JPH0647632B2 - Antifouling substance and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is designed to transmit and reflect light,
Or a substrate that absorbs, for example, glass (for construction, show windows, showcases, furniture, automobiles,
For trains, airplanes, ships, watches, lighting fixtures, frames, covers for various instruments and cameras, aquariums, etc., plastic (for construction, automobiles, motorcycles, CRTs)
Covers, stationery, household items, etc.), glass lenses (cameras, video cameras, binoculars, riflescopes, measuring instruments, etc.), plastic lenses (glasses, etc.), anti-reflection coating on the surface Glass lenses or plastic lenses (for glasses, etc.), mirrors (home, automobiles, construction, etc.), video display tubes (for CRT cathode ray tubes, CRT cathode ray tubes, LCDs, TFTs, FL)
Ceramics, ceramic foam (for waste gas treatment of automobiles, smoke exhaust treatment for kitchens, etc.), porcelain and pottery (artwork, tableware, toilet bowls, tiles, insulators, etc.) , Various metals, leather, wood,
Or wood with a coating (wood for construction, furniture furniture,
Crafts, tableware, Buddhist altars, altars, etc., stones (ornamental stones, rocks,
Tombstones, etc.), animal fiber, plant fiber, chemical fiber woven fabric, painted metal, plastic (ships, automobiles, motorcycles, bicycles, civil engineering machinery, agricultural machinery, airplanes, missiles, etc.), etc. The present invention relates to an antifouling substance which imparts antifouling properties such as water repellency and oil repellency to the base material and has abrasion resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, for example, a plastic lens or a glass lens for eyeglasses has an antireflection film on its surface, but since this antireflection film is poor in water repellency and oil repellency,
Water, fingerprints, oils, dust, etc. tend to adhere, and once attached, fingerprints, oils, dust, etc. cannot be easily wiped off, requiring careful handling. Therefore, it is desired to impart antifouling property.

It is known that antifouling property can be obtained by forming a film of polytetrafluoroethylene or silicone oil on the surface of a base material such as metal. However, a film made of polytetrafluoroethylene or silicone oil cannot be thinly formed. For example, when a film of polytetrafluoroethylene is formed on the antireflection film of a plastic lens or a glass lens, since the film of polytetrafluoroethylene is thick, interference occurs between this film and the antireflection film. The light transmitted through is colored or does not transmit the light, and therefore cannot be used for a lens. If the film formed on the antireflection film of this lens is a thin film such as a monomolecular film (film thickness of one molecule length), mutual interference can be prevented.

To form such a monomolecular film on a base material, a monomolecular film is formed on a water surface, and the base material is immersed in the water surface to form a monomolecular film on the surface of the base material. The Langmuir method in which the film is transferred is known. The Langmuir method monolayers can be classified into crystalline monolayers and amorphous monolayers.If the water phase temperature is below the melting point of the monolayer, the isolated two-dimensional microcrystals immediately after the development. Are formed, and as they are compressed, these crystallites are gathered together to form a morphologically apparently uniform crystalline monolayer, and when the aqueous phase temperature is equal to or higher than the melting point of the monolayer, immediately after the expansion. As amorphous domains are formed and compress,
These domains are gathered together to form an apparently uniform amorphous monolayer. Then, by cooling and crystallization of the amorphous monomolecular film, a monomolecular film having much lower defects than the crystalline monomolecular film can be obtained.

Conventionally, the plastic lens as described above,
Alternatively, in order to form a monomolecular film on the antireflection film of a glass lens, a room temperature curable polysilazane or polysiloxazane cured film forming agent (3% by weight) is used as fluorocarbon 1.
The substrate is immersed in a solution diluted with 13 (97% by weight) for about 3 minutes. At this time, since it is difficult to control the thickness of the monomolecular film, the extra film thickness is removed after the film is formed to a thickness larger than necessary. However, when the monomolecular film is formed by the above method, foreign matter adheres to the surface. There is a risk that the extra film thickness is removed by the vapor of the Freon 113 also for cleaning the foreign matter, and then dried for about 1 hour.

[0006]

However, when a monomolecular film is formed by the conventional method as described above, it is difficult to control the temperature, and the entire surface cannot be made amorphous.
Moreover, since the temperature of the base material cannot be increased, the adhesion, durability, and abrasion resistance are poor, and the yield is poor. In addition, the equipment is large, and the process is complicated and difficult to manage. Further, the excess film thickness is removed by the steam of Freon 113. However, since the Freon 113 is consumed so much that it is difficult to manage it, and when a large amount of Freon 113 is used, a large amount of Freon gas, which causes the destruction of the ozone layer in the atmosphere, which is currently a problem, is generated.

Therefore, the present inventor conducted various tests and studies on a coating method of a cured film forming agent composed of room temperature curable polysilazane or polycyclosiloxane, and as a result, the cured film forming agent was vacuum-deposited on a substrate. To form an amorphous monolayer having antifouling properties such as water repellency and oil repellency and excellent adhesion, durability, and abrasion resistance in a short time, easily and with good yield. Moreover, by forming the monomolecular film on the base material by the vacuum vapor deposition method as described above, there is no fear of foreign matter adhering at the time of forming the monomolecular film. It has been found that it can be removed without using it, and based on this, the present invention intends to provide the antifouling substance and the method for producing the same.

[0008]

The antifouling substance of the present invention for achieving the above object is an amorphous substance formed on a substrate by a room temperature curable polysilazane or a polysiloxazane cured film forming agent. It is formed by forming an organic monolayer.

Further, the method for producing an antifouling substance of the present invention for achieving the above object comprises a room temperature curable polysilazane,
A solution of any one of the polysiloxazane cured film forming agents is evaporated in a vacuum to form an amorphous monomolecular film made of the above cured film forming agent on a substrate.

Then, the solution of the cured film forming agent is prepared by diluting the cured film forming agent with a fluorine-based solvent. As a base material for forming an amorphous monomolecular film, glass, a glass lens,
Mirrors, plastics, plastic lenses, metals, ceramics, porcelain, pottery, leather, wood, stones, fabrics, painted metals, plastics, wood, or glass with a hard coat, plastics, metals, ceramics and the like can be used. The room temperature-curable polysilazane or the cured film-forming agent comprising polysiloxazane is a curable organosilicon compound represented by the following general formula (Formula 1).

[0011]

[Chemical 1]

Here, R ¹ and R ² are each a hydrogen atom or a monovalent organic group of the same or different type, such as an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or a perfluoroalkyl group. NH ₂ containing a functional group such as a halogenated hydrocarbon group, an alkoxy group, a hydrolyzable group of the same kind or different kinds in which a part or all of hydrogen atoms bonded to carbon atoms are replaced with a halogen atom, and further an epoxy group. An atom or group selected from substituted hydrocarbon groups such as a CH ₂ CH ₂ CH ₂ — group and the like, a and b are 0 to 1.5
A positive number of m ≧ 1 and n ≧ 0. As the above-mentioned curable organic silicon compound, for example, those having the structural unit formulas shown in the following (Chemical formula 2) to (Chemical formula 5) are used.

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5] (Where P is a positive integer)

It is difficult to control the film thickness of the above-mentioned amorphous monomolecular film if the film thickness is less than 0.1 nm, and if the film thickness exceeds 300 nm, the portion exceeding the film is likely to fall off, so that the film thickness is in the range of 0.1 nm to 300 nm. It is preferable to choose the thickness. Especially when used for a plastic lens or a glass lens, if it exceeds 120 nm, for example, when a lens provided with an antireflection film is used as a base material, interference occurs with the antireflection film,
It is preferable to select the film thickness in the range of 10 nm to 120 nm.

[0018]

Therefore, according to the present invention, water repellency and oil repellency can be obtained by using a cured film forming agent composed of either polysilazane or polysiloxazane which is room temperature curable. Further, since the monomolecular film is thin, it is possible to prevent interference even when used on an antireflection film of a plastic lens or a glass lens, and the monomolecular film is amorphous and has low defects. Therefore, the hardness is excellent, and the durability and wear resistance can be improved.

Further, by forming a monomolecular film of the above-mentioned cured film forming agent on a substrate by a vacuum vapor deposition method, water of crystallization is removed in a vacuum, so that it has excellent hardness, durability and abrasion resistance. A low-defect amorphous monomolecular film that can be improved can be easily formed in a short time. Moreover, by forming an amorphous monomolecular film on the substrate by the vacuum vapor deposition method as described above, the above-mentioned cured film forming agent is rich in activity and the substrate is warmed during vapor deposition to activate its surface. Therefore, the amorphous monomolecular film having one molecule length can be firmly adhered to the base material. Further, the amorphous monomolecular film can be easily removed when it exceeds 300 nm, and therefore, it becomes unnecessary to use the CFC 113.

[0020]

EXAMPLES Examples of the present invention will be described below. _{n-C 8 F 17 CH 2} CH 2 Si C l 3 50 parts by weight, and introducing ammonia gas drying in the liquid consisting of trichloromonofluoromethane 750 parts by weight by increasing the liquid temperature, trichloromonofluoromethane Was brought to reflux. After blowing 15.5 parts by weight of ammonia gas in this way, the introduction of ammonia gas was stopped, and then
While introducing nitrogen gas under reflux, the mixture was heated and stirred for 4 hours, the precipitated ammonium chloride was filtered off, trichloromonofluoromethane was evaporated and removed from the filtrate, and a cured film formed of 39.8 parts by weight of polysilazane was formed. A white solid powder as an agent was obtained.

First, tungsten (a molybdenum, tantalum or the like may be used) in the vacuum evaporation system.
An appropriate amount of a solution prepared by diluting polysilazane with trifluoromonofluoromethane, which is a fluorine-based solvent (not subject to CFC regulation) to a concentration of 3% by weight, was prepared in a resistance heating boat consisting of. Next, the vacuum pump was driven so that the inside of the vacuum apparatus was set to a vacuum degree of about 6 × 10 ⁻⁵ (which can be selected within the range of 6 × 10 ^{−4 to} 6 × 10 ⁻⁵ ) mbar. next,
The resistance heating boat was energized to evaporate the polysilazane solution, and the polysilazane monomolecular film was attached to the unheated (normal temperature) substrate. At this time, even if the base material is not heated,
As described above, since the resistance heating boat is energized and heated to about 1600 ° C., the atmosphere of the vacuum device is heated,
Therefore, the base material is also warmed. Then, by evaporating a solution of a desired amount of polysilazane for a desired time, it was possible to obtain an amorphous monomolecular film in which the size of monomolecular microcrystals was greatly increased. After that, the amorphous monolayer was cooled and crystallized to obtain a low-defect monolayer. At this time, the size of microcrystals of polysilazane monomolecules is greatly increased to 0.1 nm to 300 nm by controlling the current value and the time to be applied to the resistance heating boat, and the polysilazane monocrystals on the substrate are greatly increased. The film thickness of the molecular film can be controlled, and the relationship between the solution of polysilazane and the film thickness of the amorphous monomolecular film at this time was as follows. 0.1 cc or less: about 10 nm or less 1.0 cc: about 100 nm 1.2 cc: about 120 nm 3.0 cc or more: about 300 nm or more

Further, in order to test the growth state of the monomolecular film, the following control was performed. (1) A polysilazane solution was continuously evaporated in a vacuum vapor deposition apparatus to form a film having a thickness of 300 nm on a substrate. (2) Evaporate the solution of polysilazane in the vacuum vapor deposition apparatus, first form a film with a thickness of 150 nm on the substrate and stop the evaporation, and then evaporate again while maintaining the vacuum state. Was formed to a film thickness of. (3) The solution of polysilazane is evaporated in a vacuum vapor deposition apparatus. First, a film with a thickness of 200 nm is formed on the substrate to stop the evaporation, and the vacuum state is maintained to evaporate again. Was formed to a film thickness of. (4) Evaporate the solution of polysilazane in a vacuum vapor deposition apparatus, first form an arbitrary film thickness of less than 300 nm on the substrate to stop the evaporation, and once put the substrate on which this monomolecular film is formed into the air. After standing, it was placed again in the vacuum vapor deposition apparatus to evaporate the polysilazane solution. As a result, (1),
In the case of (2), no omission was observed with respect to friction, but in the case of (3), 300 with respect to friction was observed.
A loss of 50 nm exceeding the nm was recognized. Also, (4)
In this case, no film thickness growth was observed during re-evaporation.

The polysilazane monomolecular film is highly active in silanol groups produced when the silazane bond is hydrolyzed, whereby the adhesiveness is remarkably enhanced and the surface of the base material is warmed to be active. Therefore, it is presumed that the polysilazane firmly adheres to the substrate. Further, as is apparent from the above test results, by evaporating the solution of polysilazane in the vacuum vapor deposition apparatus, it is possible to form one layer of amorphous monomolecular film of polysilazane up to 300 nm with one molecule length. Guessed. Then, it was found that the portion exceeding 300 nm was easily removed. Therefore, when the base material was dipped in a meta-xylene hexafluoride solution together with the amorphous monomolecular film of polysilazane attached to the base material, a part of the monomolecular film exceeding 300 nm was dropped off and the above-mentioned monomolecular length was increased. It was possible to obtain a non-crystalline monomolecular film of No. 3, and it was possible to form a thin non-crystalline monomolecular film on the base material without using chlorofluorocarbon 113.

In Examples 1 to 14, a plastic lens made of polymethylmethacrylate (PMMA) was used as the base material, and in Examples 15 to 28, diethylene glycol bisallyl carbonate ( CR-39) is used, a glass plate is used as a base material in Examples 29 to 42, and a glass plate is used in Examples 43 to 56.
A glass lens treated with an antireflection film was used as a substrate, and the polysilazane solution and the vapor deposition time were changed to perform vapor deposition. The part where the film thickness exceeded 300 nm could be easily removed by the meta-xylene hexafluoride solution. In each of the embodiments, the convex surface of the lens is kept as horizontal as possible (± 3 ° is an allowable range) and the planar surface is kept horizontal (± 3 ° is an allowable range), and the contact angle meter (contactor) is used. (Table 1) to (Table 4) below show the results of measuring the contact angle with a contact angle meter.
There is an error of °, and the table below shows the maximum value of the measurement. ).

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

As is clear from the contact angles of the above-mentioned examples, it was confirmed that the amorphous monomolecular film made of polysilazane formed on the substrate had excellent water repellency. In addition, it is possible to obtain an amorphous monomolecular film with a film thickness of 0.1 nm or more, and a contact angle of 102.0 ° or more to obtain water repellency by selecting the amount of polysilazane and the vapor deposition time. I was able to confirm. Further, as a result of forming an ornamental water tank using the glass plate of the above-mentioned example and performing a moss generation test by filling it with water, it did not occur at all after 60 days and could be slightly confirmed after 90 days. did it. Since it was possible to confirm the water repellency as described above, as a result of testing together with the anti-fog effect, it was also possible to confirm that the anti-fog effect was provided. Further, in each example, fingerprints, oils, and dust could be wiped off very easily, and it was confirmed that the oil repellency was also excellent. In addition, as a result of conducting a wear resistance test at a pressure of 3 kgs in each example, it was confirmed that each of them was able to endure 10,000 times and was excellent in durability and wear resistance. Further, in the plastic lens, glass plate, and glass lens of each of the above-mentioned examples as the base material, Vickers hardness of 8, that is, hardness equivalent to that of sapphire was obtained from the measurement result by the Vickers hardness tester, and excellent abrasion resistance was obtained from this. I found out.

Next, another embodiment of the present invention will be described. Using ceramics or ceramic foam as a substrate, an amorphous monomolecular film of polysilazane was formed in the thickness range of 0.1 nm to 300 nm as described above. As a result, similar to the above, it was found that the water repellency and the oil repellency can be obtained, the Vickers hardness can be 8, that is, the hardness equivalent to that of sapphire can be obtained, and the wear resistance can be improved. . Particularly, in the case of ceramic foam, it is most suitable for treating waste gas of automobiles and flue gas of the kitchen. Further, in any case, since the polysilazane has an electric insulating property, it is also effective as an electric insulator.

Amorphous monomolecular film of polysilazane having a film thickness in the range of 0.1 nm to 300 nm as described above is used as a base material using porcelain and pottery which constitute works of art, tableware, toilet bowls, tiles and insulators. Was formed. As a result, similar to the above, it was found that the water repellency and the oil repellency can be obtained, the Vickers hardness can be 8, that is, the hardness equivalent to that of sapphire can be obtained, and the wear resistance can be improved. . Further, since the polysilazane has an electric insulation property, it is effective as an electric insulator.

Using various metals as the substrate, an amorphous molecular film of polysilazane was formed with a film thickness in the range of 0.1 nm to 300 nm as described above. As a result, similar to the above, it was found that the water repellency and the oil repellency can be obtained, the Vickers hardness can be 8, that is, the hardness equivalent to that of sapphire can be obtained, and the wear resistance can be improved. . Further, since the polysilazane has an electric insulation property, it is effective as an electric insulator, for example, a covering material for a conductive wire.

As a base material, coated metal or plastic parts of various transportation equipment such as automobiles and various machines such as civil engineering construction machines are used, and the above-mentioned coating film is used to form the above-mentioned material.
An amorphous monomolecular film of polysilazane was formed with a film thickness in the range of 1 nm to 300 nm. As a result, similar to the above, it was found that water repellency and oil repellency can be obtained, sufficient hardness can be obtained, and abrasion resistance can be improved. In particular, it has been found that the water repellency of the base material used in the sea can prevent the adhesion of shellfish.

Using a plastic as a base material, an amorphous monomolecular film of polysilazane was formed in the thickness range of 0.1 nm to 300 nm as described above. As a result, similar to the above, it was found that the water repellency and the oil repellency can be obtained, the Vickers hardness can be 8, that is, the hardness equivalent to that of sapphire can be obtained, and the wear resistance can be improved. .

In addition, as a base material, leather (including fur), wood, or painted wood (wood for construction, furniture furniture, crafts, tableware, Buddhist altars, altars), tombstone, animal fiber, vegetable A woven fabric made of fibers and chemical fibers was used to form an amorphous monomolecular film of polysilazane in the thickness range of 0.1 nm to 300 nm as described above. As a result, in all cases, water repellency, oil repellency and abrasion resistance could be obtained as in the above case.

[0036]

In summary, according to the present invention, water repellency and oil repellency can be obtained by using a cured film forming agent composed of polysilazane or polysiloxazane. Further, since the monomolecular film is thin, it is possible to prevent interference even when used on an antireflection film of a plastic lens or a glass lens, and the monomolecular film is amorphous and has low defects. Therefore, the hardness is excellent, and the durability and wear resistance can be improved.

Further, by forming a monomolecular film of the above-mentioned cured film forming agent on a substrate by a vacuum vapor deposition method, water of crystallization is removed in a vacuum, so that it has excellent hardness, durability and abrasion resistance. It is possible to easily form a low-defect amorphous monomolecular film that can be improved in a short time, and thus to improve the manufacturing yield. Moreover, by forming an amorphous monomolecular film on the substrate by the vacuum vapor deposition method as described above, the above-mentioned cured film forming agent is rich in activity and the substrate is warmed during vapor deposition to activate its surface. Therefore, the amorphous monomolecular film having one molecule length can be firmly adhered to the base material. Further, the amorphous monomolecular film can be easily removed when it exceeds 300 nm, and can be removed by a meta-xylene hexafluoride solution or the like without using Freon 113.
Therefore, it is possible to prevent environmental pollution such as destruction of the ozone layer due to CFC gas.

Claims (7)

[Claims] 1. An antifouling substance in which an amorphous monomolecular film made of a room temperature curable polysilazane or polysiloxazane cured film forming agent is formed on a substrate. 2. The base material is glass, glass lens, mirror, plastic, plastic lens, metal, ceramics,
The antifouling substance according to claim 1, which is selected from porcelain, pottery, leather, wood, stone, woven fabric, painted metal, plastic, wood, or glass having a hard coat, plastic, metal, and ceramics. 3. The thickness of the amorphous monomolecular film is 0.1 nm to 30.
The antifouling substance according to claim 1 or 2, which is selected in the range of 0 nm. 4. A solution of a room temperature curable polysilazane or polysiloxazane cured film forming agent is evaporated in a vacuum to form an amorphous monomolecular film comprising the cured film forming agent on a substrate. A method for producing an antifouling substance. 5. The base material is glass, glass lens, mirror, plastic, plastic lens, metal, ceramics,
The method for producing an antifouling substance according to claim 4, which is selected from porcelain, pottery, leather, wood, stone, woven fabric, painted metal, plastic, wood, or glass having a hard coat, plastic, metal, and ceramics. 6. The method for producing an antifouling substance according to claim 4, wherein the solution of the cured film forming agent is obtained by diluting the cured film forming agent with a fluorine-based solvent. 7. The thickness of the amorphous monomolecular film is 0.1 nm to 30.
7. The method for producing an antifouling substance according to claim 4, wherein the range is 0 nm.