention is used as the outermost surface of various display screens, or the outermost surface of an optical filter used in front of various display screens, or the outermost surface of an eyeglass lens. It is suitably used for an antireflection function film.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a vapor deposition apparatus used for a method for forming an organic film according to the present invention.

[Explanation of symbols]

 1. : Vacuum chamber 2, 2 ': Substrate holding chamber 3: Substrate transfer chamber 4: Vapor deposition chamber 5, 5': Substrate holding mechanism (stocker) 6: Substrate 7: Transfer roller 8, 8 ': Sealing mechanism 9: Organic substance 10: Conductive substance 11: Holding frame 12: Resistance heating boat 13: Quartz oscillator (Quartz oscillation monitor) 14: Film thickness gauge 15: Operation device 16: Output controller

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09K 3/18 104 C09K 3/18 104 G02B 1/10 C09D 183/08 // C09D 183/08 G02B 1 / 10Z F term (reference) 2K009 AA07 AA15 BB14 CC03 CC24 CC42 DD02 DD03 EE00 EE05 4D075 BB24Z BB36Z BB92Z CA09 CA34 CA36 DC24 EB16 EB43 4H020 BA36 4J038 DL011 DL031 GA12 GA15 JC35 NA09 NA09 NA09 NA09 NA09 NA09

Claims (16)

[Claims] In a method for forming a film containing an organic material containing an organic polysiloxane compound or a perfluoroalkyl group-containing compound on a film-forming target substrate, the organic material is heated and evaporated, and the amount of evaporation is increased. A method for controlling an output of a heating source so as to make the evaporation amount substantially constant based on the measurement result of (1), and providing an upper limit and / or a lower limit to the output. 2. The method according to claim 1, wherein the heating means of the heating source is a resistance heating method. 3. The method for forming an organic film according to claim 1, wherein the means for measuring the evaporation amount is a quartz film thickness meter. 4. The film thickness of a film formed on a film forming target substrate is 1
The method for forming an organic film according to claim 1, wherein the thickness is controlled to be from 30 nm to 30 nm. 5. The method for forming an organic film according to claim 1, wherein the organic substance is held by a porous material. 6. The method according to claim 1, wherein the organic substance is attached to a fibrous conductive substance. 7. The method for forming an organic film according to claim 6, wherein the conductive substance is placed in a holding frame that is open in at least one direction. 8. The organic substance, the following formula _{(I) n-C p F} p + 1 CH 2 CH 2 Si (NH 2) 3 ··· (I) ( Here, p is a natural number), a compound represented by The method for forming an organic film according to claim 1, further comprising: 9. The organic substance is represented by the following formula (II): (In the formula, Rf represents a perfluoroalkyl group. Z
Represents a fluorine or trifluoromethyl group. a, b, c,
d and e each independently represent 0 or an integer of 1 or more, and a + b + c + d + e is at least 1 or more, and a, b, c, d, e
The order of the recurring units is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R
¹ represents a hydroxyl group or a hydrolyzable substituent. R ² is
Represents hydrogen or a monovalent hydrocarbon group. l is 0, 1 or 2
Represents m represents 1, 2 or 3. The method according to claim 1, further comprising a silicon-containing organic fluorine compound having a number average molecular weight of 500 to 10,000. 10. The organic substance is represented by the following formula (III): Rf {(CH ₂ ) _n OC ONH-R ¹ —Si (OR ² ) ₃ } _m (Formula (III)) An organic group containing a fluorine oxaalkyl group or a fluorine-containing alkyl group, n is an integer of 1 to 4, R ¹
Is a divalent organic group, R ² is a monovalent organic group, and m is an integer of 1 to 4. 8. The method for forming an organic film according to claim 1, further comprising a fluorine-containing compound having an alkoxysilane structure at a terminal represented by a) via a carbamate bond. 11. The method for forming an organic film according to claim 1, wherein the surface of the substrate on which the film is to be formed is made of a film containing silicon dioxide as a main component. 12. The method for forming an organic film according to claim 1, wherein the substrate to be formed is a substrate with an antireflection film. 13. The method for forming an organic film according to claim 1, wherein the substrate for film formation is a substrate for a filter of a display screen. 14. The method according to claim 1, wherein the substrate to be formed passes through a film formation region. 15. The method according to claim 1, wherein the passing speed is substantially constant. 16. The film forming chamber has first and second stockers which can store a film formation target substrate in multiple stages before and after the film forming region, and the first stocker is closed under reduced pressure. The method according to claim 14, wherein the substrate to be film-formed is sequentially taken out from the substrate, sequentially passed through a film-forming region, and sequentially taken into a second stocker.