JPH1110768A - Method and device for manufacture of thin coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for manufacturing a thin coat uniformly on the desired face of a material to be coated regardless of the size and shape of the material to be coated by applying through injection a liquid or a gas of a chemical compound containing a functional group which can be coordinated with a metal to the material to be coated. SOLUTION: An air supply pipe 3 for an air to be supplied by a compressor 2 is connected to a spray gun 1 which discharges a coating solution, and a coating solution circulation system 6 comprising a hopper 4 and a pump 5 is connected to the spray gun 1 through a coating solution supply pipe 7, a coating solution discharge pipe 8 and a pressure regulation valve 9. A coating solution of 3 wt.% of anthranilic acid containing methanol as a solvent or a coating solution of 3 wt.% of 2-amino-4-methyl benzoic acid containing octamethyltetracyclosiloxane as a solvent, is applied through spraying to, for example, a copper cup as an object to be coated, using the spray gun 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method and an apparatus for producing a thin film. More specifically, a compound having a functional group capable of coordinating to metal is used as a coating material,
A method and apparatus for spray application are provided.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a thin film using a compound having a functional group capable of coordinating with a metal (formula 1) and (formula 2) as a material, coating is mainly performed in a solution containing the compound. A method of immersing an object for a certain period of time (hereinafter, immersion method) has been adopted. For example, Jay. Sagif, `` Journal of American Chemical Society '' (J. Sagiv, J. Am. Chem. Soc., 92, 102 (1980)), Ogawa et al., `` Langmuir '' (K. Ogawa et al., Langmuir, 6, 8)
51 (1990)). In addition, a method has been proposed in which the compound is applied on a substrate and an object is brought into contact therewith to form a film on the object (hereinafter, a transfer method).

[0003]

However, in the immersion method, it is possible to form a film irrespective of the shape of the object to be coated, but it is difficult to form a film only in a specific portion of the object to be coated. there were. For example, if a film is to be formed only on the surface of a plate-shaped object to be coated, there is no other way but to attach a material that does not peel off even in a solution on the back surface, and this method is not reliable. In addition, the immersion method requires a tank for storing the solution, and the size of the bath is determined by the size of the object to be coated. Therefore, it has been necessary to change the tank with the object to be coated. For example, when applying to the inner and outer surfaces of a pot-shaped object to be coated, the originally necessary amount of the coating liquid should be sufficient to cover the inner and outer surfaces, but in fact, the object to be coated can be completely immersed. Amount was required. In addition, an immersion tank large enough to store such a coating solution was required for that purpose.

On the other hand, in the transfer method, on the other hand, it is possible to form a film only on a desired portion of the object to be coated. And the shape of the object to be coated was limited. It has been difficult to apply to a portion where the substrate on which the coating liquid has been once applied to transfer the coating liquid onto the object to be coated cannot contact, that is, a portion where the substrate cannot enter, because the contact cannot be made.

The present invention solves the above-mentioned conventional problems by uniformly forming a thin film on a desired surface of an object to be coated, regardless of the size and shape of the object to be formed. It is an object of the present invention to provide a method and an apparatus for manufacturing the same.

[0006]

In order to achieve the above object, a method for producing a thin film of the present invention comprises a functional group represented by a chemical group capable of coordinating with a metal (formula 1) or (formula 2). The method comprises a coating step of spray-coating a liquid or gas containing a compound having the formula (1) to an object to be coated.

Next, the apparatus for producing a thin film of the present invention spray-coats a liquid or gas containing a compound having a functional group capable of coordinating to a metal (formula 1) and (formula 2) onto an object. It is provided with a configuration that includes a jetting means.

In the manufacturing method and the manufacturing apparatus,
After the spray coating step, it is preferable to further include a removing step of removing an excess coating component on the object to be coated.

In the above-mentioned production method and production apparatus, the compound preferably contains a fluorocarbon group. In the above-described production method and production apparatus, it is preferable that the liquid or gas contains a siloxane-based solvent or a fluorine-based solvent.

In the above-mentioned production method and production apparatus, the viscosity of the solvent is preferably 50 cps or less. In the manufacturing method and the manufacturing apparatus, the spray coating is preferably performed by a spray gun.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thin film using a compound having a functional group capable of coordinating with metal (formula 1) and (formula 2) as a material. It is characterized in that a gas is spray-coated on an object to be coated.

The compound capable of coordinating to a metal (formula 1) includes, for example, alkylthiol, fluoroalkylthiol, allylthiol, fluoroallylthiol, alkylalkyldisulfide, fluoroalkylfluoroalkylsulfide, alkylfluoroalkylsulfide, and the like. Alkyl allyl sulfide, fluoroalkyl allyl disulfide, alkyl fluoroallyl disulfide, fluoroalkyl fluoroallyl disulfide and the like can be mentioned, and as the compound of the above formula (2), for example, α-aminocarboxylic acid, β-aminocarboxylic acid, γ-aminocarboxylic acid, α- (aminomethyl) carboxylic acid, β- (aminomethyl) carboxylic acid, γ
-(Aminomethyl) carboxylic acid, α- (aminoethyl)
Carboxylic acid, β- (aminoethyl) carboxylic acid, γ-
(Aminoethyl) carboxylic acid, o-aminobenzoic acid, phthalic acid, o- (aminomethyl) benzoic acid, o- (aminoethyl) benzoic acid, o-aminobenzylcarboxylic acid, o
-(Aminomethyl) benzylcarboxylic acid, o- (aminoethyl) benzylcarboxylic acid and the like can be mentioned.

[0013] As a specific example of the spray coating method, a liquid or a gas pressurized in advance is discharged from one or a plurality of openings, and the liquid or the gas is applied to an object to be coated previously set in front of the openings. Is achieved. As a method for pressurizing the liquid, any of a method of directly applying pressure to the liquid and a method of mixing the pressurized gas and the liquid are suitable. When a pressurized gas such as compressed air is used, it may be appropriate to dry the coating solution by passing it through a drying filter or the like before reaching the solution.

Further, the state of ejection and discharge outside the opening may be any of mist and flux. The state of thin film deposition, that is, the thickness and density of the thin film, can be controlled by the spray time, spray angle, number of openings, opening diameter, distance to the object, how to move the object, how to move the opening, etc. It is. It is needless to say that the ejection unit may be fixed and the object to be applied movable, or the ejection unit may be movable to fix the object to be applied, as necessary.

When forming a thin film using a compound having a functional group capable of coordinating with a metal (formula 1) and (formula 2) as a material, the transition metal is exposed on the surface thereof. It is necessary to be. In particular, gold, silver, copper, and platinum are preferred. For example, when the transition metal is exposed on the surface of the material, when a treatment is performed using, for example, an alkylthiol of the above formula (Formula 1), a thin film is formed by a reaction represented by the following formula (Formula 3).

[0016]

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When the treatment is performed using, for example, anthranilic acid of the above formula (Formula 2), a thin film is formed by a reaction represented by the following formula (Formula 4).

[0018]

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[0019]

When a liquid is used, a film can be formed by directly spraying the liquid state of a compound having a functional group represented by the chemical formula (1) or (2) which can be coordinated to a metal. However, a method of spraying a solution state in which the compound is dissolved in a solvent is preferable. In particular, when a compound having a functional group (formula 1) or (formula 2) capable of coordinating to a metal is used, as a solvent to be used, water, alcohols, and ketones are preferable. The viscosity of the solution is suitably 50 cps or less, preferably 15 cp.
It is desirable to adjust to about s or less.

The injection pressure must be adjusted by the air pressure supplied from the compressor. For example, when the air pressure is 5 kgf / cm ² , 0.1 to ² kgf / cm ²
cm ² , preferably 0.5 to 1.5 kgf / cm ² . Also, the spray coating step is suitably performed in a low humidity environment. For example, when the reaction is performed at 25 ° C., it is desirable that the relative humidity is not more than 30%, preferably not more than 10%.

Also, parts that come into contact with the compound having a functional group represented by the general formula (Formula 1), for example, pipes,
For nozzles and the like, it is appropriate to take measures against corrosion. Preferably, it is desirable to use a fluororesin (for example, Teflon (DuPont)) or the like.

After the spray coating, it may be appropriate to add a step of removing excess coating. For example, when the outside of the environment of the spray coating process has high humidity, it is appropriate to add a removing process before the object to be coated comes out of the environment. Specific examples of the removal method include a method by jetting a pressurized gas or a pressurized liquid, a method by immersion in a liquid, and the like, but are not limited thereto.

In some cases, the coating liquid or the coating gas collected without being applied onto the object after the spray coating can be used for coating again. Although it depends on the state of deterioration of the recovered liquid or gas, it can be usually reused at least several times, and about 10 times if the state of deterioration is not significant. If the deterioration state is remarkable, and if not, it is preferable to add a removing means such as a filter for mainly removing the deteriorated substance in the middle of the circulating system for reuse. .

[0025]

The present invention will be described more specifically with reference to the following examples. In the following examples,% means% by weight.

Example 1 First, coating solutions A, B and C were prepared. Using methanol as a solvent, add 3 vol. Of anthranilic acid.
% Dissolved to give a coating solution A. Using octamethyltetracyclosiloxane as a solvent, 3 vol.% Of 2-amino-4-methylbenzoic acid was dissolved to prepare a coating solution B. Using ethanol as a solvent, 1 vol.% Of benzenethiol was dissolved to prepare a coating solution C.

FIG. 1 shows the configuration of the coating apparatus. An air supply pipe 3 from a compressor 2 is connected to the spray gun 1 for discharging the coating solution, and a coating solution circulation system 6 including a hopper 4 and a pump 5 forms a coating solution supply pipe 7, a coating solution discharge pipe 8, It is connected via a pressure regulating valve 9. A copper cup was used as an object to be coated.

Coating experiment 1: The coating solution A is filled in a hopper, and a spray gun (discharge port diameter 2 mm, funnel-shaped spraying is possible)
2 as shown in FIG.
0 kg, set at a distance of 30 cm, 1 kgf / cm ²
The coating solution A was sprayed at a pressure of 5 seconds for 5 seconds, and the cup was rotated at a speed of 8 m / min to form a film on the outer peripheral surface of the cup. After being left in the air for 10 minutes, the glass was sprayed with water without any visible change. The inner surface of the glass was wet with water, but no water droplets remained on the outer surface of the glass. That is, it was shown that the water-repellent thin film was formed only on the outer surface of the cup.

Coating experiment 2: Using coating solution B, an experiment was conducted in the same manner as in coating experiment 1, and it was confirmed that a similar water-repellent thin film was formed only on the outer surface of the cup.

Coating experiment 3: Filling hopper with coating solution A, spray gun (discharge port diameter 2 mm, funnel-shaped spraying possible)
As shown in FIG. 3, placed at a position 45 cm above the cup 10 at a distance of 10 cm, spraying the coating solution A at a pressure of 1 kgf / cm ² for 5 seconds, and rotating the cup at a speed of 8 m / min. To form a film on the inner peripheral surface of the cup.

After standing in the air for 10 minutes, the glass was sprayed with water without any visible change. The outer surface of the glass was wet with water, but no water droplets remained on the inner surface of the glass. That is, it was shown that the water-repellent thin film was formed only on the inner surface of the cup.

Coating Experiment 4: An experiment was performed in the same manner as in Coating Experiment 3 using Coating Solution B, and it was confirmed that a similar water-repellent thin film was formed only on the inner surface of the cup.
The above examples show that a desired thin film can be formed only on a desired curved surface. Considering that this was impossible with the conventional immersion method and transfer method, it was shown to be an extremely versatile and efficient method for producing a thin film.

Coating experiment 5: Using coating solution A, an attempt was made to form a film on a glass substrate on which copper was deposited. Glass substrate (5
1kgf / cm from the position 30cm above
^The coating solution A was sprayed at a pressure of ² for 3 seconds. 10 in the air
After standing for a minute, the contact angle to water on the glass substrate, on which no change was observed visually, was 113 °.

Analytical experiment: A thin film was formed on a copper vapor-deposited glass substrate using the coating solution A in the same manner as in the coating experiment 1. After that, when analyzed by Fourier transform infrared spectroscopy (FTIR), as shown in FIG. 4, 3200 cm ⁻¹ (N
H), 1630 cm ^-1 (C = O), 1600 cm ^-1 , 146
0 cm ^-1 (benzene backbone), was confirmed each signal 1120cm ^-1 (CO). From this, it was found that the obtained thin film had a structure as in the above formula (Formula 4).

Coating experiment 5: A copper thin glass was used as an object to be coated, and a thin film was formed using coating solution C in the same manner as in coating experiment 1. As a result, it was confirmed that the same thin film as in the coating experiment 1 was formed only on the cup surface.

Comparative Experiment 1: Using the coating solution A, an attempt was made to form a film on a glass substrate on which the same copper was deposited by a dipping method. After immersion for 20 minutes, washing with water for 10 minutes, and standing in the air for 10 minutes, the contact angle with water on the glass substrate where no change was visually observed was 114 °. From this, it was shown that a thin film having the same performance as a thin film formed by the conventional method was formed on the object by the method of the present invention in a very short time without soiling the object. .

[0036]

According to the present invention, a desired thin film can be formed only on a desired surface. The desired surface is a plane,
Regardless of the curved surface. It is possible to form a film on an object to be coated, which cannot be applied by the conventional immersion method and transfer method, and it has an effect that it can be used very widely. The apparatus for carrying out the method of the present invention is much simpler than the large-scale apparatus required for the conventional method, and has an effect that it can be used in various fields.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration of a coating apparatus according to an embodiment of the present invention.

FIG. 2 is a view showing a coating method according to one embodiment of the present invention.

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

FIG. 4 shows an analysis chart of Fourier transform infrared spectroscopy (FTIR) performed in the analysis experiment of the present invention.

[Explanation of symbols]

 1: spray gun 2: compressor 3: air supply pipe 4: hopper 5: pump 6: coating solution circulation system 7: coating solution supply pipe 8: coating solution discharge pipe 9: pressure regulating valve 10: cup

Claims (12)

[Claims] 1. A thin film comprising a coating step of spray-coating a liquid or gas containing a compound having a functional group represented by a chemical group represented by formula (1) or (2) to a coating object. Manufacturing method. -S-M1, or -SS- (where S is sulfur and M1 is a hydrogen atom or a metal atom) (However, B ¹ ~B6 Is (CH ₂ ) _n COOM (n is 0 to
3, M is a hydrogen atom or a metal atom) or (CH ₂ ) _m NXY (m is 0 to 2, X and Y are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a carbon atom. A hydrogen group). The double bond in the formula may be part of a benzene ring or another aromatic ring. 2. The method for producing a thin film according to claim 1, further comprising a removing step of removing an excessively applied portion on the object to be coated after the spray coating step. 3. The method according to claim 1, wherein the coating compound contains a fluorocarbon group. 4. The method for producing a thin film according to claim 1, wherein the liquid or gas contains a siloxane-based solvent or a fluorine-based solvent. 5. The method according to claim 1, wherein the solvent has a viscosity of 50 cps or less. 6. The method according to claim 1, wherein the spray coating is performed by a spray gun. 7. An apparatus for producing a thin film including a spraying means for spray-coating a liquid or gas containing a compound having a functional group (formula 1) and (formula 2) capable of coordinating to a metal to an object to be coated. . 8. The thin-film manufacturing apparatus according to claim 7, further comprising a removing unit for removing an excessively applied portion on the object after the spray coating. 9. The thin film manufacturing apparatus according to claim 7, wherein the coating compound has a fluorocarbon group. 10. The thin film manufacturing apparatus according to claim 7, wherein the liquid or gas contains a siloxane-based solvent or a fluorine-based solvent. 11. The apparatus for producing a thin film according to claim 7, wherein the viscosity of the solvent is 50 cps or less. 12. The thin film manufacturing apparatus according to claim 7, wherein the spray coating is performed by a spray gun.