DE4112632A1 - A DIRT REPELLENT SUBSTANCE AND THE METHOD OF MAKING IT - Google Patents

Description

The present invention relates to a dirt-repellent Substance, the surfaces a dirt-repellent property gives and has a low coefficient of friction, the upper surface also gives water and oil repellent properties that let the light through, reflect or even extinguish, such as Glass (for construction purposes, shop windows, furniture, automobiles, electric vehicles, aircraft, ships, wristband, wall, Longcase and tower clocks, lighting devices, housings, ver various instruments, camera covers, water basins and the like ches); Plastic (for construction purposes, automobiles, bicycles the, SRT covers, writing paper, household products, etc.); Glass lenses and lenses (for cameras, video cameras meras, binoculars, riflescope for rifles, surveying instru elements and the like) plastic lenses (for glasses and similar ches) Lenses and lenses made of glass or plastic, the upper surfaces are provided with a non-reflective film (for Glasses, etc.); Mirroring (for use in the home, in automobiles, for construction purposes and the like); Tubes for pictorial Representations (Braun tube for television sets, Braun tube for CRT, LCD, TFT, FL, cathode ray tube, etc.); other ceramics and ceramic model (for exhaust gases from automobiles and kitchens derive thinnest and the like); Porcelain (art objects, table dishes, toilets, tiles, insulating devices, etc.); all Types of metal, leather, etc., wood and wood with a Cover are provided (for construction purposes, furniture, crafts objects, dishes, Buddhist altar installations, bud dhist household altars, etc.); Rock (for garden decoration, grave paintings, etc.); Textiles made from animal, plant and plastic fibers exist, coated metal, plastics (for Ships, automobiles, motorcycles, bicycles, civilian machines construction purposes, agricultural machinery, airplanes, Parts of missiles, etc.); in addition, the present refers to term invention on a method, this substance mentioned above  to manufacture.

Non-reflective films are commonly used e.g. B. on the waiter surface of lenses and lenses made of plastic and glass carried. Such a non-reflective film is therefore required a special treatment because fingerprints, grease, dust and similar too easily deposited on such a surface will. Once deposited on the surface, you can they cannot be easily wiped away because of the inferior water and oil repellent properties of the film. It would be that half the use, the film with a dirt-repellent property shaft.

It is known to have a dirt-repellent property th when on the surface of a substrate such as Metal or the like a film of polytetrafluoroethylene or Silicone oil is formed. Still, the film can be made from polytetrafluor ethylene or silicone oil into an even thinner film be changed. For example, if the polytetrafluoroethy lenfilm on the non-reflective film on a lens or a lens made of plastic or glass a coherence between the polytetrafluoroethylene film and the non-reflective coating of the lens or lens the thickness of the polytetrafluoroethylene film. That through the two films let light color or it may no light penetrate through the two films. Because of this, can such a film on such a lens or such Lens not to be used. If the on the non-reflec coating of a lens to be formed a thin film Film such as a monomolecular film (i.e., the thickness of this film is the length of a single molecule) coherence is prevented.

The cured, film-forming active ingredient, which be from the above wrote cold-curing polysilazane or polysiloxazane is a curing, organic silicone compound that  can be represented by the following generic formula:

wherein R ¹ and R ^{2 are} each a hydrogen atom or a monoval ter organic radical, which are identical or different from one another, such as. B., an alkyl radical, an alkenyl radical, an aryl radical, a cycloalkyl radical, or a halogenated hydrocarbon radical which are identical to one another or the radicals or mutually different radicals, such as a perfluoroalkyl radical, in which the hydrogen atoms bonded to hydrocarbon atoms in part or be completely replaced by halogen atoms, a substituted hydrocarbon residue which contains, for example, a functional residue such as an alkoxy residue, a hydrolyzable residue and, in addition, an epoxy residue, e.g. B. NH ² , CH ₂ , CH ₂ residue, where a, b each represent a positive number of = 0-1.5 and m 1, n 0.

As the curing organic silicone ver bond, those are used, e.g. B. the following structure own unit:

CH₃Si (NH) _1.5
CH₃Si (OCH₃) NH
R³O
CH₂ = C- (CH₂CH₂Si (NH) _1.5 ),

where R³ represents a hydrogen atom or a methyl radical, 1 = 1-3.

As a method to make such a monomolecular film on a The Langmuir process is known to form a substrate consists of a monomolecular film on a water surface form the substrate in contact with the water surface bring to the monomolecular film from the water surface surface to transfer to the substrate. One by the Langmuir Processed monomolecular film can, as is well known, either  that as a crystal-like or amorphous, monomolecular film be classified. If the temperature of an aqueous phase is below the melting point of the monomolecular film two-dimensional, separated crystallites immediately after of the expansion formed on the substrate, and then when under Use compression to bring them together morphologically a uniform, crystalline, monomolecular film seem to form; when the temperature of the aqueous phase is higher than the melting point of the monomolecular film, will be cupid phe domains immediately after expansion of the film on the substrate formed, and then when and the use of compression brought together, they seem a uniform, amorphous, to form monomolecular film. The cooling and formation of the amorphous, monomolecular film can be a monomolecular film with fewer defects than those in the crystalline, monomolecular films can be found.

Not a monomolecular film on the aforementioned reflective film of a lens or lens made of art To form fabric or glass, the surface of the substrate is about moistened for three minutes with a solution made by the Dilution of 3%, by weight one from a cold-curing Polysilazane or polysiloxazane selected, hardened, film-forming active ingredient with 97%, fleon 113 by weight prep is riert. Since the thickness control over the manufacture of the monmolecular film is difficult to handle, the film first in a more than necessary thickness on the substrate applied. The excessive thickness is subsequently removed. If a monomolecular film by the above-mentioned method is produced, foreign materials can come into contact with the Surface of the film are coming. Therefore, the unnecessary Layers of this film removed with gaseous fleon 113. Then the film is dried for about an hour. After this Processes can be washed off the foreign matter.

It is still very difficult to keep the temperature at the familiar Check the process so that when producing a monomolecular film the film ever made completely  becomes amorphous. The temperature cannot with this method either be increased because this is an inferior adhesion of the film cause, as well as its durability and Keep wearability low and also a low product activity in the production of the film. In addition, also because the known method Devices with a large scale and a complex process process is control over the steps of the process rens difficult. In addition, the excess is used in this process part of the film was removed with gaseous fleon 113. Yet control of the Fleon 113 material is difficult because of the huge amount that needs to be used. Additionally generated the enormous amount of fleon 113 that is used, fleon gas that part of the current problem of the destruction of the Ozone layer in the atmosphere.

Based on the above knowledge, the current he finder the intention of an improved dirt-repellent substance and an improved method of making them put.

To achieve this object, the invention provides that the dirt-repellent substance a formed on a substrate, amorphous, monomolecular film made from a cold-hardened material tendency Polysilazan or Polysiloxazan selected, hardened film-forming active ingredient.

As a process for the production of the dirt-repellent substance The invention provides that a solution to a cold out curing polysilasan or polysiloxasan selected, cured teter, film-forming agent is vacuum evaporated and that on an amorphous monomolecular film from a substrate cold-curing polysilazane or polysiloxazane selected hardened, film-forming active ingredient is formed.

The above solution is made by diluting one cold-curing polysilizane or polysiloxazane selected hardened, film-forming active ingredient with a from a fluo  prepared compound prepared solvent.

The following materials can be used as a substrate, which carries the amorphous, monomolecular film: glass, lenses and Lenses made of glass, mirrors, plastics, lenses and lenses Plastic, metal, ceramic, porcelain, leather, wooden, stone, Textiles, coated metals, coated plastic, be laminated wood or hard-coated glass, hard-coated Plastic, hard-coated metals, hard-coated ceramics and similar.

It is difficult to determine the film thickness of the amorphous, monomolecular Check film if it is less than 0.1 nm; it it is easy to remove the excessive thickness when it is 300 nm exceeds. If they, e.g. B., exceeds 120 nm, becomes coherence between the amorphous, monomolecular film and the non-reflective tive film of a lens take place when this as a substrate is used. The film thickness is therefore within the realm width chosen from 1 nm to 120 nm. The film thickness between the Range 10 nm to 20 nm selected if the amorphous, monomole kular film in a plastic or glass lens or lens is used.

Unlike in the examples above, plastics can or metals that have been coated with a film are used as a substrate on which the amorphous, monomole kular film is applied.

According to the present invention, the film can be water and oil repellent Send properties by using a cold hard one cured polysilazane or polysiloxazane th, film-forming active ingredient are awarded to the film.

In addition, the film formed is thin because it is monomolecular is. The film can therefore also be subject to the occurrence of coherence tie, even if this is on the non-reflective coating a plastic or glass lens or lens is used; furthermore, the monomolecular film cannot  be crystallized out and has fewer defects that too improved strength and durability as well as a lower wear resistance.

On the other hand, through the formation of a monomolecule ren film of a cold-curing polysilazane or polysiloxa existing hardened, film-forming active ingredient on the Substrate using a Kritallisa vacuum evaporation process tion water in a vacuum removed from the process, leading to the rapid Formation of an amorphous, monomolecular film that leads to a excellent hardness, durability and low wear owns, but also has fewer defects.

In addition, through the formation of an amorphous, monomolecular Films made from a cold-curing polysilazane or polysi loxazan selected, cured, film-forming active ingredient on a substrate using the vacuum evaporation method the formation of an amorphous, monomolecular film with a thickness of the length of a single molecule possible that is the substrate firmly adheres because the hardened, film-forming active ingredient is high active and the substrate at the time of the vacuum evaporation process has been heated. In addition, since the amorphous, monomolecular lare film can be removed easily. If the thickness of the film is more than 300 nm, the use of Fleon 113 is not more needed.

Incarnations

The present invention is exemplified below in embodiments:
Anhydrous gaseous ammonia was introduced into a solution of 50 parts by weight of nC ₈ F ₁₇ , CH ₂ , CH SiOl ₃ and 750 parts of trichloromonoflouromethane by weight to raise the temperature of the solution to bring trichloromonofluoromethane into the reflux. After 15.5 parts of gaseous ammonia by weight was introduced in this way, the supply of ammonia was stopped. The solution was then stirred under heat for four hours, during which gaseous nitrogen was introduced by reflux. Deposited ammonium fluoride was separated by filtration and tricloromonoflouromethane was removed from the filtrate by evaporation to obtain a white solid powder which formed a cured film-forming agent consisting of 39.8 parts by weight of polysilasane. An appropriate amount of a polysilasane solution, to a 3% by weight concentration, using trichloromonofluoromethane as the solvent of a fluorinated compound (excluded from the Fleon regulations) in a tungsten (molybdenum and tantalum could be used instead), heat-resistant vessel was prepared. The degree of vacuum within the vacuum evaporator was set to approximately 6 · 10 ^-5 mb by means of a driven vacuum pump (the precise degree can be selected within the scale 6 · 10 ^-4 to 6 · 10 ^-5 ). The heat resistant vessel was then energized to allow the polysilazane solution to evaporate. This resulted in the deposition of the monomolecular polysalazane film on an unheated (ie at normal temperature) substrate. Since the heat-resistant vessel was heated to approx. 160 ° C by means of electrical voltage, the atmosphere inside the vacuum evaporator was also heated - together with the resulting heating of the substrate - even if heat was not directly added to it.

By evaporation of a required amount of one Polysilazane solution could produce an amorphous monomolecular film where the size of the monomolecular crystallites increases significantly. With subsequent cooling and crystal removal lization of the amorphous, monomolecular film made a monomolecular film with fewer defects will. By checking the voltage of the electric current as well as its application time on the heat-resistant vessel the size of the monomolecular crystallite from 0.1 nm to 300 nm be increased; the thickness of the monomolecular polysilasan film could be controlled on the substrate, as in the relationship between the volume of the polysilazane solution and that produced Film thickness of the amorphous monomolecular film can be shown:

In addition, the following procedures were used to control the To test the state of growth of the monomolecular film:

• 1) A polysilazane solution was in a vacuum evaporator continuously evaporated to a 300 nm film on the sub to form strat.
• 2) A polysilazane solution was in a vacuum evaporator evaporated and, when a 150 nm film was first created, the evaporation was interrupted. After that, again evaporates in a vacuum to a second 150 nm film, d. i.e., to form a 300 nm film as a whole.
• 3) A polysilazane solution was in a vacuum evaporator evaporates to first form a 200 nm film on the substrate form. Then the evaporation was stopped. After that was evaporated again in a vacuum to make another 150- nm film, i.e. i.e., to form a 350 nm film as a whole.
• 4) A polysilazane solution was in a vacuum evaporator evaporated to form a film with one on the substrate manufacture thickness of less than 300 nm; the Evaporation was then stopped. After that, the Vacuum evaporator substrate again the polysilazane solution evaporation process exposed.
• The result was that in cases (1) and (2) there was no abrasion effect could be observed during a 50 nm defect for the films whose thickness was more than 300 nm was put. In addition, the continued Evaporation in case (4) no further growth in film thickness be perceived.

Because silanol residues, which are produced by hydrolysis of the silazane compound adhesion, is highly active remarkably increased and the surface of the substrate through Heating also activated, it can be assumed that in the Polysilazane film that adheres to the substrate. About that addition, as from the results of the previous test close, it can be assumed that the amorphous, monomole kular film, the thickness of which is the length of a single polysilazane corresponds to the molecule, by means of the evaporation of the polysilazane solution solution in a vacuum evaporator up to a thickness of 300 nm is formed. It was found that the further evaporation of the silazane solution to a loss of those exceeding 300 nm Film thickness led.

After the substrate together with the amorphous, monomolecular polysilazane film in an m-xylene-hexafluoride solution solution was moistened, the part of the monomolecular Film that was thicker than 300 nm should be stripped off desired amorphous, monomolecular film with a thickness of To get the length of a single molecule. A thin, amorphous, monomolecular film, the thickness of which is the length of a single Could match without using Fleon 113 and without forming a gap on the substrate will.

Plastic lenses were made from Embodiments 1 through 14 Polymethyl methacrylate (PMMA) used as substrates; in the Embodiments 15 through 28 were made up of diethylene glycol lenses Allyl carbonate (CR-39) used as substrates; in the body 29 to 42 glass lenses were used as substrates and in Embodiments 43 to 56 glass lenses were used with had been provided with a non-reflective coating.

When the metal evaporation was carried out, the volume a solution of cold-curing polysilazane or polysi loxazan selected, cured, film-forming active ingredient and the duration of metal evaporation varies. In cases of over  the film thickness could exceed 300 nm liquid film easily removed using metaxylene hexafluoride the.

In each embodiment, the contact angle was one contact angle meter measured while the apex of the convex surface from the lens as well as the flat surface as horizontally as possible was held (+ or -30 was the maximum allowed rejection area). The results are shown below (+ or -2 ° Deviation arises when dimensioning with the contact angle meter. The maximum value of the measurement is shown in the following table shown).

Substrate: Polymethylacrylate plastic lens

Substrate: a CR-39 plastic lens with a non-reflective film

Substrate: glass plate

Substrate: glass lens with a non-reflective film

As can be seen in the contact angles of the individual embodiments has been shown to confirm that the amorphous, monomole kular films made from a cold-curing polysilasan or polysi loxasan selected, hardened, film-forming active ingredient, which were formed on the substrates, an excellent one have water-repellent properties.

The amorphous, monomolecular film with a thickness that is larger than 0.1 nm, the choice between the Volume of cold-curing polysilazane or polysiloxazane selected, cured, film-forming active ingredient and Evaporation time can be achieved, and the contact angle reached more than 102.0 °. It has been confirmed to be water repellent Had properties.

In contrast, the glass plates of the above embodiments used to construct aquariums, which are then filled with water were filled out to experiment on moss development perform. Moss growth never occurred 60 days ago and only after 90 days was there a slight moss growth the glass plates. Just like the water-repellent Property has been experimentally confirmed as described above the anti-fog effect of the coated glass plates tested at the same time. This also confirmed the anti-fog Effect of the treated glass plates.

Fingerprints, grease and dust could be found on every embodiment to be wiped extremely easily, which demonstrated that the films possessed excellent oil-repellent properties.

The films Ver subjected to wear resistance tests at a pressure of 3 kg. Each film could withstand such pressure up to 10,000 times what the excellent durability and wear resistance of the Movies of the current invention confirmed.  

In addition, the plastic lenses, the glass plates and the glass lenses as substrates of the above-described body a Vickers resistance of 8 after the Vickers Strength measuring device can be determined: That is. a firmness degree that resembles that of sapphire, which is why one drawn wear resistance means.

Comments on the other incarnations

Ceramic or ceramic molds have also been used as a substrate. As mentioned above, they became the amorphous, monomolecular Film made from a cold-curing polysilazane or polysiloxazane selected, hardened, film-forming active ingredient in one Thickness between 0.1 nm and 120 nm formed. The result of how already noted above, it was confirmed that water and oil-repellent properties can be obtained and also a Vickers strength grade of 8, d, i, a sapphire like Strength achieved so as to improve the wear resistance ser. Especially when using ceramic molds is a such film is optimally suited for exhaust gas discharge for automobiles bile as well as for deriving kitchen fumes. Furthermore, the Film used as electrical insulation in both cases because silicon fluoride has electrical insulating properties owns.

Porcelain for art objects, dishes, toilets and ceramic Insulators have also been used as substrates. As noted above the amorphous, monomolecular film could be made from one cold-curing polysilazane or polysiloxazane selected hardened, film-forming active ingredient on them with a thickness from 0.1 nm to 3000 nm are formed. After that, as well above, confirm that water and oil repellent properties were present, as was a Vickers strength grade of 8 (the same as with a sapphire) and thus became a verbes achieved wear resistance. In addition, the prepared objects can be used as insulators because Silicon fluoride has insulating properties.  

Various metals have also been used as substrates. How As mentioned above, the amorphous, monomolecular film was made from one selected from cold-curing polysilazane or polysiloxagane, cured, film-forming active ingredient on them with a thickness from 0.1 nm to 300 nm. As confirmed above, that water and oil repellent properties were present and that a Vickers strength level of 8 was also reached, i.e. a grade similar to that of a sapphire, and so one could improved wear resistance can be achieved. Furthermore, can the film on such prepared objects as electrical Insulating material can be used, e.g. B. as a coating for electrical wires because silicon fluoride is electrically insulating Possesses properties.

Coated metals for all types of transport vehicles, including automobiles and the like, or plastic parts were also used as substrates. As noted above, could the amorphous, monomolecular film made from a cold-curing Polysilazane or polysiloxazane selected, hardened, film-forming active ingredient on the coating membranes of the Metals with a thickness of 0.1 nm to 300 nm are formed. As above, it was subsequently confirmed that water and oil repellent properties were present and that a Vickers Strength grade of 8 could be achieved, i. i.e., a festive degree of similarity to that of a sapphire; and thus could improved wear resistance can be achieved.

In addition, leather (including skins), woods (for Construction purposes, furniture, handicrafts, dishes, Buddhist altar fittings, Buddhist house altars), grave male, and textiles made from animal, plant and synthetic fibers as Substrates used. As noted above, the amorphous, mono molecular film made from a cold curing polysilazane or Polysiloxazane selected, cured, film-forming Active ingredient on them with a thickness of 0.1 nm to 300 nm be det. It could then be confirmed that water and oil-repellent properties were present and in all cases  a higher degree of wear resistance could be achieved.

According to the present invention, the use provides one cold-curing polysilazane or polysoloxazane selected hardened, film-forming active ingredient the film with water and oil-repellent properties. Because the film as a monomolecular Film is thin, it can prevent coherence from occurring, even if the film is on a non-reflective film one Plastic or glass lens is applied. Beyond that the monomolecular film is amorphous and therefore has fewer Defects, and the excellent hardness, durability and Wear resistance can be improved in this way.

By making a monomolecular film from a cold curing Polysilazane or polysiloxazane selected, hardened, film-forming active ingredient on a substrate by means of the vacuum ver vaporization process is applied, water of crystallization can be removed in vacuum, resulting in light and fast Formation of the amorphous monomolecular film, which is what hardness, Concerns durability and wear resistance, is superior and has fewer defects. Therefore the production yield of the Process improved. By making a monomolecular film from one selected from cold-curing polysilazane or polysiloxazane, cured, film-forming agent on a substrate by means of of a vacuum evaporation process described above, the substrate is z. Z. the evaporation warmed and the surface thus activated. After that, a first layer of with a Thickness of a single molecular length amorphous, monomolecular laren film connect to the substrate, so that the second Layer and those lying on this second layer Layers can be easily removed from the first layer. The second layer and the other layers lying on it can with a solution such as a meta-xylene hexafluoride solution be removed without the use of Fleon 113. Accordingly, pollution, including destruction prevent the ozone layer.

Claims (7)

1. dirt-repellent substance, characterized in that it is an amorphous, monomolecular film formed on a substrate from a selected from a cold-curing polysilazane or polysiloxazane, cured film-forming active substance. 2. The dirt-repellent substance according to claim 1 characterized in that the substrate made of glass, Glaslin sen, plastic, plastic lenses, metals, ceramics, Porcelain, leather, wood, stone, textiles, coated Metal, coated plastic, coated wood, hard-coated glass, hard-coated plastic, hard coated metal or hard-coated ceramic. 3. The dirt-repellent substance according to claim 1 or 2, characterized in that the thickness of the amorphous, monomolecular film made from a cold-curing Polysilazane or polysiloxazane selected, hardened, film-forming active ingredient is between 0.1 nm and 300 nm. 4. Process for producing a dirt-repellent substance characterized in that a solution of one of a cold-curing polysilazane or polysiloxazane th, cured film-forming active ingredient is evaporated under vacuum and that an amorphous, monomolecular on a substrate rer film from a solution of a from a cold-curing Polysilazane or polysiloxazane selected, hardened, film-forming active ingredient is formed. 5. The method according to claim 4, characterized in that as substrate glass, a glass lens, a mirror, plastic, a plastic lens, metals, ceramics, porcelain, leather, Wood, stone, textiles, coated metal, coated plastic, coated woods, hard-coated Glass, hard-coated metal, or hard-coated Ceramic is used.   6. The method according to claim 5, characterized in that the solution is one from a cold-curing polysilazane or polysiloxazane selected, cured, film the active ingredient with a solvent from a fluorinated Compound is diluted. 7. The method according to any one of claims 4 to 6, characterized characterized in that the amorphous, monomolecular film in a thickness between 0.1 nm to 300 nm is generated.