JPH1133470A - Method for manufacturing protective film and apparatus for manufacturing protective film - Google Patents

Abstract

(57) [Summary] [Problem] A means for supplying a chemical adsorption liquid into a chamber (8).
(9, 11, 12), means for applying the supplied chemical adsorption liquid to the surface of the substrate (15) located outside the chamber, and means (3, 13) for supplying a low-humidity gas into the chamber. The coating device or the base material is moved using the coating device provided with the above, and the chemical adsorption liquid is efficiently applied to the surface of the substrate having an arbitrary curvature on the surface. The chamber includes a coating roll (5).
(8) The coating apparatus was moved while being filled with dry air, and the chemical adsorption liquid was applied to the surface of the glass substrate (15) on the holding table (14), and was installed before or after the coating apparatus with the movement of the coating apparatus. Dry while removing excess chemical adsorption liquid with an air knife (6, 7). When the glass substrate (15) has a curvature like window glass, the application roll (5)
Of a narrow width and reciprocated a plurality of times to apply.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a protective film formed by covalently bonding a silane-based chemisorbed compound to a substrate surface via a siloxane bond, and to a protective film producing apparatus.

[0002]

2. Description of the Related Art Conventionally, as a method for producing this kind of film, a substrate is immersed (dipped) or sprayed in a solution containing a silane compound in an atmosphere of nitrogen gas or dry air containing almost no water. By coating and drying, a protective film covalently bonded to the substrate surface via a siloxane bond has been manufactured.

[0003]

However, in the conventional immersion method, the thickness of the chemically adsorbed liquid containing the silane compound applied to the surface of the substrate is increased, and the waste of the adsorbed liquid is large. In addition, it is difficult to control the thickness of the applied film, and an excessive amount of the silane-based compound remains after drying, resulting in poor appearance such as white turbidity on the surface of the base material. Furthermore, since the solution is applied over the entire surface of the base material, masking or the like is required on the surface that does not require application. Furthermore, when the immersion method is used, it is necessary to control the pot life of the adsorbed liquid in the adsorption tank. There is also a problem that foreign substances such as dust enter the adsorption solution.

In order to solve the above-mentioned conventional problems, the present invention is free from poor appearance due to excessive application of a chemical adsorption solution containing an excessive amount of a silane-based compound, and can be applied to a specific surface of a large-area substrate. It is a first object of the present invention to provide a method of manufacturing a protective film capable of forming a whole film only. A second object of the present invention is to provide a method and an apparatus capable of uniformly forming a protective film on a large-area substrate surface having a large curvature. A third object of the present invention is to effectively use a chemical adsorption solution containing a silane-based compound for forming a protective film, so that no special consideration is required for solution management, and the protective film is low in coating cost. It is to provide a manufacturing method and an apparatus.

[0005]

In order to achieve the above object, a method for producing a protective film according to the present invention comprises forming a chemically adsorbed film on a substrate containing a hydrophilic group or imparting a hydrophilic group to the surface of the substrate. Means for supplying a chemical adsorption liquid into the chamber, means for applying the supplied chemical adsorption liquid to the surface of a substrate located outside the chamber, and supplying a low humidity gas into the chamber. Using a coating device having at least one of the following means, by moving at least one selected from the coating device and the substrate, applying the chemical adsorption liquid to the surface of the substrate, and covalently bonded to the substrate surface It is characterized by obtaining a chemisorption film. According to the method, a necessary amount of the chemical adsorption liquid can be supplied to a required portion without deactivating, and there is no need to recover and utilize an excess of the chemical adsorption liquid, and as a result, a low-cost coating can be performed. it can. In the above description, the term “substrate containing a hydrophilic group on the surface of the substrate” refers to, for example, glass, metal, hydrophilic plastic (such as hydroxyethyl acrylate resin) containing a —OH group on the surface, etc. The term "substrate provided with" refers to a substrate obtained by performing a plasma treatment or the like on a surface of a hydrophobic plastic (eg, polyolefin) to make the surface hydrophilic.

In the above method, the means for applying the chemically adsorbed liquid to the surface of the substrate includes a roll coat, a knife coat, and a knife coat.
It is preferably at least one coating means selected from a brush coat, a film coat, a fiber sheet coat and a coat using a sponge body. Here, the roll coating is a means for coating a substrate surface with a paint by a roll, and is a known method per se.
The knife coat is a means for coating a substrate surface with a paint using a blade, and is a known method per se. The knife (blade) is preferably made of synthetic rubber, plastic, or the like so as not to be damaged even if it comes into contact with the substrate surface. The brush coat is a brush coating conventionally used, and is a known method. A film coat is a slightly thicker film (for example, 80
５００500 μm) means for hanging a plastic film or sheet on the surface of a substrate and coating the surface of the substrate with a paint by utilizing the flexibility of the film or sheet. The fiber sheet coat is a means for hanging a nonwoven fabric, a woven fabric, a knitted fabric, or the like on the surface of a base material and coating the base material surface with a paint. When the substrate is a large-area substrate and the surface has a large curvature, the above-described coating means is convenient for moving the coating roll along the large curvature to perform uniform coating.

In the above method, the low-humidity gas may be dry air or nitrogen gas, but dry air having a relative humidity of 35% or less is preferable in terms of cost and safety. . In particular, it is convenient to use dry air having a relative humidity of 35% or less, since the coating film does not become cloudy.

In the above method, it is preferable that the substrate has a predetermined curvature, and the application is performed by moving a coating apparatus along the predetermined curvature. When the application device is moved along the curvature of the substrate, the adsorption liquid can be applied uniformly. Here, the predetermined curvature refers to, for example, a curvature of a windshield or the like of an automobile.

In the above method, it is preferable that the chemical adsorption liquid is applied to the entire surface of the substrate by reciprocating the coating apparatus a plurality of times on one substrate. A substrate having a curvature, such as a windshield of an automobile, has a portion that cannot be applied by one roll coating, but can be uniformly applied by reciprocating the coating device a plurality of times.

In the above method, it is preferable that the adsorbing substance used in the chemical adsorption liquid is a chlorosilane-based substance. Chlorosilane-based chemisorbed molecules (for example, RS
iCl ₃ and R are a fluorocarbon group or an organic group containing an alkyl group) and a hydrophilic group (eg, —OH
Group) and the dehydrochlorination reaction, and the more the reaction proceeds at room temperature or room temperature in a short time, the higher the reaction activity.

In the above method, it is preferable that the main component of the solvent of the adsorbing liquid is a silicone-based organic solvent. This is because the silicone-based organic solvent does not deactivate the chemisorbed molecules and is scientifically stable and highly safe. In other words, the water content is low, and there is little evaporation residue, which is convenient.

In the above method, it is preferable that an air knife is further provided in the coating apparatus or in the vicinity of the coating apparatus, and the substrate surface is dried while the excess chemical adsorption liquid is blown off by the air knife. When an air knife is provided in the coating device or in the vicinity of the coating device, drying can be performed together with the coating operation of the coating device, so that the coating operation can be performed in one step, and efficient coating can be performed.

Next, the apparatus for manufacturing a protective film according to the present invention comprises: means for supplying a chemical adsorption liquid into the chamber; means for applying the supplied chemical adsorption liquid to the surface of a substrate located outside the chamber; A coating apparatus is provided with at least means for supplying a low-humidity gas into the chamber, and means for moving at least one selected from the coating apparatus and the substrate is provided. According to the apparatus, a necessary amount of a chemical adsorption solution can be supplied to a necessary portion without deactivating, and there is no need to recover and use an excess of the chemical adsorption solution, and as a result, a low-cost coating can be performed. it can.

In the above apparatus, the means for applying the chemically adsorbed liquid to the surface of the substrate may be a roll coat, a knife coat,
It is preferably at least one coating means selected from a brush coat, a film coat, a fiber sheet coat and a coat using a sponge body. Further, in the above apparatus, it is preferable that the application roll of the roll coating apparatus is paired with a doctor roll, and that a liquid reservoir is provided between the application roll and the doctor roll. This is because the coating liquid can be supplied to the substrate surface without waste.

In the above apparatus, the low-humidity gas is
Dry air having a relative humidity of 35% or less is preferable.
Further, in the above apparatus, it is preferable that the substrate has a predetermined curvature, and a means for moving the coating apparatus along the predetermined curvature is provided. Preferably, the apparatus further comprises means for reciprocating the coating apparatus a plurality of times with respect to the substrate.

In the apparatus, the means for reciprocating the coating apparatus a plurality of times is preferably a robot having a free arm. If a robot having a free arm is installed, versatility is increased and it is convenient. Further, in the above-mentioned apparatus, it is preferable that an air knife is further provided in the coating apparatus or in the vicinity of the coating apparatus, and the substrate surface is dried and reacted while the excess chemical adsorption liquid is blown off by the air knife.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION
As the chemisorbent used for
A silane compound containing a fluoroalkyl group can be used.
Such a silane-based compound can be used as a water-repellent material for the formed protective film.
It is preferable for improving oil repellency. Fluoroalkyl group
As a specific example of a compound containing, heptadecafluorodex
Siltrichlorosilane, heptadecafluorodecylt
General formula C such as limethoxysilane _nH_{2n-m + 1}F_m-SiX
_Three(N = 0, 1, 2,..., M = 0, 1, 2,.
n + 1, X = halogen atom or alkoxy group)
Fluoroalkylsilane compounds are available.
More specifically, a substance represented by the following formula can be used. CF_Three− (CF_Two)_n-(R)_m-SiX_pCl_3-p (Where n is 0 or an integer, preferably an integer of 1 to 22,
R represents an alkyl group, a phenyl group, a vinyl group, an ethynyl group,
A substituent containing a silicon or oxygen atom, m is 0 or
1, X is H, alkyl group, alkoxyl group, fluorine-containing
A substituent of an alkyl group or a fluorine-containing alkoxy group, p is 0,
1 or 2) CH_Three− (CH_Two)_n-(R)_m-SiX_pCl_3-p (Where n is 0 or an integer, preferably an integer of 1 to 22,
R represents an alkyl group, a phenyl group, a vinyl group, an ethynyl group,
A substituent containing a silicon or oxygen atom, m is 0 or
1, X is H, alkyl group, alkoxyl group, fluorine-containing
A substituent of an alkyl group or a fluorine-containing alkoxy group, p is 0,
1 or 2) Further, (1) to (5) shown in the following formulas are also included. (1) CH_Three− (CH_Two)_rSix_pCl_3-p (2) CH_Three− (CH_Two)_rSix_pCl_3-p (3) CH_Three(CH_Two)_sO (CH_Two)_tSix_pCl_3-p (4) CH_Three(CH_Two)_u-Si (CH_Three)_Two(CH_Two)_v-S
iX_pCl_3-p (5) CF_ThreeCOO (CH_Two)_wSix_pCl_3-p (However, in a preferable range, r is 1 to 25 and s is 0 to 1
2, t is 1 to 20, u is 0 to 12, v is 1 to 20, w is
1 to 25 are shown. A compound containing a fluorocarbon group and a chlorosilyl group
When used, water repellency, oil repellency, antifouling property, lubricity, etc.
Is preferred. Furthermore, as a specific adsorption compound,
(1)-(7) shown in the following formula. (1) CH_ThreeCH_TwoO (CH_Two)_FifteenSiCl_Three (2) CH_Three(CH_Two)_TwoSi (CH_Three)_Two(CH_Two )_FifteenSi
Cl_Three (3) CH_Three(CH_Two)₆Si (CH_Three)_Two(CH_Two )₉ Si
Cl_Three (4) CH_ThreeCOO (CH_Two)_FifteenSiCl_Three (5) CF_Three(CF_Two)₇− (CH_Two)_Two-SiCl_Three (6) CF_Three(CF_Two)_Five− (CH_Two)_Two-SiCl_Three (7) CF_Three(CF_Two)₇-C₆H_Four-SiCl_Three Also, as a chlorosilane-based crosslinking agent, SiCl_Four , S
iHCl_Three , SiH_TwoCl_Two Or Cl- (SiCl
_TwoO)_n-SiCl_Three(Where n is an integer)
More durable single molecules
It has the effect of providing a membrane.

The non-aqueous solvent dissolving the silane-based chemically adsorbed substance may be any organic solvent containing no active hydrogen or water that reacts with the non-aqueous solvent. For example, for the fluoroalkylsilane compound, a general formula C _n H _{2n-m + 2} such as a hydrocarbon solvent such as n-hexadecane or a halogenated hydrocarbon solvent such as octadecafluorooctane is used.
X _m (n = 1, 2, 3,..., M = 0, 1, 2,...
· 2m + 2, X = compound represented by halogen atom), a linear alkyl siloxane, such as hexamethyldisiloxane (linear silicones) and general formula R1- (R ₂ R ₃ Si
O) _n -R ₄ (n = 1, 2, 3,..., R ₁ , R ₂ ,
Compounds represented by the general formula (R ₁ R ₂ SiO) _n (n = 1,2,2) such as compounds represented by R ₃ and R ₄ = alkyl groups, and cyclic alkylsiloxanes (cyclic silicones) such as octamethylsiloxane;
3,..., R ₁ , R ₂ = alkyl group) or a mixture thereof arbitrarily can be used.

Further, in the above protective film manufacturing apparatus, as the humidity adjusting means, a method of installing a chamber covering the coating apparatus and replacing the inside of the chamber with dry nitrogen gas is preferable. A sufficiently clean coating can be obtained even by supplying dry air.

[0020]

The present invention will be described below in detail with reference to examples.

[Embodiment 1] FIG. 1 shows, as an example of the present invention, a schematic configuration of an apparatus for producing a protective film when an application roll is used as an application apparatus. The apparatus of the present invention has a robot 1 and a robot arm 2 for moving a coating device. Further, an adsorbent supply nozzle 9 for supplying the chemical adsorbent 10 from the chemical adsorbent tank 11 via the pump 12 into the chamber 8 of the coating apparatus is provided. Further, it has a blowing nozzle 3 for supplying dry air from a dry air supply source 13 into the chamber 8 of the coating apparatus. Further, it has a doctor roll 4 and an application roll 5 for applying a chemical adsorption liquid to the surface of the substrate 15. In addition, it has air knives 6 and 7 for blowing off excess chemical adsorption liquid. Then, the coating device is moved while filling the inside of the chamber 8 covering the coating roll with dry air,
The chemical adsorption liquid is applied to the surface of the glass substrate 15 on the holding table 14, and is dried while the excess chemical adsorption liquid is blown off by the air knives 6, 7 installed before or after the coating apparatus while the coating apparatus is moved.

At this time, the robot 1 is installed as means for running the coating apparatus while partially contacting the coating roll on the surface of the glass substrate, and a robot having a three-dimensional free arm is usually used. The application roll 5 is paired with the doctor roll 4, and has a structure having a liquid reservoir 10 between the application roll and the doctor roll (FIG. 2). Note that, in FIG.
Are flanges provided integrally with the doctor roll 4 at both ends of the doctor roll 4. Due to the flanges 16 and 17, the liquid stored in the liquid reservoir 10 does not leak from both ends of the roll. Reference numeral 18 denotes a center axis (rotation axis) of the doctor roll 4. Further, reference numeral 19 denotes a center axis (rotation axis) of the application roll 5.

Further, the air knives 6 and 7 are provided before and after the coating roll 5, respectively, and are always provided with a mechanism for operating the rear side in the running direction, so that excess chemical adsorption liquid applied by the coating roll is blown off. To operate. The chemical adsorption solution put in the tank 11 is supplied from the chemical adsorption liquid supply nozzle 9 to the contact surface (chemical adsorption liquid pool) 10 between the doctor roll 4 and the application roll by the pump 12.

Further, a chamber 8 for covering the doctor roll and the application roll is provided, and a low humidity gas (dry air in this embodiment) is supplied into the chamber 8 so that the surroundings of the doctor roll and the application roll have low humidity. Desirably, the relative humidity is maintained at 35% or less.
Here, since the chamber 8 is installed so as to cover the application roll 5 leaving a margin for application, dry air leaks from the gap between the chamber 8 and the application roll 5, and the
The glass substrate surface 15 which is in contact with is always locally covered with dry air. Therefore, since the coating device and the vicinity of the coating portion inside the chamber 8 are maintained at low humidity,
It is possible to prevent the reaction between the chemical adsorption liquid containing the silane compound applied to the base material and the moisture in the atmosphere of the room where the apparatus is installed.

In the above-described coating apparatus, the coating roll 5 is pressed in contact with the doctor roll 6.
During the coating, the chemical adsorption liquid reservoir 10 at the contact portion is automatically supplied with the chemical adsorption liquid from the chemical adsorption liquid tank 11 so that a constant amount of the chemical adsorption liquid is always stored. In addition, the glass substrate 1
In the case where 5 has a curvature only in one dimension, the width of the application roll 5 may be wide, but if it has a curvature over two dimensions such as a windshield of a car, for example,
It is necessary to optimize the width according to the curvature. That is, when the curvature is large, the width of the roll 5 is reduced as shown in FIG. 3, and the number of times of applying the glass substrate 15 while shifting the roll 5 in a line shape is increased.

As described above, in the apparatus of the present embodiment, the application roll is brought into contact with the surface of the glass substrate while the chemical adsorption solution containing at least the silane compound is supplied to the outer peripheral cylindrical surface of the application roll in a low humidity atmosphere. Alternatively, it has a structure in which the adsorption liquid is applied to the surface of the base material by being moved while being pressed and rotated.

Using the above-described manufacturing apparatus, a protective film having a siloxane bond with the substrate surface was manufactured. That is, butyl rubber was used as the material of the application roll 5 and the doctor roll 4. The silane compound has a chemical formula of C ₈ F ₁₇ C ₂ H ₄
A fluoroalkyltrichlorosilane represented by SiCl ₃ was used, and octamethylcyclotetrasiloxane, a non-aqueous solvent containing no water, was used as the solvent. The concentration of the fluoroalkyltrichlorosilane was 1 vol%. In order to make the inside of the application roll 5, the doctor roll 4, and the chamber 8 a low humidity atmosphere, the relative humidity is 5%.
The following dry air was supplied. Note that nitrogen gas can be used instead of dry air.

A float glass plate (1000 mm in length, 2000 mm in width, 5 mm in thickness) was used as the glass substrate 15, and was fixedly mounted on the holder 14 so that the application surface was a non-tin surface. The chemical adsorption coating solution was applied to the surface of the glass substrate as shown in FIG. 3 while operating the application roll (diameter 70 mm, length 300 mm) at room temperature. The application amount of the chemical adsorption coating solution was 20 g / m ² . The air knife uses the same dry air as described above, and is provided before and after the application roll, and always operates the rear side in the running direction so that the excess chemical adsorption liquid after application is applied to the application roll. It was blown off in the direction to cause a dry reaction. The nozzle width of the outlet of the air knife was 350 mm, and the blowing amount of dry air was 10 l / min. At this time, a large number of hydroxyl groups are contained on the surface of the glass substrate, and these hydroxyl groups and C ₈ F
The chlorosilyl group of ₁₇ C ₂ H ₄ SiCl ₃ was subjected to a dehydrochlorination reaction, and the reaction represented by the following formula (Formula 1) proceeded.

[0028]

[Chemical 1] C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ + HO− substrate → C ₈ F ₁₇ C ₂ H ₄ S
iCl ₂ -O-substrate + HCl

Further, after the coating apparatus has run, the coating section is exposed to a normal air atmosphere containing moisture.
Further, the moisture in the air and the silane-based compound applied to the float glass plate cause a condensation reaction as shown in the following formula (Formula 2), and a transparent repellent covalently bonded to the substrate surface via a siloxane bond. Water- and oil-repellent protective film (chemical adsorption film,
Visible light transmittance 101%, provided that the visible light transmittance of the glass before treatment is 100%. ) Formed. In the above, the reason why the visible light transmittance of the product of the present example was higher than that before the treatment is considered to be that the surface reflection was reduced.

[0030]

[Chemical Formula 2] C ₈ F ₁₇ C ₂ H ₄ SiCl ₂ −O− substrate + H ₂ O → C ₈ F ₁₇ C
₂ H ₄ Si (-O-) ₃ + 2HCl

When the obtained coating film was exposed outdoors as a durability test, the contact angle with water was 114 ° at first, but it deteriorated to 95 ° three years after the weather resistance test. However, even in this state, there was still sufficient practicality as an antifouling film. Furthermore, using a glass plate having a non-alkali thin film such as SiO ₂ or Al ₂ O ₃ formed on the surface was effective in further improving the weather resistance.

In addition to butyl rubber, chloroprene or silicone sponge is also effective as a material of the coating roll used in the present invention, in addition to butyl rubber, as long as it is not damaged by the chemical adsorption liquid and has a proper wettability.

Further, in addition to a glass plate such as a float glass as a base material, a plate-shaped base material containing active hydrogen on the surface is a metal,
It can also be used for plastics. Furthermore, as an organic solvent for preparing the adsorbing liquid, any solvent which does not contain water and active hydrogen and has an appropriate boiling point (100 to 250 ° C.) is basically applicable to the present apparatus without any problem. The siloxane (silicone) solvent was found to be the best in terms of low evaporation residue, no toxicity, and no environmental destruction. The silicone solvent is
Since the effect of suppressing the reaction between the silane-based compound and the moisture in the atmosphere is great, the practicability in forming a more transparent film was high.

In the above embodiment, an example of a manufacturing method using a coating roll has been described. However, other coating methods include a brush coating method, a knife coating method, a film coating method, and the like.
A fiber sheet coat or a coat using a sponge body can be used under the same conditions.

[0035]

Comparative Example 1 In order to confirm the effects of the manufacturing method of the present invention, the chemical formula C ₈ F ₁₇ C ₂ was used under the same conditions as in Example 1 except that an air atmosphere having a relative humidity of 40% was used instead of dry air. H
Fluoroalkyltrichlorosilane represented by ₄ SiCl ₃ was dissolved in octamethylcyclotetrasiloxane.
A vol% chemisorption solution was applied and dried as it was at room temperature without using an air knife. As a result, a white turbid coating film (visible light transmittance of 63%, but the visible light transmittance of the glass before treatment is set to 100%) was obtained on the surface, and the transparency of the glass protective film was not good. It was not enough and practical.

[0036]

Example 2 In order to confirm the effect of the manufacturing method of the present invention, when an air knife was operated using air having a relative humidity of 35% under the same conditions as in Example 1, the visible light transmittance was 87%.
(However, the visible light transmittance of the glass before the treatment was set to 100%).

[0037]

Example 3 A fluorocarbon group and a chromate
CF containing rosilane groups_Three(CF_Two) ₇(CH_Two)_TwoSiC
l_ThreeWith 5 vol.% And hexachlorodisiloxy as a crosslinking agent
3 vol.% Of sun and octamethyl
Example except that 92 vol.% Of clotetrsiloxane was used.
The experiment was performed in the same manner as in Example 1. At this time, the thickness of the formed film
Was about 5 nm. In addition, this coating was subjected to a goth test.
It did not peel at all. So further,
In order to evaluate the durability of this coating, the wiper
Abrasion test under almost the same conditions as automobiles.
went. Table 1 shows the evaluation results of the contact angle with water.
Withstands 10,000 rubbing tests and has extremely high wear resistance
Was good. In addition, visible light transmittance 101% (however,
The visible light transmittance of the glass is set to 100%. ) Is formed
Was.

Table 1 Initial value After rubbing test 5,000 times After rubbing test 10,000 times Example 3 111 ° 110 ° 106 °

[0038]

As described above, according to the present invention, a water-repellent material having excellent transparency and durability is provided on the surface of a substrate having an arbitrary curvature, such as a window glass of an automobile, a vehicle, a building, or a window glass. There is an effect that an oil-repellent protective film can be efficiently formed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a structural concept of an apparatus for manufacturing a protective film having a siloxane bond according to one embodiment of the present invention.

FIG. 2 is a view conceptually showing a liquid pool formed at a contact portion between a coating roll and a doctor roll in one embodiment of the present invention.

FIG. 3 is an explanatory view showing a coating method according to one embodiment of the present invention.

[Description of Signs] 1 Robot 2 Robot Arm 3 Dry Air Blowing Nozzle 4 Doctor Roll 5 Coating Roll 6,7 Air Knife 8 Chamber 9 Adsorbent Supply Nozzle 10 Chemical Adsorbent 11 Chemical Adsorbent Tank 12 Supply Pump 13 Dry Air Supply Source 14 Holder 15 Glass substrate 16, 17 Collar at both ends of doctor roll 18 Center axis of doctor roll (rotation axis) 19 Center axis of application roll (rotation axis)

Claims (16)

[Claims] 1. A method for forming a chemisorption film on a substrate having a hydrophilic group or having a hydrophilic group on the surface of the substrate, comprising: means for supplying a chemisorption liquid into a chamber; Using a coating device having at least means for applying the chemically adsorbed liquid to the surface of the substrate located outside the chamber, and means for supplying a low-humidity gas into the chamber, and selecting from the coating device and the substrate. Wherein at least one of the substrates is moved to apply the chemical adsorption liquid to the surface of the substrate, thereby obtaining a chemical adsorption film covalently bonded to the surface of the substrate. 2. The means for applying the chemical adsorption liquid to the surface of the substrate is at least one coating means selected from a roll coat, a knife coat, a brush coat, a film coat, a fiber sheet coat and a coat using a sponge body. The method for producing a protective film according to claim 1. 3. The method according to claim 1, wherein the low-humidity gas is dry air having a relative humidity of 35% or less. 4. The method of manufacturing a protective film according to claim 1, wherein the substrate has a predetermined curvature, and the coating device is moved along the predetermined curvature. 5. The method for producing a protective film according to claim 1, wherein the chemical adsorption liquid is applied to the entire surface of the substrate by reciprocating the application device a plurality of times on one substrate. . 6. The method for producing a protective film according to claim 1, wherein the adsorption substance used in the chemical adsorption liquid is a chlorosilane-based substance. 7. The method for producing a protective film according to claim 1, wherein a main component of the solvent of the adsorbing liquid is a silicone-based organic solvent. 8. A coating apparatus or an air knife in the vicinity of the coating apparatus, wherein the surface of the substrate is dried while blowing off excess chemical adsorption liquid with the air knife.
8. The method for producing a protective film according to any one of 7. 9. A means for supplying a chemical adsorption liquid into the chamber, a means for applying the supplied chemical adsorption liquid to a surface of a substrate located outside the chamber, and supplying a low humidity gas into the chamber. And a protective film manufacturing apparatus having means for moving at least one selected from the coating apparatus and the substrate. 10. The means for applying the chemical adsorption liquid to the surface of the substrate is at least one coating means selected from a roll coat, a knife coat, a brush coat, a film coat, a fiber sheet coat, and a coat using a sponge body. An apparatus for producing a protective film according to claim 9. 11. The apparatus for producing a protective film according to claim 10, wherein an application roll of the roll coating device is paired with a doctor roll, and a liquid reservoir is provided between the application roll and the doctor roll. 12. The protective film manufacturing apparatus according to claim 9, wherein the low-humidity gas is dry air having a relative humidity of 35% or less. 13. The protective film manufacturing apparatus according to claim 9, wherein the substrate has a predetermined curvature, and a means for moving the coating device along the predetermined curvature is provided. 14. The protective film manufacturing apparatus according to claim 9, further comprising means for reciprocating the coating apparatus a plurality of times with respect to one substrate. 15. A means for reciprocating the coating device a plurality of times,
The apparatus for manufacturing a protective film according to claim 14, which is a robot having a free arm. 16. A coating apparatus or an air knife provided in the vicinity of the coating apparatus, wherein the surface of the base material is dried while blowing off excess chemical adsorption liquid with the air knife.
16. The protective film manufacturing apparatus according to any one of items 15 to 15.