FR2690454A1 - Stain resistant material of the polysilazane or polysiloxazane type, and process for its manufacture. - Google Patents

Abstract

The present invention provides a hydrophobic and oleoresistant stain resistant material comprising an amorphous monomolecular film of a cured film former selected from polysilazane or polysiloxazane, cold setting, having hardness, durability and wear resistance. which are excellent. The material can prevent the appearance of coherence, even if the film is used on the anti-reflective films of plastic and glass lenses. By the vacuum deposition technique, the easy formation, in a short time, of the amorphous monomolecular film, with a higher yield, is obtained without the use of Freon 113. The present process does not cause any pollution of the environment in that which concerns the destruction of the ozone layer.

Description

The present invention relates to a stain-resistant material which can

  These substrates include those which transmit, reflect and absorb light, for example glass (for the construction, showcases, etc.). displays, furniture, automobiles, electric cars, airplanes, boats, watches and clocks, lighting devices, housings, various instruments, photographic camera covers, water tanks and like); plastics (for construction, automobiles, mopeds, cathode ray tube covers, office supplies, household products and the like); glass lenses (for cameras, video cameras, binoculars, glasses

  sights, measuring devices and the like); the len

  plastic cups (for spectacles and the like); glass or plastic lenses having anti-reflective films on the surface (for spectacles and the like); mirrors (for home use, for automobiles, for construction and the like); image display tubes (for Braun tubes for television sets, Braun tubes for cathode ray tubes, liquid crystal displays, thin film tubes, FLs, cathode ray tubes and the like); ceramics and ceramic forms (for exhausting automobile exhaust gases, exhausting cooking fumes and the like); porcelain and earthenware (works of art, dishes, toilet bowls, tiles, insulators and the like); metals; leathers, woods and woods covered with a membrane (for construction, furniture, handicrafts, tableware, Buddhist altar fittings, domestic Buddhist altars and the like); stones (for valuable jewels, gravestones and the like); textile materials consisting of animal fibers, plant fibers and chemical fibers; coated metals, plastics (boats, automobiles, mopeds, bicycles, machines for civil constructions, agricultural machinery, airplanes, missile parts and the like) Furthermore, the present invention relates to

  a method of manufacturing this material.

  Anti-reflective films are applied in a conventional manner to the surface, for example of plastic and glass lenses. The anti-reflective film requires particular care in its handling because fingerprints, greases, dust and the like are deposit on its surface, and these, once deposited, are not easily removed by wiping due to the lower hydrophobicity and oleophobicity of the film Therefore, it is expected that it is

  proposed a film having the property of stain resistance.

  It is known that one can get the property of

  stain resistance by forming a polytetrafluoro film

  ethylene or silicone oil on the surface of a substrate,

  such as a metal and the like However, the poly-film

  For example, when the polytetrafluoroethylene film is formed on the antireflection film on a plastic lens or glass, a coherence is induced between the polytetrafluoroethylene film and the polytetrafluoroethylene film. the anti-reflective film, because of the thickness of the polytetrafluoroethylene film Thus, the light transmitted through the two films is colored or no light can be transmitted through them For this reason, the stain resistant film can not be used on such a lens However, if this film could be formed on the anti-reflection film on a lens, in the form of a thin film such as a monomolecular film (its film thickness is equal to the length of a film). only molecule), so we

could prevent consistency.

  As a technique for forming such a mono-

  substrate on a substrate, the Langmuir technique is known, including forming a monomolecular film on the surface of the water and soaking a substrate on the surface of the water to remove and transfer the monomolecular film from the substrate. surface of water on the surface of the substrate The monomolecular films formed by the Langmuir technique can be classified into crystalline monomolecular films and amorphous monomolecular films when the water surface temperature is below the melting point of the monomolecular film, two-dimensional crystallites, each isolated, are formed immediately after spreading on the substrate, and they are then combined since the compression is facilitated, so that they appear morphologically as forming a uniform crystalline monomolecular film;

  when the temperature of the water surface is

  above the melting point of the monomolecular film, amorphous domains are formed immediately after spreading on the substrate, and they are then gathered since the compression is facilitated, so that they apparently form a uniform amorphous monomolecular film. and crystallization of the amorphous monomolecular film can produce a monomolecular film with far fewer defects than those found in the crystalline monomolecular film. Moreover, in the prior art, to form a

  monomolecular film on the antireflection film mentioned above.

  on top of a plastic lens or a glass lens, the substrate is soaked for about three minutes in a solution which is prepared by dilution of 3% by weight of a cured film-forming agent selected from polysilazane and cold-hardening polysiloxazane with 97% by weight of Freon 113 Since control of the thickness of the monomolecular film is difficult, the film is first formed with a thickness greater than that required, and a portion If a monomolecular film is formed in accordance with the above method, extraneous material may be deposited on the surface of the film. Therefore, the unnecessary part of the film is removed. film thickness is removed with Freon 113 gas, then the film is dried for about an hour. By this procedure, the foreign material is also

eliminated.

  However, it is so difficult to control the temperature to form a monomolecular film by the

  classical method that the formed film can not be complete-

  The substrate temperature can not be increased by this method either, because this can result in lower adhesion, durability and wear resistance, and lower film performance. In addition, since the method requires large apparatus and a complex process, the process control is difficult. Moreover, the unnecessary part of the film is removed with Freon 113 gas, according to the method. , the control of Freon 113 is difficult because of the large amount of it that must be consumed In addition, the high consumption of Freon 113 generates a significant amount of Freon gas, gas known to be at the root of the current problem of the destruction of

  the ozone layer in the atmosphere.

  The present inventor has experimented and researched coating techniques using a cured film former selected from a cold hardening polysilazane or polysiloxazane. Accordingly, he has discovered that by forming such a cured film former selected from a polysilazane or a cold-setting polysiloxazane on a substrate by a vacuum deposition technique, an amorphous monomolecular film having hydrophobicity and oleophobicity can be easily formed in a short time in a short time. stain resistance property and having an excellent adhesion, durability and resistance to wear As there is no possibility of deposition of foreign matter at the time of film formation on the substrate by the vacuum deposition technique, the unnecessary part of the film thickness can be removed without the use of Freon 113, but can be removed by conventional solvents, for example meta-xylene hexafluoride. Based on the above findings, the present inventor has proposed a stain-resistant material and the method for making it. To achieve the above object, the stain-resistant material of the present invention comprises an amorphous monomolecular film consisting of a cured film former selected from a cold-setting polysilazane or polysiloxazane, the amorphous monomolecular film being

formed on a substrate.

  To achieve the above objective, the method of making the stain resistant material of the present invention comprises vacuum evaporation of a solution of a cured film former selected from polysilazane or polysiloxazane, cold hardening and forming, on a substrate, the amorphous monomolecular film of a cured film former selected from a polysilazane or a

  polysiloxazane, cold hardening.

  The solution of a hardened hydrophobic agent selected from a cold-hardening polysilazane or polysiloxazane, which is mentioned above, is prepared by diluting a cured film former selected from polysilazane or polysiloxazane, cold-setting, by a conventional fluorinated solvent. The following materials may be used as the substrate on which the amorphous monomolecular film is formed: glass lenses, mirrors, plastics, plastic lenses, metals, ceramics, porcelain, earthenware, leather, wood, stone, textile materials, coated metals, coated plastics, coated or hard-coated glass, hard-coated plastics, hard-coated metals, hard-coated ceramic and the like.

  The cured film-forming agent consisting of

  cold-setting silazane or polysiloxazane described above

  In the prior art, this is a curable silicon organic compound. Representative compounds among these known compounds have the following general formula: (R a Si (NH) 4) m (R 2 Si O 4-b) na 4-amb 4-b

2 2

  in which: R 1 and R 2 each represent a hydrogen atom or a monovalent organic group, these groups being identical or different from each other, for example an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, which are identical to or different from each other, such as a perfluoroalkyl group in which the hydrogen atoms bonded to the carbon atoms are partially or totally replaced by halogen atoms, a substituted hydrocarbon group containing, for example, a functional group such as an alkoxy group, a hydrolyzable group and, moreover, an epoxy group, for example an NH 2 CH 2 CH 2 group; a, b each represent a positive number; and m = 1 and n, 0, and preferably m = 1 to 5 and N = 1 to 5. As specific examples of curable silicon organic compounds described above, those having the following structural units can be used: If (NH), 5 and CH 3 Si (OCH 3) NH As indicated above, these compounds are known

  in the prior art and therefore do not call for a description

more detailed.

  It is difficult to control the thickness of the amorphous monomolecular film, if it is less than 0.1 nm. However, it is easy to remove any excess film if the thickness of the film exceeds 300 nm. Finished film is chosen in the range from 0.1 nm to 300 nm. However, if it exceeds 120 nm, for example, there will be a coherence between the amorphous monomolecular film and the anti-reflective film of a lens used as a substrate. Therefore, the thickness of the film is preferably selected in the range of 1 nm to 120 nm. The thickness of the film is selected in the range of 10 nm to 20 nm, in the case where the monomolecular amorphous film is used. on a lens in

  plastic material and a glass lens.

  Apart from those described above, plastics or metals with a coating film, for example, can be used as a substrate to form the

  amorphous monomolecular film on the coating film.

  In accordance with the present invention, the hydrophobicity and oleophobicity can be achieved by using a cured fumigant selected from a cold-curing polysilazane or polysiloxazane. Further, the formed film is thin because it is a monomolecular film. Thus, the film can prevent the occurrence of coherence even if it is used on the antireflection film on a plastic lens or glass; moreover, the monomolecular film is non-crystallizable and has fewer defects, which leads to hardness, durability and

  wear resistance of it which are improved.

  Moreover, by forming a monomolecular film of a cured film-forming agent consisting of polysilazane or polysiloxazane, cold hardening, on a substrate, by the vacuum deposition technique, the water of crystallization is removed by the effect of vacuum, resulting in the formation, in a short time, of an amorphous monomolecular film having excellent hardness, durability and wear resistance, but with fewer defects. amorphous monomolecular film of a cured film-forming agent selected from polysilazane or polysiloxazane, cold-setting, on a substrate, by the vacuum deposition technique, since the cured fuming agent is very active and the substrate is When heated to vacuum deposition, the amorphous monomolecular film having a length of one molecule can be strongly adhered to the substrate. In addition, the amorphous monomolecular film can be easily removed. if it exceeds 300 nm, the use of Freon 113 is no longer

necessary for this purpose.

Examples

  The present invention will now be explained

in the Examples below.

Example A

  Anhydrous ammonia gas was introduced into a solution comprising 50 parts by weight of

  n C 8 F 17 CH 2 CH 2 Si C 1 3 and 750 parts by weight of trichlo-

  romonofluoromethane to raise the temperature of the

  solution to reflux the trichloromonofluorocarbon

  After blowing 15.5 parts by weight of gaseous ammonia in this manner, the introduction of gaseous ammonia was stopped, and the reaction mixture was stirred under reflux for 4 hours, while stirring. Non-refluxing nitrogen gas The deposited ammonium fluoride was filtered off and the trichloromonofluoromethane was evaporated from the filtrate to obtain a white solid powder which was a hardened film former comprising 39.0 parts by weight of polysilazane A suitable amount of a solution of polysilazane diluted to a concentration of 3% by weight with trichloromonofluoromethane as solvent was prepared and placed in a resistance heating boat in a vacuum metallization device, the pod being composed tungsten (molybdenum or tantalum can be used instead) The degree of vacuum inside the metallis device Vacuum filtration was set at about 6 x 10-5 mb (6 x 10-3 Pa) and the vacuum could be selected within a range of 6 x 10-4 mb (6 x -2 Pa). at 6 x 10-5 mb (6 x 10-3 Pa) l by actuation of a vacuum pump Subsequently, an electric current was applied to the resistance-heated nacelle to evaporate the polysilazane solution. , leading to the deposition of a monomolecular film of polysilazane on an unheated substrate (at normal temperature) Due to the fact that the nacelle with resistance heating was heated to about 1600 C with the electric current, the atmosphere at The interior of the vacuum metallization device was also heated, together with the subsequent heating of the substrate, even though the substrate itself was not heated directly. By evaporation of a required amount of a polysilazane solution, could obtain an amorphous monomolecular film in which the dimension Crystallites were greatly increased By subsequent cooling and crystallisation of the amorphous monomolecular film, a monomolecular film with fewer defects could be obtained by controlling the intensity of the electric current and its duration of application to the resistance heating boat. , the size of the monomolecular crystallites was increased from 0.1 nm to 300 nm and the film thickness of the monomolecular polysilazane film

  on the substrate could be adjusted, following the relationship

  after between the volume of the polysilazane solution and the film thickness of the resulting amorphous monomolecular film: less than 0.1 cm 3: less than about 10 nm 1.0 cm 3: about 100 nm 1.2 cm 3: about 120 nm more than 3.0 cm 3: more than about 300 nm In addition, to determine the growth state of the monomolecular film, the following procedures were followed: (1) Continuous evaporation was carried out in a vacuum metallization device, a polysilazane solution

  to form on the substrate a film of 300 nm.

  (2) A polysilazane solution was evaporated in a vacuum metallization device and when a 150 nm film was first formed on the substrate, evaporation was stopped and then evaporated again the solution (keeping it under vacuum) to form another film 150 nm thick; other

  said, a film of 300 nm in total thickness was formed.

  (3) A polysilazane solution was evaporated in a vacuum metallization device, then a nm film was first formed on the substrate. Evaporation was stopped, then the mixture was evaporated again. solution (keeping it under vacuum) to form a film 150 nm thick; in other words, a

  350 nm film in total was formed.

  (4) A polysilazane solution was evaporated in a vapor phase metallization device, and a film of a thickness of about 300 nm was formed on the substrate, and the evaporation was stopped. substrate on which the monomolecular film was formed, was again placed in the vacuum metallization device to again evaporate the

polysilazane solution.

  As a result, no abrasion defects were observed in cases (1) and (2), whereas a defect for nm in excess of 300 nm was observed in the case (3). , it was not detected additional growth of

  the thickness of the film after re-evaporation in (4).

  In the monomolecular polysilazane film, since silanol groups, formed by hydrolysis of the silazane coupling, are very active, the adhesion is remarkably increased in this way and when the surface of the substrate is activated by heating, the polysilazane adheres In addition, as is apparent from the results of the previous tests, the amorphous monomolecular film having a thickness of a single polysilazane molecule can be formed up to 300 nm by evaporation of the polysilazane solution in the metallization device. under vacuum Then we found that the part

  in excess of 300 nm can be easily removed.

  When the substrate was immersed, together with the deposited amorphous polysilazane monomolecular film, in a m-xylene hexafluoride solution, a portion of the monomolecular film in excess of about 300 nm could be removed, to obtain the monomolecular film. The above-mentioned amorphous film having a thickness corresponding to the length of a molecule. Also, a thin amorphous monomolecular film, corresponding to the length of a single molecule, has been formed on the substrate with great

  precision and without the use of Freon 113.

Examples 1-56:

  In Examples 1 to 14, poly (methyl methacrylate) (PMMA) plastic lenses were used as substrates; in Examples 15 to 28, diethylene glycol bis (allyl carbonate) plastic lenses (CR-39) were used as substrates; in Examples 29-42, glass lenses were used as substrates; and in Examples 43 to 56, glass lenses treated to be provided with an antireflection film were used as substrates. Deposition was performed in the same manner as in Example A, while changing the volume of the film. polysilazane solution and the deposition time In the case where one exceeds 300 nm of film thickness, one can easily remove the excess

  thick with meta-xylene hexafluoride.

  In each example, the contact angle was measured with a contact angle measuring device, while the vertex of the convex surface of the lens was maintained as horizontally as possible (3 was the acceptable range) and the surface plane was also

  maintained horizontally (3 was the acceptable range).

  The results are presented below (There was + 2 of aberration at the time of measurement with the contact angle measuring device The maximum value of the measurement is presented in the following tables) lSubstrate: lens in PMMAl plastic Poly volume Silazane Angle duration (cm 3) Contact metallization (seconds) Example 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 0.8 90 111.8 Example 7 0.9 90 112.7 Example 8 2.0 90 114.0 Example 9 3.0 90 114 Example 10 4.0 90 114.0 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 90 114.0 lSubstrate: Lens made of CR-39 plastic with anti-reflective film Poly volume Silazane Angle time (cm 3) Contact metallization (seconds) Example 15 0.1 15 103.0 Example 16 0.3 30 104.0 Example 17 0.5 60 106.4 Example 18 0.6 90 110.0 Example 19 0.7 90 112.2 Example 20 0.8 90 112, Example 21 0.9 90 113.2 Example 22 2.0 90 114.0 Example 23 3.0 90 114.0 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 lSubstrate: glass plate Poly volume Silazane Angle time (cm 3) contact metallization (seconds) Example 29 0.1 EXAMPLE 30 0.3 30 107.6 Example 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 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 lSubstrate: Glass lens with antireflection film As is clearly indicated by the contact angles of the various Examples, amorphous monomolecular films of polysilazane, which have been formed on

  substrates, have been confirmed to have excellent hydro-

  phobicité. The amorphous monomolecular film having a thickness of more than 0.1 nm could be obtained by selecting between the volume of polysilazane and the metallization time, and the contact angle became greater than 102.0, which

  confirmed that it exhibited hydrophobicity.

  The glass plates of the above Examples were used to construct aquariums, which were polyurethane volume. Silazane Angle Time (cm 3) contact metallization (seconds) Example 43 0.1 15 110.0 Example 44 0, Example 45 0.60 114.0 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 Example 52 4.0 90 114.0 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 Then filled with water to perform foam development experiments Foam never developed during the first 60 days, then a slight degree of foam development was observed 90 days later As the hydrophobicity was confirmed as described above, the demisting effect of the glass plates was tested simultaneously It was also confirmed that

  the glass plates had defogging effects.

  In each example, fingerprints, greases, and dust were extremely easily wiped away, demonstrating that the films

  exhibited excellent oleophobicity.

  In the various examples, wear resistance tests were carried out on the films under the pressure of 29.4 N (3 kg). Each film could withstand this pressure up to 10,000 times. On the basis of this discovery , it has been confirmed that the films of the present invention have a durability and resistance to

wear that are excellent.

  On the other hand, in the plastic lenses, the glass plates, the glass lenses of the above Examples as substrates, a Vickers hardness 8 was obtained as a result of the measurement with a Vickers hardness tester. , the hardness is equal to that of sapphire, and, consequently, an excellent

  wear resistance, has also been confirmed.

  Now, other Examples are given in the following: Ceramics or ceramic forms have been used as a substrate As mentioned above, the amorphous monomolecular film of polysilazane has been formed, with a film thickness lying in the range ranging from 0.1 nm to 300 nm As a result, as mentioned above, it was confirmed that the hydrophobicity and the oleophobicity could be obtained and that also a Vickers hardness 8, that is, a hardness equal to that of sapphire has been obtained, and that it has thus been possible to improve the wear resistance. In particular, in the case of the use of the ceramic form, the invention provides optimum results for the evacuation of In addition, in both cases, since the polysilazane has an electrical insulating property, it can be used for electrical insulators. Porcelain and earthenware for works of art, dishes, toilet bowls, tiles, insulators, were used as a substrate As mentioned above, the amorphous monomolecular film of polysilazane was formed with a thickness of As a result, in the same way as above, it was confirmed that the hydrophobicity and theophobicity could be obtained and that also a Vickers hardness was obtained in the range of 0.1 = n to 300 nm. 8, in other words, a hardness equal to that of sapphire, could be obtained, and that it was thus possible to improve the wear resistance Moreover, since the polysilazane has an electrical insulation property,

  it is usable for electrical insulators.

  Various metals have been used as a substrate.

  As mentioned above, the amorphous polysilazane monomolecular film was formed with a film thickness in the range of 0.1 nm to 300 nm. As a result, in the same manner as above, it was confirmed that the hydrophobicity and the oleophobicity could be obtained and that also a hardness Vickers 8, in other words, a hardness equal to that of sapphire, could be obtained, and that it was thus possible to improve the resistance to In addition, since the polysilazane has an electrical insulating property, it is useful for electrical insulators, for example, for coating materials for conducting wires. Coated metals for all kinds of transport machinery including automobiles and the like, machines for civil and similar constructions or

  pieces of plastic material were used as a substrate.

  As mentioned above, the amorphous polysilazane monomolecular film was formed on the coated substrate with a film thickness in the range from

  0.1 nm to 300 nm As a result, in the same way as above

  above, it has been confirmed that the hydrophobicity and the oleophobicity could be obtained and that sufficient hardness could also be obtained and that it was thus possible to improve the wear resistance. In particular, in the case of the use of the substrate in the sea, it was confirmed that it could prevent the shells from adhering,

  for example, to a boat hull, thanks to the hydrophobicity.

  Plastics were used as a substrate As mentioned above, the amorphous monomolecular film of polysilazane was formed with a thickness of

  film in the range of 0.1 nm to 300 nm.

  As a result, in the same manner as above, it was confirmed that the hydrophobicity and the oleophobicity could be obtained and that also a Vickers hardness 8, that is, a hardness equal to that of sapphire, could be obtained. be obtained, and

  that it was thus possible to improve the wear resistance.

  In addition, leather (including furs), wood (for construction, furniture, handicrafts, tableware, fittings for Buddhist altars, domestic Buddhist altars), tombstones, textile materials In animal fibers, plant fibers, chemical fibers, were used as the substrate. As mentioned above, the amorphous monomolecular film of polysilazane was formed with a film thickness ranging from 0.1 nm to 300 nm. result, in the same way as above, it has been confirmed that hydrophobicity, oleophobicity and

  wear resistance could be obtained in all cases.

  According to the present invention, the use of a cured film-forming agent selected from a polysilazane or a

  polysiloxazane, hardening cold, gives the film a hydro-

  phobicity and oleophobicity Due to the fact that the film is a monomolecular film and is thin, it can prevent the appearance of coherence even if the film is used on the anti-reflective film of a plastic lens or In addition, the monomolecular film is amorphous and has fewer defects and exhibits excellent hardness, durability and wear resistance. By forming a monomolecular film of an agent

  cured film former selected from a polysilazane or a poly-

  siloxazane, cold hardening, on a substrate, by the vacuum deposition technique, it is possible to eliminate, under the effect of vacuum, the water of crystallization, which leads to the easy formation, in a short period of time, amorphous monomolecular film, which is superior in hardness, durability and wear resistance and has fewer defects. Thus, its production efficiency can be improved by forming a monomolecular film of an agent. cured ionogen selected from polysilazane or polysiloxazane, cold hardening, on a substrate, by the

  vacuum deposition technique, as described below.

  above, the substrate is heated at the time of deposition so that the surface of the substrate is activated. Accordingly, the amorphous monomolecular film, having a thickness corresponding to the length of a single molecule, can be strongly adhered to the substrate. a portion of the amorphous monomolecular film can be easily removed from the substrate in the case where the thickness exceeds about 300 nm. It can be removed with a conventional solvent such as meta-xylene hexafluoride and the use of Freon 113 does not occur. It is not necessary As described above in connection with the prior art, a large amount of Freon 113 must be used to eliminate the

  unnecessary part of the film of the prior art.

  The use of Freon 113 can contribute to the destruction of the atmosphere's ozone layer. In the present invention, Freon 113 is not required as a solvent, and other conventional solvents such as hexafluoride m-xylene, which is not subject to the rules concerning Freon, can be used to eliminate the excess film thickness. Therefore, with the present invention, it is possible to avoid environmental pollution, including the destruction of the ozone layer.

Claims (6)

  A stain-resistant material formed on a substrate, characterized in that it comprises an amorphous monomolecular film, consisting of a cured film-forming agent selected from polysilazane or polysiloxazane, cold hardening.   Stain-resistant material according to Claim 1, characterized in that the substrate is selected from glass, glass lenses, mirrors, plastics, plastic lenses, metals, ceramics, porcelain, earthenware, leather, wood, stone, textiles, coated metals, coated plastics, coated woods, hard-coated glass, hard-coated plastics, hard-coated metals and ceramics hard-coated.   Stain-resistant material according to Claim 1 or 2, characterized in that the thickness of the amorphous monomolecular film is chosen from   the range from 0.1 nm to 300 nm.   Process for producing a stain-resistant substrate, characterized in that it comprises vacuum evaporation of a solution of a cured film-forming agent selected from a cold hardening polysilazane or polysiloxazane, and deposition, on a substrate, of a task-resistant amorphous monomolecular film constituted by this agent.   Manufacturing method according to claim 4, characterized in that the substrate is selected from glass, glass lenses, mirrors, plastics, plastic lenses, metals, ceramics, porcelain, faience , leather, wood, stone, textiles, coated metals, coated plastics, coated woods, hard-coated glass, hard-coated plastics,   hard-coated metals and hard-coated ceramic.   6. Manufacturing process according to claim 4 or 5, characterized in that the solution of a hardened fuming agent is prepared by dilution of the f ilmogene agent hardened by a fluorinated solvent.   7 Manufacturing process according to one of   Claims 4 to 6, characterized in that the thickness   amorphous monomolecular film is chosen in the range ranging from 0.1 nn to 300 nm.