GB2266309A - Silazane monomolecular film - Google Patents

Abstract

The invention provides a water- and oil-repellent stainproofing substance comprising an amorphous monomolecular film of a cured film-forming agent selected from a cold curing polysilazane or polysiloxazane, with excellent hardness, durability and wear resistance. The substance may prevent the occurrence of coherency, even if the film is used on the antireflection films of plastic- and glass-lenses. By the vacuum depositing technique, an easy, short-time formation of the amorphous monomolecular film at a high yield is achieved with no use of freon 113. The present process will not cause any environmental pollution concerning the destruction of the ozone layer.

Description

2266309

FIELD OF TRE IRVERTIOU

The present invention relates to a stainproof ing substances which can give stainproof ing properties, abrasion resistant properties.and waterand oil-repellencies to substrates. The Substrates Include those which transmit, reflect and absorb light, e.g.

glass (tor construction, ehow windows, showcases, furniture. automobiles, electric cars, airplanes, ships.

watches and clocks, illuminating devices., casings, various Instruments, camera coverings, water tanks and the like); plastics (for construction, automobiles, motorbikes, CRT coverings, stationery, household products and the like). glass lenses (for cameras, video-cameras, binocular glasses, rifle scopest measuring devices and the like); plastic lenses (for glasses and the like),, glass- or plastic-lenses with antireflection films on the surface (for glasses and the like);. mirrors, (for use at home, automobiles, construction and the like); inagre-displety tubes (for Braun tubes for TV sets, Braun tubes for CRT, LCDr TFT, FL, cathode-ray tubes and the like); ceramics and ceramic forms (for disposing waste gas of automobiles, disposing smoke of kitchens and the like); porcelain and china (art objects, tableLware, toilet stoolf tilei insulator and the like).. metals. leather; woods and woods having 6 coated merabrane (for construction, furniture, objects of craftwork, tableware, Buddhist altar tittings, household Buddhist altar and the like); stones (for appreciation rocks, tombstone and the like); textiles of animal fiber, vegetable fiber and chemical riber; coated metal and plastics (ships, automobiles, motorbikes, bicycle, machine for civil construction, agricultural machine, airplanes, parts of missiles and the like) Furthermore, the present invention relates to a method for producing the same.

PRIOR ART

Antireflection films have been conventionally applied to the surface of, for example, plastic- and glass-lenoes. The antireú1ection film requires special care in handling because fingerprints, fats, dust and the like are easily deposited on the surface thereof.

and those, once deposited, are not readily wiped off due to the inferior water- and oil-repollencies of the film.

Therefore, it has been suggested to provide the f ilm with a stainprooting property.

is It has been known that the stainproofing property can be provided by forming a f llin of polytetrafluoroethylene or silicone oil on the surface of a substrate such as natal and the like. However, the f ilin of polytetrafluoroethylene or silicone oil cannot be formed Into a thin film. For example. when the film of polytetrafluoroethylene is formed on the antireflection film on a plastic- or glass-lens, coherency is induced between the polytetraf luoroethylene film and the antireflection film, due to the thickness of the polytetrafluoroethylene film. Thus, the light transmitted through the two films is colored or no light may be transmitted through them. For that reason, the stainproofing film cannot be used on such lens.

However,, if the stainproof ing could be formed on the antireflection f ilm. on a lons as a thin f ilm. such as monomolecular film (its film thickness is the length of a single molecule) thdLn such coherency may be prevented.

As a technique to form such a monomolecular film on a substrate, there is known the Langrauir technique comprising forming a monomolecular film on a water surface and' soaking a substrate on the water surface to remove and transfer the monomolecular film from the water surface to the surface of the substrate.

The monomolecular film formed by the Langnuir technique may be described as a crystalline- and amorphous-nonomolecular film. When the temperature of the water surface Is below the nelting point of the monomolecular film, two-dimensional crystallitep. each being Isolated, are formed immediately after spreading on the substrate. and they are then collected together as compression is facilitated, so thait they is morphologically appear to form a uniform crystalline monomolecular film. When the temperature of the water surface 1ti above the melting point of the monomolecular film, amorphous domains are formed immediately after spreading on the substrate, and they are then collected together as compression is facilitated, so that they are apparently a uniform amorphous monomolecular film. The cooling and crystallization of the amorphous monomolecular f 11m may produce a monomolecular film with far leae: defects than tho2e found in the crystalline monomolecular film.

Also, in the prior art, in order to form a monomolecular film on the aforementioned antireflection f ilra of a plastic lens or a glass lens, the substrate is soaked, for about three minutes, in a solution which is prepared by diluting 3 weight percent of a cured film-forming agent selected from cold curing polysilazane and polysiloxazane with 97 weight percent of treon 113. since the control of the thicknesB of the monomolecular film is difficult, the film Is firstly formed in a thickness more than necessary,, and the unnecessary Part Of the film thickness is subsequently stripped. when a monomolecular film. is formed according to the above method, foreign matters may possibly be deposited on the surface of the film. Therefore, the unnecessary part of the film thickness Is stripped with gaseous freon 113 and is then dried for about one hour.

By the procedure. the foreign matters are also washed off.

However,, it is so difficult to control the temperature to form a monoinolecular film by this conventional method that the film formed cannot be wholly made amorphous. Neither can the temperature of the substrate be raised by the method, because this may cause. Inferior adhesion, durability and wear resistance, and a lower yield of the film so formed. Furthermore, becausethe method requires large-scale apparatuses and a complex process, the control of the process is difficUlt. Still further, -the unnecessary part of the film is stripped with gaseous freon 113. according to the method. However, the control of freon 113 is difficult due to the large amount which Is consumed.

Additionally, the high consumption of freon 113 generates a large quantity of waste freon gas. which is a cause of the current problem that the ozone layer is destroyed In the atmosphere.

SUMMARY OF THE INVENTION

The present inventor has carriod out experiments and investigations concerning coating techniques using such cured film-forming agent selected from a cold curing polysilazane or polysiloxazane. It has been found that by forming such cured film-forming agent selected from a cold curing Polysilazane or polysiloxazane on a substrate by a vacuum deposition technique, an amorphous monomolecular film having water and oil-repellencies as the stainproofing property and possessing excellent adhesion, durability and wear resistance may be formed readily at a high yield in a short period. Because there is no possibility of deposition of foreign matters at the time of forming the film on the substrate by the vacuum deposition technique., any unnecessary. part of the film thickness need not be stripped of f with freon. 113, but may be stripped off with conventional solventex,, e.g.

neta-xylene hexafluoride. Based on the above findings, the present inventor has provided a stainprooting substance and the process for producing the same.

In order to achieve the above objective, the stainproofing substance of the present invention comprises an amorphoug monomolecular film consisting of a cured rilm-forming agent selected from a cold curing polysilazane or polysiloxazane, the amorphous monomolecular film being formed on a substrate.

In order to achieve the above objective, the process for producing the stainproof Ing substance of the present Invention comprises vacuum evaporating a solution of a cured film-t6rming agent selected from a cold curing polysilazane or polysiloxazane, and forming the amorphous monomolecular film of a cuted film-forming agent selected from a cold curing polysilazzine or polysiloxazane on the substrate.

DETAILED DESCRIPTION OF THE INVENTION

The solution of a cured film-f orming agent selected from a cold curing polysilazane or.

polysiloxazane aforementioned is prepared by diluting a cured film-forming agent selected from a cold curing 6 polysilazane or polysiloxazane with aconventional fluorinated solvent.

The f allowing materials can be used as the substrate for the amorphous monomolecular film: glass lens; mirror; plastics; plastic lens; netal; ceramics; porcelain; china; leather; woods; stone; textiles; coated metal; coated plastics; coated woods or hard-coated glass; hard-coated plastics; hard-coated metal#, hard-coated ceramics and the like.

The cured film-forming agent consisting of the cold curing polysilazane or polysiloxazane, as described above in connection with the prior art, Is a curing organic silicon compound. Representative of these known compounds are compounds of the general formula#.

(Rl S i (NH SIO.

4..) M (RJ 4'b) n 2 2 where R1 ' and R each represents a hydrogen. atom or a monovalent organic group identical or different with each other, for example, an alkyl group, an alkenyl group. an aryl group, cycloalkyl group, a halogenated hydrocarbon group identical or different with each other such as a perfluoroalkyl group in which hydrogen atoms bonded to carbon atoms are partially or entirely substituted with halogen atoms, a substituted hydrocarbon group containing,---forexample, a functional group such as an alkoxy group, hydrolyzable group and, further, an epoxy group, for example, M.CH.CH2- group., a, b each represents a positive number and where mkl and nkO, pref erably in = 1 to 5 and n - 1 to 5.

As specific examples of the curing organic silicon compound, described above, those having the following constructional units may be used; CH3SI(NH)1.5 and CH3Si(OCH.MR. As noted above, these compounds are known to the art and need not be described herein in detail.

it Is difficult to control the film thickness of the amorphous monomolecular film, it it is less than 0. 1 nm. It is, however. easy to strip of f any excess filmi if the film hickness exceeds 30-0 nm. Therefore, the finished film thickness is within the range of o.l nm to 300 nm. However.. if it exceeds 120 nm, for example, coherency will occur between the amorphous monomolecular film and an antireflection film on a lens used as a substrate. Therefore, preferably, the film thickness is within the range of 1 nm to 120 ran. The film thickness Is selected within the range of 10 nm to nm, in case that the amorphous monomolecular film is used on a plastic leno and a glass lens.

Other than those described above, plastics or is metal with coated filmsi for example, may be used as a oubsteate to form the amorphous monomolacular film on the coated film.

According to the present invention, water- and oil-repellencieg may be obtained by using a cured film-forming agent selected form a cold curing polysilazane or polyE;Iloxazane. rurther, the formed film is thin because it is a monomolecular film. Thus, the film may prevent the occurrence of coherency even if it is used on an antiref lection film on a plastic- or glass-lens; still furthermore, the monomolecular film is uncrystallizable and has less defects, leading to the Improved hardness# durability and wear resistance thereof.

on the other hand, by forming a monomolecular film of a cured film-forming agent consisting of the cold curing polysilazane or polysiloxazane on a substrate by the vacuum deposition technique, water of crystallization is removbd by the vacuum, leading to the short-time formation of an amorphous monomolecular film - a - with excellent hardness, durability and wear reGistance but with less defects. In addition, by forming an amorphous monomolecular film of a cured film-forming agent eelected ftom, a cold curing polysilazane or polysiloxazane on a substrate by the vacuum deposition technique. since the cured film-forning agent Is highly active and the subatrate is warmed at the time of the vacuum deposition, the amorphous monomolecular film of one molecule thickness will strongly adhere to the substrate. Further, the amorphous monomolecular film may be easily stripped, If it exceeds. 300 nM# with a fluorinated solvent. and use of freon 113 is not necessary for such stripping.

EXAMPLES

The present invention will now be explained in Examplea hereinafter.

EXAMPIAC A Anhydrous gaseous ammonia wag introduced into a e;olution comprising so parts by weight of 11-C8P17C"?-C-H?SiC,; and 750 parts by weight of trichloromonofluoromethane to elevate the teraperature of the solution and to the reflux trichloromonotluoromethane. After blowing 15.5 parts by weight of gaseous ammonia in this way, introduction of the gaseous ammonia was stopped, and th G reaction mixture was stirred under reflux heating for 4 hours while introducing nitrogen gas under reflux. Deposited ammonium fluoride was separated by filtration and trichloromonofluoronathane was removed by evaporization from the filtrate. to obtain a white solid powder which was a cured filin-forming'agent comprising 39.0 parts by weight of polysilazane. An appropriate amount of a 9 solution of the polysilazane diluted to a 3 weight percent concentration with trichloromonof luoromethane as a solvent was prepared and placed in a resistive-heating boat in a vacuum me4--allizer. the boat being composed of tungsten (molybdenum or tantalum may be used instead).

The vacuum inside the vacuum metallizer was controlled to about 6 X ITS mb (the vacuum might be selected within a range of 6 x 10"4 to 6 x 1T5) by driving a vacuum pump.

subsequently, an electric current was applied to the resistive-heating boat to evaporate the polyisJ-lazane solution,. resulting in the deposition of a monomolecular film of polysilazane on an unheated substrate (at normal room temperature). Because the resistive-heating boat was hoated to about 16006C with the electric current, the atmosphere inside the vacuum metallizer was also warmed, together with subsequent warming of the subatrate, even though the substrate itself was not directly heated. By evaporating a required amount of a solution of polysilazane, there was produced an amorphous monomolecular filia in which the size of crystallites was profoundly Increased. BY subsequent cooling and crystallization of the amorphous nonomolecular film, a monomolecular film with less defects was produced. By the control of the intensity of the electric cu;rent and the application period thereof to the resistive-heating boat, the size of the monomolecular crystallite was increased from 0.1 nm to 300 nm and the film thickness of the monomolecular film of polysilazane on the substrate could be controlled, as is shown in the following relationship be.tween the volume of the polysilazane solution and the film thickness of the amorphous monomolecular film produced:

- 10 less than 0.1 cc less than about 10 nm 1.0 cc about 100 = 1.2 cc about 120 nn more thah 3.0 Cc more than 300 Further, for testing the state of the growth of the monomolecular film.. the following procedures were conductod.

(1) A solution of polysilazane war continuously evaporated in a vacuum metallizer to form a ú11M of 300 nn on the substrate.

(2) A solution of polysilazane was evaporated in a vacuum netallizer and when a film of 150 nm was at f irst formed on the substrate, the evaporation was stopped, and then again the solution was evaporated is (being kept in a vacuum state) to forra a further f ilz of nra thickness., that is., a film of 300 nm thickness in total.

(3) A solution of polysilazane was evaporated in a vacuum metallizer and a film of 200 = was at first formed on the substrate. Evaporation was stopped and then again the solution was evaporated (being kept in a vacuum state) to torn a film of 150 nm thickness,, that is, a filia of 350 nm thickness in total was formed.

(4) A solution of polysilazane was eVaporated in a vapor metallizer and a film of a thickness of about 300 = was formed on the substrate and evaporation was stopped. Then. the substrate on which the monomolecular film was formed was again disposed in the vacuum vapor metallizer to further evaporize the solution of polysilazane.

As a result, no defects were observed to abrasion in the cases of (.1) and (2),, whereas a defect for so nm in excess of joo nm to abrasion was observed in the case of (3). Further. no further growing of the film thickness was achieved upon re-evaporation In (4).

In the monomolecular film of polysilazane, since silanol groups, formed upon hydrolysis of the silazane coupling. 'are highly active, the adhesion Is remarkably increased therey. and when the surface of the oubstrate is activated by warming. the polysilazane strongly adheres to the substrate. Further. as Is apparent from the results of the foregoing. tests. the amorphous monomolecular film with a thickness of a single molecule of polysilazane can be formed up to 300 nm by evaporizing the solution of polysilazhne in the vacuum metallizer. Then. it has been: found that a portion In excess of 300 n= is easily removed.

When the substrate was soaked. together with the deposited amorphoua mononolecular film of polysilazane, in a solution of m-xylene hexatluoride, a portibn of the monomolecula r f ilm in excess of about 300 im could be stripped, to obtain the aforementioned amorphous monozolecular f llm of a thickness of the length of one molecule. Thus, a thin amorphous monomolecular f Ilm corresponding to the length o ú a single molecule was formed on the substrate with great accuracy and without using freon 113.

ZXAMPLBS 1 - 56 In Examples 1 to 14. plastic lenses of polymethylizathacrylate (PMA) were used as substrates; in Examples 15 to 28, plastic lenses of diethlene glycol bis (&llylcarbonate) (CR-39) were used as substrates; in Examples 29 to 42, glass lenses were used as substratesi and in Examples 43 to 56, glass lenses with a treatment of antireflection film were used as substrates. The deposition was carried out in the manner of Example A while altering the volume of a solution of polysilazane 12 - and the period of deposition. in case of exceeding 300 nia of the f 11m thicknes5, excess thicknesa was easily stripped off by zota-xylene hexafluorlde.

In each Example. the contact angle was measured with a contact-angle meter, while the peak of the convex surface of the lens was maintained as horizontally as possible (± 3 " was the pormisrible range) g and the plane surface was also maintained horizontally (± 3' was the permissible 'range). The results are shown below. (± 20 of aberration arises at the time of measuring with the contact-angle meter. The maximum value of the measurement Is shown In the following tables.) Substrate: Plastic Lens of PMMA Volume of Metallizing Contact PoIV.silatane Ppriod -(see) AnctleExample 1 0.1 15 102.0 EXaMple 2 0.3 30 103.7 Example 3 0.5 60 105.4 Example- 4 0.6 90 108.0 Example 5 0,7 90 110.2 Example 6 048 90 111.8 Example 7 0.9 90 112.7 Example 8 2.0 90 114.0 Example 9 3.0 90 114.0 Example 10 4.0 90 114.0 is Example 11 7.0 90 114. 0 Example 12 10.0 90 114.0 Example 13 15.0 90 114.0 Example 14 20.0 90 1-14.0 SUbStrata: Plastic Lens of CR-39 Provided With Antireflection Film volume of Metallizing Contact Polvsilazane Period (sep) Angle Example 15 0.1 15 103.0 Example 16 0.3 30 104.0 Example 17 0.5 60 106.4 Exanple 18 0.6 90 110.0 Examplet 19 0.7 90 112.2 Example 20 0.8 90 112.8 Example 21 0.9 90 113.2 Example 22 2.0 90 114.0 Example 23 3.0 90 114.0 is Example 24 4.0 90 114.0 Example 25 7.0 90 114.0 Example 26 10.0 90 114.0 Example 27 15.0 90 114.0 Example 28 20.0 90 114.0 - Substrate: Glass Board Volume of Metailizing Contact Polysilazane, Period (s@qI AncrIc Example 29 0.1 is 104.8 Example 30 0.3 30 107.6 Exe=pl 31 0.5 60 110.3 Example 32 0.6 90 110.0 Example 33 0.7 90 112.4 Example 34 0.8 90 112.8 Example 35 0.9 90 113.2 Example 36 2.0 90 114.0 Example 37 3.0 90 114.0 Example 38 4.0 90 114.0 Example 39 7.0 90 114.0 Example 40 10.0 90 114.0 ExaMple 41 15.0 90 114.0 Example 42 20.0 90 114.0 Substrate; Glass Lens Provided with Antireflection Film Volume of Xetallizing Contact Polysilazane, Period Iseal Angle Example 43 0.1 15 110.0 Example 44 0.3 30 112.0 Example 45 0.5 60 114.0 Example 46 0.6 90 114.0 Example 47 0,7 90 114.0 Example 48 0.8 90 114.0 EXaMple 49 0.9 90 114.0 Example 50 2.0 90 114.0 Example 51 3.0 90 114.0 ExaYaplp- 52 4.0 90 114.0 is Example 53 7.0 90 114.0 Example 54 10.0 90 114.0 Example 55 15.0 90 114.0 Example 56 20.0 90 114.0 As is ClearlY indicated by the contact angles of the individual Examples, the amorphous monomolecular films of polysilazane, which were formed on the substrates, were cionfirmed to have excellent water repellency.

The amorphous monomolecular film with the thickness of more than 0.1 ma could be obtained by selection between the volume of polysilazane and netallizing period and the contact angle became more than 102.01 which was confirmed to have water repellency.

Also, the glass boards of the above Examples were used to construct aquariums, which wore then filled with water to carry out experiments regarding moss is development. Moss never developed until 60 days had passed. and then a slight degree of moss development was confirmed 90 days later. As the water repellency was confirmed as described above, the defogging effect of the glass boards was tested simultaneously. It was also confirmed that the glass boards had defogging effects.

In each Example, fingerprints, fats and dust were extremely easily wipod off. demonstrating that the films had excellent oil repellency.

in the individual Examples, wear resistance tests were carried out on the films under the pressure of 3 kga. Each f ilm could endure that pressure up to 10j000 times. BaGed on the finding. It was confirmed that the films of the present Invention had excellent durability and wear resistance.

Furthermoret In the plastic longo glass boards,, and glass lens of the above Examples as the substrates. Vickerg hardness 8 was obtained as measured with a Vickers hardness testing device. That is, the hardness was equal to sapphire and, therefore, excellent wear resistance was also confirmed according to this.

Rext, other Exaxaples are as follows.

Ceramics or ceramic forms were used as the substrate. As ' inentioned above, the amorphous monozolecular film of polysilazane was formed with the film thickness within the range of 0.1 nia-to 300 nm. As a result., as mentioned above, it was confirmed that water repellency and oil repellency could be obtained and also Vickers hardness 8. that is, the hardness equal to sapphire could be obtained, and improved wear resistance. Especially. in the case of'. using the ceramic form, this is optimum for disposing of waste gas of automobiles and disposing of smoke of kitchens.

Further. In both cases, since polysilazane has an electric insulated property. it is available, therefore, as an electric insulator.

Porcelain and china for art objects, tablewaret toilet stool and tile insulator were used as the substrate. As mentioned above. the amorphous monomolecular film polysilazane was formed with the film thickness within the range of 0. 1 nm to -300 nm. As a result. like the above, it was confirmed that water repellency and oil repellency were obtained and also a Vickers hardness 8, that is, the hardness equal to sapphire was obtained. and improved wear resistance.

Further. since polysilazane has electric insulating properties. It is available as an electric insulator.

Various metals were used as the substrate. As mentioned above, the amorphous monomolecular film of polysilazane was formed with the film thickness within the range of 0.1 nz to 3oo nm. As a result, like the above, it was confirmed that water repellency and oil repellency were obtained.and also a Vickers hardness 8, that is, the hardness equal to sapphire, and improved 19 - wear resistance. Purther, since polysilazane has electric Insulating properties, It is available as an electric insulator, e.g. for coating material for lead wires.

Coated metal for all sorts of transporting machinea, including automobiles and the like, machines for civil construction and the like, or plastic parts may be used as the substrata.

As nentioned above, the amorphous monomolecular film of polysilazane was formed on the coated substrata with the film thickness within the range of 0.1 nm to 300 nm. AS a result, like the above, it was confirmed that water repellency and oil repellency could be obtained and also sufficient hardness could be obtained and improved wear resistance.

Especially in case of using the substrate in the sea, it was confirmed that It could prevent sea-shall animals from sticking to, for example. a boat hull, by means of water repellency.

Plastics were used as the substrate. As mentioned above, the amorphous monomolecular film of polysilazane was formed with the film. thickness with the range of 0.1 nia to 300 nm. As a result. like as the above, it was confirmed that water repellency and oil repellency were obtained and also a Vickers hardness 8, that is, a hardness equal to sapphire, and improved wear renistance.

Also, leather (including furs),, woods (for construction, furniture, objects of craftwork, tableware, Buddhist altar fittings. household Buddhist altar), tombstone, textiles consisting of animal fiber, vegetable fiber, chemical fiber were used as the substrate. As mentioned above, the amorphous monomolecular film of polysilazane was formed with the film thickness within the range of 0.1 to 300 nTa. AS a result, like the above, It was confirmed that water repellency,, oil repellency and wear resistance could be obtained in all caes.

According to the present invention, the use of a cured film-forming agent selected from a dold curing polyailazane or polysiloxazane provides the film with water- and oil-repellencies. Because the film is a monomolocular film and is thin, it may prevent the occurrence of coherency even It the film is used on the antireflection film of a plastic lens or a glass lens.

Furthermore, the monomolecular film is amorphous and has less defects, and has excellent hardness, durability and wear ratistance.

is By f orming a monomolecular f ilm of a cured f ilm-forming agent selected from a cold curing polysilazane or polysiloxazane on a substrate by the vacuum deposition technique. water of crystallization may be removed in the vacuum, leading to an easy short-time formation of the amorphous nonomolecular film, being superior in hardness, durability and wear resistance and having less detects. Thus, the production yield thereof may be Improved. By forming a monomolecular film of a cured film-forming agent selected from a cold curing polysilazane or polysiloxazane on a substrate by the vacuum deposition technique, as is described above, the substrate is warmed at the time of deposition so that the surface of the substrate is activated. Consequently. the amorphous nonoraolecular film of a thickness of one molecular length will strongly adhere to the substrate. Also, a portion of the amorphous monomolecular film may be readily stripped off from the substrate in cases of the thickness exceeding 300 nm, or so. It can be stripped 1 of f with a conventional solvent, such as meta-xylene hexatluoride, and use of freon 113 Is not required. As described in connection with the prior art. a large quantity of freon 113 raust be used In order to strip the unnecessary part of the prior art film. The use of freon 113 can contribute to the destruction of the ozone layer of the atmosphere. in the present invention.

freon 113 is not necessary as a solvent,, and other conventional solvents, such as m-xylene hexafluoride, which Is exempt from the Regulations regarding freon, rday bo used for stripping excess thickness o"f the film.

Accordinglyf with the present Inventionj environmental pollution, including contributing to the destruction of the ozone layer. may he prevented.

Claims (7)

wRAT 10 CLAIMED IS:

1. Stainproof ing substance formed on a substrate and being an ala6rphous monomolecular film consisting of a cur' ed f ilm-forming agent solacted from a cold curing polysilazane or polysiloxazane.

2. The stainproofing substance in claim li x,xho-rein the substrate is selected f rom glass, glass lens, mirror, plastics, plastic lens, metal. ceramic, porcelain, china, leather, woods, stone, textile. coated metal# coated plastics, coated woods or hard-coated glass. hard-coated plastics, hard-coated matalo hard-coated ceramics.

3. The stainproofIng substance in claim lr wherein the thJoknesG of the amorphous mononolecular is film is within the range of 0.1 nTa to 300 nm.

4. Process for producing a stainproofed substrate, comprising vacuum evaporating a solution of a cured filx-forming agent selected from a cold curing polysilazane or polysiloxazane and depositing an amorphous monomolecular stainproofing film thereof on a subetrate.

5. The process for producing the stainproofed substrate of claiX 4, wherein the substrate is selected from glass, glass lens, mirror. plastics plastic lens, metal. ceramics. porcelain, china, leather, woods, stone, textile, coated metal, coated plastics, coated woods or hard-coated glass, hard-coated plastics. hard-coated metal. hard-coated ceramics.

6. The proceas for produoing the stainproofed substrate of claim 5, wherein the solution of a cured film-forming agent is prepared by diluting the cured f 11m-forming agent with a fluorinated solvent.

7. The process for producing the stainproofed substrate of claim 61 wherein the thickness of the amorphous nonoraolecular film is within the range of 0.1 nm to 300 nm.