DE2310046A1 - COATING FILM - Google Patents

Description

PATENT LAWYERS

on. O. DITTMANN

K. L. SCHIFF im. A. v. FUNER Dipl. Ing. P. STREIIL, UH. U. SCHCBKL-IIOPF you ·!., inc. D. KllHINGIIAUS

DA - I0.392 NIPPON HYDRON CO. LTD.

NIPPON SHEET GLASS CO. LTD,

D-E MVNCHKN OO MARIAHILFPLATZ 2 & 3

POSTADRERSK D-8 MÜNCHEN ¹ O5 POSTBOX 1) 5 Ol 150

TELEPHONE (O811) 4ö 83 54 TELBOH. AUHOMAHCPAT MUNICH

TELEX 5-2! » ΠΟΠ AURO Ti

February 28, 1973 Dr.SL/ka

Coating film

(Priority: February 28, 1972, Japan, No. 1973o / 1972

Feb 28, 1972, Japan, # 19731/1972

Apr 11, 1972, Japan, # 35681/1972

26-.Junil972, Japan, No. 63195/1972)

The invention relates to a protective surface coating for molded parts or moldings that consist of synthetic resins at least on the surface, as well as a Process for making such coating films. So concerns the invention specifically relates to a protective surface coating for an object or body having at least one surface which consists of a synthetic resin, in particular:

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a hydrophilic polymer having numerous desirable properties, for example im With regard to the properties, there must be no fogging (non-fogging property) and the surface hardness of this molded body is increased without the desirable properties of the molded body inherent properties.

In recent times, the use of transparent plastics as window glass for buildings, automobiles, railroad cars or airplanes or as doors has been sought, and plastic windows or doors have already been put into practical use in some fields of application. However, plastic windows or plastic doors have the disadvantage of being easily scratched due to their low surface hardness. Attempts have also been made to apply a transparent hydrophilic polymer coating layer to the surface of an inorganic window glass for buildings, automobiles, railroad cars or airplanes, spectacle glasses, protective goggles or optical lenses in order to make them opaque by absorbing water droplets deposited on their surface through the coating layer . However, coating films made of hydrophilic polymers are easy to scratch even in the dried state, like ordinary plastic moldings, because they have low surface hardness. This is even more true when it is wet because a hydrophilic polymer film swells by absorbing water.

Eb is known, the surface hardness of plastic substrates to improve by adding an inorganic protective coating made of a metal oxide, nitride, fluoride or -silicide or another inorganic solid is applied. However, even if an uninterrupted one Film made of such an inorganic substance has sufficient initial surface hardness, but it is subject to

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the formation of cracks or is otherwise affected due to the internal stresses that are due to the difference in the coefficient of thermal expansion of the coating film and the substrate when it is practically used or the Weathering, boiling temperature, repeated handling and cooling or exposure test. By the cracking or other damage, a reduction in surface hardness is achieved, holes appear in the Film on and eventually the film peels off the substrate.

The problem of internal tension has so far been at least partially by applying a protective coating to a substrate heated to an elevated temperature by heat treatment in vacuum or in air immediately after applying one Protective coating to reduce internal stresses, or by adding one or more additives to one Coating compound dissolved, the difference in the coefficient of thermal expansion of the coating and the substrate was reduced. E3 is difficult, however, through the first described Method of completely eliminating internal tension and, moreover, this method is unsuitable for use for Plastic substrates because these plastic substrates are inadequate Have heat resistance in order to be able to subject them to sufficient heat treatment. The latter The method is difficult to carry out in practice because it is necessary, in each case, to compose a coating to determine.

The previously known protective coating films are completely continuous over the entire surface, so that in use of an opaque coating material, the body coated therewith becomes opaque. If such an opaque Protective coating is applied to an object that is made of

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a glass substrate with a coating layer made of a hydrophilic polymer applied thereon, so loses this object cannot transmit its light and the above-mentioned hydrophilic polymer layer also cannot prevent its haze Have an effect because they are through the continuous and uninterrupted film of the protective coating is completely isolated from the air.

The invention is therefore based on the object of an improved To find protective coating film for an object or molded article, * the at least one of a synthetic Has resin formed surface.

Another object of the invention is to provide a protective coating film for a clear synthetic item To make resin accessible, 'which is essentially no unfavorable Has an influence on the light transmission of the object.

The invention also aims to provide an anti-haze protective coating film for an object which has at least one surface formed from a hydrophilic polymer will.

Another object of the invention is to provide a method for improvement to make the surface hardness of moldings with relatively low surface hardness accessible.

The protective coating films for surfaces of the present invention are intended to also show decreased haze or haze formation.

According to the invention, these objects are achieved by an inorganic a protective coating film, which is from 400 Angstrom units to 5 microns thick,

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and from separate islands of an inorganic solid which each have an area of 7 x Io microns or have less and between those openings remain free in which the surface of the object covered with it to communicate with the air.

The invention also relates to a method for production a protective coating film on a molded body which has at least one surface made of plastic, in which a film of inorganic material consisting of separate islands, 400 angstroms thick up to 5 microns in a vapor deposition process through a vapor deposition mask, which is designed in such a way that the individual islands have an area of at most 7 x 10 square microns each, and openings in which the surface of the molded body is exposed to the air remain free between these islands will.

The invention also relates to a coated molded body, the one coating film made up of separate islands of an inorganic material from 400 Angstroms thick 5 microns with the discrete islands having an area not greater than 7 χ Io square microns. According to a In a preferred embodiment of the invention, the molded body has a coating layer made of a polymer, preferably one hydrophilic polymers, and the coating film from the separate islands is arranged on the polymer layer.

Thus, according to the invention, the surface of an object or molded body made of synthetic resin with low surface hardness is applied an inorganic film of sufficient hardness is applied, consisting of discrete islands between them uniformly distributed openings remain free, which enable the surface of the object to communicate with the air, so that the surface hardness of the item or

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Shaped body is increased without impairing the properties inherent in the body, such as transparency and Hydrophilicity, and without the risk of peeling off the coating film.

The invention will be readily understood from the following description with reference to the accompanying drawings.

In these drawings, Fig. 1 is a graph showing the relationship between the property of freedom from haze and the percentage of the opening area of an inventive protective coating film showing on the surface einer'hydrophilen Kunetstoffkörpers is formed.

Figs. 2 to 4 are illustrations of sections through coated articles illustrating the principle of formation and reduction show a haze.

Fig. 5 is an enlarged section of an article having a protective coating film of the present invention;

Fig. 6 is a top plan view of the above item.

Fig. 7 is a graph showing the change in the amount of light transmitted through a sample of a plate of a hydrophilic Resin which does not have a protective coating film when water vapor is continuously supplied to the sample and then the feed is interrupted.

Fig. 8 is a graph showing the corresponding change in the amount of light transmitted through a sample which comprises a protective coating film of the invention.

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Fig. 9 is an oblique view of a sample with one according to the invention Protective coating, which consists of regularly arranged circular elements, with the anisotropy of abrasion hardness is shown.

Fig. Loa and lob show an example of the pattern formation on a shadow mask used in the practice of the method according to the invention.

Fig. 11 is a photomicrograph of an example of an evaporation mask or shadow mask.

Fig. 12 is a simplified sketch of an apparatus for determining anti-fogging properties, and

13 to 15 show examples of patterns of the masks suitable for forming the protective coating film of the present invention.

Molded articles or molded bodies on which according to the invention A protective coating is applied can be formed from any hydrophilic and hydrophobic polymer. Suitable hydrophobic polymers include, for example

Polycarbonate, poly (methyl methacrylate), polyvinyl chloride, Polystyrene, polypropylene, polyethylene and unsaturated polyester resins. Suitable hydrophilic polymers include two e.g. hydrophilic acrylate and methacrylate polymers, Polyvinyl alcohol, polyvinyl acetal, polyacrylamides, polyvinyl pyrrolidone, Poly (ethylene oxide), poly (ethylene imine), hydroxyethyl cellulose and regenerated cellulose. These materials can themselves represent moldings or can be used as surfaces of moldings made of other plastics, glass, metal / Wood, cement or porcelain and ceramics are available. As a hydrophilic

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Polymers are preferably used water-insoluble, hydrophilic acrylate and methacrylate polymers.

Examples of hydrophilic acrylate and methacrylate polymers are polymers of hydroxy-lower-alkyl-acrylates, hydroxy-lower-alkyl-methacrylates, Hydroxy-lower-alkoxy-lower-alkyl-acrylates and hydroxy-lower-alkoxy-lower-alkyl methacrylates, as of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Diethylene glycol monoacrylate, diethylene glycol monomethacrylate, Triethylene glycol monoacrylate, triethylene glycol monomethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, Dipropylene glycol monoacrylate and dipropylene glycol methacrylate.

The polymer specified above can, if necessary, be crosslinked by copolymerization with 0.05 to 20, preferably 0.1 to 2.5 °, of a crosslinking agent, such as, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diviny1-benzenes and N, N'-methylene -bis-acrylamide.

The above polymer can; if necessary by copolymerization, for example with acrylic acid, methacrylic acid, itaconic acid, fumaric acid or mono-2-hydroxypropyl itaconate be modified.

As polyvinyl alcohol, partial saponification products of polyvinyl acetate, which are different from the product of the complete Saponification. Suitable polyvinyl acetals include polyvinyl formal, polyvinyl acetoacetal and polyvinyl butyral. Suitable polyacrylamides include polymers of acrylamide, methacrylamide, N-methylolacrylamide,

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N-methylol methacrylamide, diacetone acrylamide, diacetone methacrylic ■ araid and similar acrylamide and methacrylamide derivatives.

In the protective coating film of the present invention based on formed on a hydrophilic polymer substrate, the effect of increasing surface hardness and various Advantages such as air permeability, light permeability and the avoidance of the risk of peeling, combined. So has the protective coating film of the present invention applied to an article is formed, which has at least one surface formed from a hydrophilic polymer, a structure, which consist of discrete bzv /. separate dots or stripes or other shaped islands of an inorganic pesticide and there is arranged between these openings or spaces, which the surface of the substrate with the air in Connect. This structure prevents peeling of the protective coating film and deformation of the ^ iIτη « prevented by thermal stress and also allows gas molecules to hit the surface of the object or Achieve Pormkörper from the hydrophilic polymer. The structure, made up of individual particles, should be spaced apart which is smaller than the diameter of the fibers of a cloth that is used to clean the surface or which is smaller than the diameter of grains which have a scratching effect or an abrasive effect. This structure can be achieved by forming an inorganic protective coating film through a sheet of a perforated mask or a combination of different webs of perforated masks on the surface of a porous body which has at least one surface formed from a plastic, wherein an evaporation method is used, such as for example the method of resistance heating, the electron beam method or the atomization method.

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- Io -

In the resistance heating method, the material to be evaporated becomes heated by the Joule heat generated by the application of an inr Intense electric current is generated on a wire or film with a high melting point, and the bond between the protective coating and the substrate are largely due to physical adsorption and van der Waalsohe forces. Because in this case the structural strength is insufficient is high, it is desirable to preheat the substrate prior to vapor deposition or to activate it by ion bombardment, to increase liability.

In the electron beam method, the material is impacted by impact a beam of electrons accelerated to high speed.

With the atomization method, the material is bombarded with cations, caused by glow discharge, low pressure glow discharge in a magnetic field or electric field of high frequency, Low pressure plasma, ion beams or similar physical * sputtering methods were generated.

In the electron beam method and the sputtering method, particles of a metal or metal oxide have a very high energy content (Io to loo eV) compared to particles, which are vaporized with the resistance heating method (approx. 0.2 eV) are shot out of a collecting electrode (target), so that they locally heat the surface of the substrate and create an essentially complete chemical bond enter with the surface.

It will therefore generally, although depending on the melting point and decomposition point of the material used preferred for the resistance heating method a material with a low melting point and for the electron beam or

* or chemical

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23100A6,

Atomization method to process a material with a high melting point. In all cases, however, the temperature should of the substrate must be carefully controlled to prevent thermal degradation of the substrate. A pretty solid one Bonding between the substrate and the protective coating is achieved when the surface of the substrate is subjected to ion bombardment is cleaned. It is believed that this is due to the formation of oxygen bonds on the polymer molecules is.

The protective coating film can not only with the help of the above physical methods mentioned, but also with the help of a chemical method.

A protective overlay film with the desired percentage area of openings or spaces and a desired one Patterns or a desired arrangement of stripes or islands can be formed by applying a mask that of one or more layers of a mask plate with numerous through holes with the desired outline or consists of numerous slots. The outline of the through holes or strips and their location are not critical. The protective coating film can consist of separate islands or strips, which are regular or random are arranged. The area of each stripe or island is preferably 7 x Io square microns or less, more preferably 3 x Io square microns or less, because if it exceeds 3 x Io square microns, that will be transmitted Light is uneven, and there are occasional deviations in the transmitted light, and the coating film becomes brittle. Particularly when bodies made of hydrophilic polymers are used, it is preferred that in view of the anti-fogging property and the hygroscopicity the area 8 χ lo ^ square microns or less. The thickness of the invention

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Coating layer, which consists of numerous separate islands, is preferably 400 angstroms to 5 microns because a film is one

Thickness less than 400 angstroms will not have sufficient effect and because, on the other hand, a film of more than 5 microns thick leads to haze and poor adhesion to it Has substrate.

The shape or outline of each element of the protective coating film may be circular, oval, or stripe, although it is preferred that the short axis ratio be to the long axis in the range between o, l and l, o.

It is preferred that the openings or spaces between the islands or strips are uniformly distributed over the entire surface to be protected. The percentage surface area of the openings can be varied depending on the requirements, although it is usually 5 to 99 ° /> . When using a substrate made of a hydrophilic polymer, a surface area of the openings from 30 to 99 $ is preferred in order to achieve the desired goal of surface protection without the desirable properties of the substrate being impaired. If a hydrophobic polymer substrate is used, a range from 5 # to 70 $ is preferred because in this case the protective coating is applied only for the purpose of surface protection.

The term "percentage area of openings" means the percentage of the area obtained by subtracting the total area of the islands from the area of the substrate covered by the protective coating on the substrate surface. The percentage surface area of the openings is represented, for example, by the following equation (for the case of a two-dimensional zigzag pattern;: S Ho) - (1 - 2 TTr ² / / ~ 3 j.?) _X I ₀₀

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23100A6

in which S is the percentage surface area of the openings, r is the diameter of an island and 1 is the average distance between two neighboring islands.

More detailed tests have shown that when bodies made of hydrophilic polymers are used, the anti-haze properties assume the highest value when the percentage surface area of the openings is in the range from 60 to 99 ″ .

In theoretical terms, it is believed that when the aforesaid protective coating film is applied to the surface of a hydrophilic polymer, the anti-haze properties deteriorate as the total area of the islands increases, in other words, as the percentage area of the openings decreases. On the other hand, as indicated in Fig. 1, it has surprisingly been found, as a result of experiments, that a coated molded article or article having a protective coating film with an area percentage of openings of $ 60 to $ 99 has better anti-haze properties than one Molded body with a coating film with a percentage surface area of the openings of 100 io (a molded body without a protective coating film). This is indicated by the maximum of the curve in FIG. 1. The curve in Fig. 1 is obtained by plotting the anti-haze properties T / T against the percentage area of the openings, which were determined by the method described below on shaped bodies obtained by vapor deposition of silicon oxide through various masks on substrates, a protective coating film having a thickness of 1,000 to 1,500 angstroms was formed thereon. The percentage surface area of the openings is determined by measuring the total area of the islands by photomicrograph, because of the incomplete contact between the surface of the substrate and the mask

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the pattern of the protective film is not always identical to that of the mask used.

The invention is therefore based on a position which is contrary to the usual theory that an uncoated body made of hydrophilic plastic is better with regard to the anti-haze properties than an at least partially coated body. The exact mechanism on which the invention is based is uncertain, but it is believed that the diffusion of the water deposited on the surface into the interior of the hydrophilic plastic body through the
porous protective coating film is delayed, and that by
this delay results in an improvement in the anti-haze properties.

In the practice of the invention, various inorganic substances can be used to form a protective coating film. Oxides, nitrides,
Fluorides and sulfides of various metals are used. That
Material can be applied to a substrate by any suitable method depending on the material used.

Materials that are suitably applied using the resistance heating method include, for example, tin oxide, cadmium oxide, indium oxide, zinc oxide, bismuth oxide, antimony oxide, silicon monoxide, cadmium sulfide, zinc sulfide, magnesium fluoride, beryllium fluoride, calcium fluoride, lithium fluoride,
Sodium fluoride, thulium fluoride, cerium fluoride and cryolite.

Materials that are suitable for application by the electron beam or sputtering method include, for example, thulium oxide, beryllium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, magnesium oxide, zirconium oxide, cerium oxide,
Silicon dioxide, niobium oxide, titanium oxide, tar.tal oxide, lanthanum oxide,

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Hafnium oxide, niobium nitride, boron nitride, aluminum nitride and Silicon nitride.

To form a protective coating film of the present invention, Both clear and opaque materials are used. However, if a see-through protective When a coating film is formed on a transparent substrate, the phenomenon is sometimes observed the clouding due to the scattering of light, the so-called fogging. It is desirable to train one Avoid veils especially in the case of lenses. The veil or haze is due to the scattering of light at the edge or in the center of each element or island of a protective coating film.

Like in Pig. 2, separate elements or islands 2 are connected to the surface of a substrate 1 which has a relatively low surface hardness. Of the rays P impinging on the body, rays Pp and P proceed in a straight line after having passed through the body and come at Q _? and Q. at. This means that they are not scattered and do not give rise to fogging. The rays P, and P, on the other hand, arrive at Q ₁ and Q, respectively, because they are refracted on the surface of the body. This is the reason for the formation of a haze or a veil in the transmitted light radiation. This causes the disadvantage that the view through the body is somewhat obstructed, although the surface hardness of the body is largely improved by applying a protective coating film composed of individual particles which is free from cracking and does not show peeling.

As a result of further investigation, it was found that

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these disadvantages can be eliminated by the following measures.

According to the invention, the formation of fog is suppressed in that an inorganic solid is used as the coating material is used, which has high hardness and relatively low transparency. First, one of the individual Particulate coating layer of an inorganic pesticide applied, the high transparency and has good adhesion to a substrate, and to which a pesticide is applied, which is relatively low Transparency shows. According to another embodiment, a mixture of these pesticides with high Transparency and low transparency can be applied.

To explain this in more detail, hitherto, for example, in order to form a protective coating film, silicon dioxide SiO _{2 has been used} as a material having high transparency and hardness and exhibiting excellent adhesiveness to a plastic substrate. According to the invention, fogging is reduced to a great extent by applying a mixture of a small amount of a metal and SiO ₂ or by applying a material with low light transmittance such as metallic aluminum, chromium or a similar material from a coating layer of SiO ₂ to decrease the light transmission.

It is characteristic of the invention that the amount of light transmitted and thereby the proportion of the scattered Light that causes fog is reduced by reducing the permeability of the individual particles protective coating film, which is applied to a substrate to increase surface hardness.

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The invention is explained below with reference to FIGS. 3 and 4. Elements 2 of a protective coating film, which consist of a material with low light permeability, are applied to a substrate 1 to be protected. The proportions of the light rays P ₁ , P ₂ and P ₅ which arrive at Q _{1, Q 2} and Q, are reduced by the element or reduced to 0, so that the rays P ₄ predominate in the light transmitted through the body whereby the haze is reduced to a great extent.

According to an embodiment shown in FIG. 4, a transparent material 3 is applied to a substrate 1 and a. opaque material 4 is applied, whereby elements 2 of a protective coating film are formed. In this case, of the incident rays P ₁ to P _4, only the rays P ₄ pass through the body, whereby the fogging is reduced to a great extent.

The invention thus reduces the formation of fog by intercepting the scattered light and allowing only the light passing through the body in a straight line so that the arrangement of the transparent material 3 and the opaque material 4 in FIG. 4 can also be reversed The same result is also achieved if the opaque material is applied in a ring shape only to the edge area of each element or island of the clear material. To turn off the fog by pushing back or eliminating the scattered light, it is necessary to reduce the permeability of each element to 5o $ or less, preferably 3o i> or less.

In the practice of the invention, the aforementioned various transparent materials uses v / ground to form elements of a protective coating

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and on the other hand, can be used as opaque material in combination with the transparent material metals such as chromium, nickel, aluminum, gold, silver, tantalum, titanium, iron oxides, Chromium oxide, cobalt oxide and similar colored metal oxides as well as niobium nitride, chromium nitride, titanium nitride and similar nitrides and carbides, silicides, fluorides, and like refractory materials can be used.

According to the invention, the protected area of the surface of a substrate is increased when the density of the arrangement of Elements or islands which have been applied to form a protective coating layer is increased, while on the other hand the percentage area of the openings on the .Substrat is reduced, so that the inherently desirable Properties of the substrate such as hygroscopicity and anti-haze properties in the case of a hydrophilic resin, be affected. The invention is of great value for increasing the surface hardness of a molded article made of a hydrophilic one Plastic that does not have sufficient surface hardness. For this reason, the invention is explained in detail below with reference to such a substrate, it must of course be taken into account that the invention can in principle be applied to any substrate.

As shown in Figs. 5 and 6, if each element or each island 7 formed on a substrate 5 and a coating layer 6 made of a hydrophilic resin, has a large area, water droplets 8 on the surface of each element due to the lack of hygroscopicity of the protective coating itself, which causes local fog formation on contact with water vapor or water vapor will. In order to avoid this phenomenon, it is desirable that each element have as small a surface area as possible. This is true for drying one

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hydrophilic plastic body after absorbing water. The water Io, which through the plastic 9 directly below an element 7 of a protective coating film is absorbed, must diffuse in the plastic layer up to the free section 11 in order to evaporate in the air. Even In view of this, it is desirable for the rapid evaporation of moisture that the area of each element 7 is as low as possible, because if moisture is absorbed by the plastic immediately below an element 7 is, remains there permanently, the element has a different optical appearance than the openings or uncoated ones Areas and causes the phenomenon of so-called "fluctuation". This phenomenon is hereinafter referred to as "Dehumidification response" and will be described in detail with reference to FIG.

FIG. 7 shows the change in the amount of light that passes through a sample of a hydrophilic or hygroscopic plastic layer which does not carry a protective coating film. This change is determined by the addition of Steam at a constant flow rate onto the sample and continuation of the measurement after the steam supply has ended. A laser beam is applied to a point on the surface of the plastic layer

while water vapor is supplied to this surface. In the initial stage of supplying the steam, the permeability becomes the plastic layer for the laser beam passing straight through the sample is not changed in any way, because the steam is absorbed by the hygroscopic resin. During the constant supply of water vapor for a long time The resin becomes saturated with moisture, after which some of the vapor condenses on the surface, whereby water droplets are formed which cause mist formation. As the condensation of the vapor progresses

«Or" drying response "

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- 2ο -

Due to the scattering by the water droplets, the inside of the light is gradually reduced, which is picked up by a light detector which is arranged on the optical axis of the laser beam. In Fig. 7, the amount of transmitted light arriving in the detector is shown on the ordinate and the supply time of the steam is shown on the abscissa. In this graph, there is no change in the amount of transmitted light from point A to point B because vapor is absorbed by the sample and no water droplets are formed on this sample. From point B to point C, however, the amount of light abruptly decreases to green. the formation of mist on the surface after the resin is saturated with moisture. If the supply of steam is stopped at point G, the amount of transmitted light gradually increases thereafter due to the evaporation of the water droplets in the air, and the sample returns to the original transparent state at point D. The elapsed time between point A and point B is the time value indicative of the antifog or anti-haze property, and the value of the elapsed time between point C and point D time indicates the drying behavior.

In one sample a by vapor deposition of silicon dioxide on a hydrophilic polymer layer through a mask from rostfreiein steel with numerous circular through holes, each loo micron diameter at intervals of 2oo microns to form a coating layer having a thickness of 2oo angstroms, the circular from individual elements Each about 100 microns in diameter, the amount of transmitted light changes in the manner indicated by curve a * in FIG. 8. That is, the amount decreases somewhat at point Q and returns to the original value at point R and during the fog formation it decreases from point R to point S. When the supply * in a solid line

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is interrupted by steam at point S, the transparency of the sample at point T returns to the original value. In this case, the difference at point Q corresponds to the light scattering caused by water droplets. which are condensed on each element of the protective coating and the return at point R is likely to correspond to the formation of a transparent water film due to the condensation of a sufficient amount of moisture. On the other hand, it takes a longer time for the amount of transmitted light to return after the steam supply is stopped than in the case of an uncoated sample, and the amount of light _% at point T is less than that at point D in FIG If the vapor is identical, this appears to be due to the difficulty of evaporation of the moisture absorbed by the sample immediately below the elements, the response to drying not being sufficiently high.

Curve b in Fig. 8, on the other hand, is obtained with a sample having a protective coating made of the invention Elements, each element measuring 157 microns χ 50 microns (same area as the loo micron circular elements described above Diameter) and the density of the elements is equal to the density of the circular elements in that described above Sample is. In this case, the deviation in the amount of transmitted light in point U is smaller than that in Point * Q and the return to point V require less duration and the amount of transmitted light is greater than at point T on curve a and point D in Fig. 7. It is believed that the reason is that the amount of transmitted Light at point V is greater than at point T on curve a and the time to reach V is shorter than that to reach

♦ (dashed

of T i is the average distance the moisture immediately beneath each element must travel until it reaches uncovered areas or openings, is shorter, whereby a higher response on drying is achieved. From this newly found fact it can be concluded that as the surface hardness is increased the surface of a hydrophilic plastic body by applying a protective coating made of consists of numerous evenly distributed individual elements, the shape or the outline of each element when fixed Area should be other than circular.

To illustrate the abrasion resistance of a sample having a protective coating in which the elements are arranged in a simple regular pattern, a pattern with diagonal arrangement of the elements is shown in FIG. Reference number 12 indicates the openings or spaces in which the surface of a hydrophilic plastic is directly exposed to air, and number 13 indicates the elements of a protective coating. In this case, the coating film shows sufficient hardness against scratching or abrasive action in the direction of the line 1 ^ because an abrasive object slides over numerous hard protective elements. In the direction of the line I ₂ and 1, however , it is easy to scratch because an object with an abrasive effect only passes through the openings. Therefore, anisotropy of abrasion resistance is observed with respect to the patterns used. In order to ensure sufficient resistance to abrasion, it is necessary to determine the pattern of the arrangement of the elements.

The first rule is to arrange the protective elements in an irregular or statistical distribution. In from a practical point of view, however, it is difficult to use a mask

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completely irregular pattern so that it is a reasonable one Solution represents to form a mask by a number of basic patterns with one or a few elements in Form a basic pattern are formed, several of these Basic pattern combined to form a block pattern and several of the block patterns combined in a regular arrangement will. In this case it is necessary to determine the arrangement of the basic pattern and / or the elements so that the Elements in the basic patterns and / or the block patterns do not form arrangements with simple regularity. For example a hexagon shown in Fig. 10a is considered to be the basic pattern in which few protective elements are arranged in an irregular arrangement, and the basic pattern is then standing around its perpendicular to the plane of the paper Z-axis rotated 5 times by 60 ° to form a block pattern, which is shown in Fig. Lob, in which the elements are also are arranged statistically. A mask is created simply by expanding the block pattern two-dimensionally Flip, translate, or other translation methods made while in the completed mask the elements are arranged essentially in an irregular distribution.

As is apparent from the foregoing description, it is also an object of the invention to provide a specific shape or outline of a protective member of a protective coating film and a pattern of an arrangement of through holes in a mask for making a protective coating film, which (1) do not interfere with the inherently desirable properties of a substrate, such as hygroscopicity and freedom from fogging, and (2) the moisture absorption and moisture desorption response of a hydrophilic plastic "

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and (3) do not lead to anisotropy in abrasion resistance.

The surface protection according to the invention is thus used to increase the surface hardness of an object achieved by being irregular Distribution of numerous fine elongated islands of an inorganic pesticide on a surface of an art substance substrate, in particular a substrate made of a hydrophilic, hygroscopic plastic, with the formation of a coating layer which has openings, .which bring the plastic surface into contact with the air. A good result is achieved if this is applied under A mask is used which consists of numerous Blocl <~ pattern is formed in the manner described above,

The preparation of the coating film by the method of the present invention is explained in more detail below. The opening percentage is appropriately selected so as to provide a sufficient area of the openings for the resin as the substrate so as not to hinder the hygroscopicity and anti-haze properties, that is, 40 # or more, preferably 70 $ or more. To a. To ensure high moisture absorption and desorption response and high abrasion resistance, the element of the protective coating layer must have an elongated * shape. In order to reduce the isotropy of the abrasion resistance of a protective coating film, ie to prevent the substrate from being scratched or damaged, regardless of the direction in which it is exposed to the abrasive action, the elements are arranged in an irregular distribution, ie in arranged in a statistical pattern. It is characteristic of the invention that a pattern based on the three fundamental rules given above ♦ (dashed line)

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is designed to provide a sufficient increase in surface hardness to ensure an object.

An example of a pattern formed based on these fundamental rules is shown in FIG. First, a basic hexagonal pattern is provided, the side length of which is 124 microns, and which has four irregularly arranged through holes, each consisting of a square with a side length of 15 microns and two semicircles with a diameter of 15 microns, which are arranged on opposite sides of the square are, as shown in Fig. loa is shown. The percent open area of the substrate in the basic pattern is $ 96. The basic pattern is rotated 5 times by 60 °, a block pattern shown in FIG. 1b being obtained. A mask is formed by alternately arranging the block pattern and its mirror image. 11 shows a microphotograph of part of a statistical pattern in the mask (objective magnification 4oo χ eyepiece - magnification 3). In this way, therefore, a vapor deposition mask having an irregular pattern is easily obtained, resulting in a vapor deposited coating film showing no anisotropy in abrasion resistance.

As explained above, it is very difficult to have grains or particles of an article having an abrasive effect in the openings between the islands or elements of a protective coating. When individual particles get into these openings, it is rare for these grains to get through the fibers of an abrasive or polishing cloth are pulled over a greater distance, which into the openings get and scratch the surface of a subatrate because the small islands or elements of a protective coating at very fine intervals on the plastic substrate, in particular

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special on a hydrophilic plastic substrate, punctiform are arranged. It is actually guaranteed that a molded body, in particular made of a hydrophilic plastic, which has been provided with a coating film in this way, has greatly increased surface hardness and is practical Can be put to use without any difficulty. If a sample of one according to the invention coated plastic body under severe conditions when rubbed in practical use to test the surface of the substrate has been found by microscopic observation that only the surface of the protective coating film was attacked, but that the surface of the substrate had not been damaged. That means that by one on the surface of one The discrete particle coating film applied to the substrate determines the surface hardness of the coated substrate as a whole is determined.

On the other hand, it is assumed that there is no local convergence of internal stresses which would lead to the destruction of the Coating filras caused because of the protective according to the invention Coating film is divided into numerous, individual small islands or elements. For this reason it is avoided that the protective coating film becomes brittle and peeled off.

The structure of the inventive device formed from individual small islands protective coating film allows the surface of a substrate to be in direct contact with the Air comes in and therefore ensures the penetration of moisture into the surface and the evaporation of the moisture from the surface. In other words, the protective coating film enables the surface hardness of a to be increased Plastic object, in particular an object or

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Molded body made of a hydrophilic plastic without its inherent properties are impaired, such as the hygroscopicity. A hydrophilic polymer layer can be damaged or damaged by lightly rubbing it with a cloth deformed when due to the absorption of humidity is completely swollen by the water, the surface hardness of such a hydrophilic polymer layer becomes however, increased to a great extent without impairing their hygroscopicity if this layer is made up of individual particles existing protective coating film is applied according to the invention.

In addition, the protective coating film of the present invention enables the free passage of light because it has openings evenly distributed over the entire surface. If therefore When an opaque protective film is applied to a transparent substrate, the transparency of the substrate becomes transparent practically not affected and the substrate can retain its inherent property of light transmission unfold.

According to the invention, therefore, a protective coating film is obtained, which does not peel and which the surface hardness of a substrate without impairing the transparency and hygroscopicity inherent in the substrate, and the firmly to the surface of pen windows or doors of buildings, Automobiles, railway wagons and plug-in vehicles, or glasses, Protective goggles, optical lenses, glass panes for water tanks and mirrors made of plastic or glass or are formed from plastics which are coated with a hydrophilic plastic layer, can be connected.

Corresponding results are achieved when a protective

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Coating film according to the invention, for example on window frames, Walls, concrete blocks, hulls and underwater structures is applied.

The individual embodiments of the invention are illustrated in more detail below with the aid of the following examples .

The following test methods are used in the examples: Determination of the absence of fog or turbidity

As shown in FIG. 12, water 15 contained in a two-necked flask 14 is raised with the aid of a heating jacket 16 4o _ + o.5 ° C and air of normal temperature becomes through a flow meter, not shown, at a rate of 1,000 ml / min. to generate steam. The steam is through a tap 18 in a thermally insulated T-pipe introduced, one of which. End 2o a through opening with a diameter of Io mra and the other end one has through opening 21 with a diameter of 3 mm. Opposite the through opening 2o is a sample arranged at a distance of 2 mm for the steam outlet.

A light beam emitted from a He-Ne gas laser 23 (6328 Å, 1, o mW) passes through a slit 24, a lens 25, a through opening 21, a through opening 2o, the sample and an aperture 26 for masking out Scattered light and arrives in a photocell 27, where it causes an electric current. The diameter of the light beam is adjusted so that it is 20 10 mm at the through opening. The electric current is read off as a voltage with the aid of a milli voltmeter 28.

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First was the light transmittance of the sample before feeding of steam to the sample is measured with the tap 18 closed. The measurement of the time starts at the same time as the tap is opened and the time is determined which elapses until the reading of the millivoltmeter reaches a value that of an Io / o Reduction in light transmission due to the deposition of water droplets on the surface of the sample. Before the test is carried out, the sample is dehydrated by heating it to 80 ° C. for 30 minutes and placing it in a desiccator cooled to room temperature. The relationship between the light transmission and the reading of the with this method The millivoltmeter used was determined using a calibration curve obtained by measuring the transmittance and the emf (Millivolt) was obtained according to this test method with the help of glass panes that allow different levels of light transmission and by grinding different pieces of glass with abrasives of different grain sizes were produced during different grinding times.

Abrasion test

In Examples 4 to 9, commercial gauze is used under a load 2 kg / cm moved back and forth on the surface of a sample until noticeable scratches are formed on it, and the number of going back and forth is counted.

In examples Io to 14 an uncoated sample is used the intensity with which spectacle lenses are usually wiped. This is done with the help of a commercially available Silicone cloths (Gelite) or with gauze. In this experiment, the view through the sample is not noticeably disturbed, if the sample back and forth about 400 times with the help of Celite

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- 3ο -

or rubbed back and forth with the gauze about 100 times. The uncoated sample rubbed off as Standard sample viewed and the abrasion resistance of a coated one Sample is indicated by the number of rubs if the sample is so with the Celite or the gauze is rubbed for a long time until it is scratched on average to the same extent as the standard sample.

Determination of the film thickness

The thickness of the protective coating film is determined using a Talysurf device (Taylor-Hobson Co.) determined.

example 1

Two 5o mm 5o mm 3 mm sheets of poly carbonate were made cleaned using an ultrasonic cleaning process and one of the panels was in the present form and the other of the plates was after covering with a stainless steel mask that had numerous circular openings of 300 microns in diameter arranged in the pattern shown in Figure 9 with a spacing of 500 microns, in placed a vacuum evaporation device. The vacuum chamber was evacuated to 1 χ lo ~ Torr and silicon dioxide was evaporated onto the plates, while the plates were set to etv / a 100 ° C. The vapor deposition was carried out with the aid of an electron beam vaporization process (acceleration voltage 4 KV, current intensity of the beam 30 mA with an evaporation time of 10 minutes and a distance between the silicon dioxide source and the substrate of 12o mm), with a uniform coating on the unmasked plate B and a off individual small islands of existing coating was formed on the masked plate G, with both coating films one

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About 5 microns thick. The percentage open area of the coating film on G was $ 50 and the transparency of the coated plate C v / ar essentially identical to that of the plate B. On the other hand, an uncoated one became Polycarbonate plate A is provided.

The surface of samples A, B and C was used to determine their Surface hardness slightly brushed with the help of a wire brush, made from a bundle of 3o copper wires of ο.2 mm in diameter duration. Some scratches were observed on the surface of Sample A after two or three touches, on the However, the surface of samples B and C became even after being repeated 100 times or even more frequent brushing no scratches observed.

When samples B and C are immersed in boiling water at 100 ° G After 30 minutes to 1 hour, the peeling of the protective coating film of Sample B and the protective coating film occurred had almost disappeared after 1 1/2 hours, while on sample G no change even after 3 hours of implementation of the boiling test was observed.

Example 2

Two plates made of PolyCmethylmethacrylat) were with the help of a Ultrasonic cleaning process cleaned and one of the panels was in the present shape and the other of the panels was after covering with a mask shown in Fig. 13, which consisted of two stainless steel masks each of which is circular 300 micron diameter holes arranged in the pattern shown in Figure 9 spaced 500 microns apart, the two masks were combined with each other at an angle of 45 °. Any of the poly (methyl methacrylate) - Plates were then put into a water-cooled one

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mounted sample holder and placed in a high-frequency atomization device. Since there was a risk that the plate would be exposed to the plasma and thermally decomposed, vacuum grease was applied to the package of the plate in order to improve the thermal contact between the plate and the plate holder. Sintered cerium oxide (CeOp) was attached to the cathode in the high frequency sputtering device and the vacuum chamber was then evacuated to 1 χ lo '^ Torr, after which dried gaseous argon was introduced until the internal pressure was ^{adjusted to 3 x lo ~ 5} Torr,

The sputtering was carried out for 5 minutes at a high-frequency voltage of 2.5 KV and an anode current of 24o mA by applying a voltage from a 1 KW high-frequency generator, a CeOp film with a thickness of about 1,000 kV A was deposited on the poly (methyl methacrylate) plate. In this way, a uniform uninterrupted film was formed on the unmasked plate B, and a particulate film with a moiré pattern was formed on the masked plate C. The percentage area of the openings of the protective film on the plate C was 65 °, and the coated plate C showed no transparency deviating from that of the coated plate B. On the other hand, an uncoated plate made of poly (methyl methacrylate) A was provided.

Samples A, B and C were prepared in the manner described in Example 1 using a wire brush and a wire pinael, respectively subjected to the surface hardness test. Sample A was made by lightly brushing through just two or three Brush movements damaged, while samples C and B were hardly scratched, even if they were touched a thousand times or more Brush were painted over. If samples B and C are as in

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2310CU6

Example 1 were subjected to the test in boiling water, so in sample B the coating film peeled off after 20 to 20 minutes Boil for 30 minutes while working on sample C itself No change was observed after boiling for 1 hour.

Example 3

Two 50 mm 50 min 3 mm cast plates made of an unsaturated polyester resin were cleaned in an ultrasonic cleaning process and one of these plates was in the present form and the other was after covering with a mask made of stainless steel, the 14 and consisted of three stainless steel masks each having circular openings 300 microns in diameter arranged in the pattern shown in FIG. 9 spaced 500 microns apart, wcboi iio three basic masks at angles of 22.5 and 45 were stacked on top of each other, placed in a vacuum chamber. Stannous oxide (SnOp) was placed in a molybdenum boat placed below the plate in the vacuum chamber. The chamber was evacuated to 2 χ Io Torr and an electric current was applied to the molybdenum boat to generate SnO _? on the plate to a thickness of about 2,000 Å ". Thus, a uniform coating layer on the unmasked cast plate B and a particulate coating layer having the pattern shown in Fig. 14 on the masked plate G were formed. The percent open area of Sample C was 75 " and there was no difference in transparency between Samples B and C. In addition, an uncoated cast plate of unsaturated polyester resin (A) was provided.

Samples A, B and C were subjected to a surface hardness test

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Subjected to using a wire brush in the same manner as in Example 1. Some scratches formed on the Sample A when brushed over once or twice while no scratch was formed on Samples B and C even when brushing was made about 100 times became. In the boiling test, the coating on sample B was peeled off after 3o to 4o moderate boiling, while on sample C no change was observed even after boiling for 2 hours.

Example 4

On a commercially available lens of glasses for myopia 63 mm in diameter, a hydrophilic acrylic resin, a polymer of 2-hydroxyethyl methacrylate (trade name Hydron) was applied to a thickness of about 7 microns, and after the coating was dried, the lens was covered with a mask stainless steel having circular holes 300 microns in diameter spaced 500 microns apart in a pattern shown in Fig. 9 and placed in a vacuum deposition chamber. A molybdenum boat was placed below the masked lens in the chamber and charged with stannous dioxide. After evacuating the chamber to 2 torr χ Io an electric current was applied to the molybdenum boat to evaporate around the Stannidioxid to the lens, wherein an existing in each island coating thickness was formed by 5oo K. The lens was then subjected to the anti-haze property test and an abrasion test. The results obtained are summarized in Table 1 below in comparison with results obtained when testing an uncoated surface made of poly (2-hydroxyethyl methacrylate). The percentage area of the openings of the protective film thus obtained was about 55 Jo.

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-i-

Table 1

Sample ■ fogging; (see) Abrasion Test

not excessive 2o 5o

overdrawn 22 2oo

As shown in the above table, the protective film of the present invention greatly improved the abrasion resistance Measure without impairing the property of freedom from fog or cloudiness. The transparency of the lenses remained unchanged.

Example 5

Two glass plates, each 50 mm by 50 mm by 3 mm, were coated with a 2-hydroxyethyl methacrylate polymer (hydron), a coating film having a thickness of 23 microns being formed. After drying, the coated surface of each panel was covered with a square cross-section mask made from standard 149 micron (100 meshes per inch) wire mesh and placed in a vacuum deposition chamber. Electric current was applied to a silicon monoxide containing molybdenum boat which was placed below the plate in the chamber after the Kamner 2 χ lo "-. ⁵ Torr was evacuated this case, an existing from each island coating film of silicon monoxide was added to a thickness of 5oo% was formed on one of the plates and to a thickness of 3,000 K on the other plate, and the samples were subjected to the determination of the property of freedom from haze or mist and the abrasion test.

The test results obtained are in the following table 2 in comparison with the properties of an uncoated: Hydron surface z ^ J | i ^ 3 ^ / s1jejLJ-fy. The percentage area

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Area of the openings of the protective coating on the two samples was about $ 60.

Table 2

Freedom from

Sample mist formation (see) abrasion test

not overdrawn I60 5o

overdrawn 5oo 15o 5oo

overdrawn 3 · οοο Ä 17o> l.ooo

As shown in the table above, the protective coatings of the present invention improved abrasion resistance without that an impairment of the freedom from fog and the transparency was caused.

Example 6

A flat glass plate 3 mm × 50 mm × 50 mm was cleaned and coated with a hydrophilic polymer, polyvinyl alcohol (PVA) to a thickness of about 5 microns. After the coating was completely dry, the plate was placed in a vacuum deposition chamber. In this case it was a combined one
Mask used, which consisted of three stainless steel plates, each of which had circular holes 300 microns in diameter formed in a pattern as shown in FIG. 9 at a spacing of 500 microns
were arranged, had and were stacked on top of one another,
that they are under a 7 / inkel of 22.5 ° and 45 ° under formation
of the pattern shown in Fig. 14 were twisted against each other. In a molybdenum boat in the lower section of the
Chamber was arranged, bismuth trioxide (BipO,) was presented.
After evacuating the chamber to 2 χ 1ο ~ ⁵ Τογγ was sent to the

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Molybdenum boat applied an electric current to evaporate Wisrcuttrioxid in a thickness of about 500 Å on the plate. The PVA film provided with a protective film was subjected to the test of freedom from fog or haze and abrasion together with an unprotected PVA film used for comparison purposes, the results summarized in Table 3 below being obtained. The percentage area of the openings of the protective film was 80 ° β.

Table 3

Freedom from

Sample fogging (see) abrasion test

uncoated PVA 2o 5

coated PVA 18 3oo

Example 7

The refractive index of PVA is usually 1.49 to 1.53, and that of PVA used in the above example was about 1.51, so that the protective film consisting of individual islands could be determined by careful observation that Bi ₂ O is one has a high refractive index of 2.42. According to the field of application, it is desirable to make the protective film invisible. In this example, therefore, V / ind shield glass with essentially the same index of refraction of 1.52 was used. The glass plate was coated with the PVA used in Example 6 and then coated with a glass film which is commonly used for making a windshield. For this purpose, the same glass was used as in Example 6 and the coating was carried out under a vacuum of 1 lo "Torr with the aid of an electron beam

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of 20 mA which was accelerated by a voltage of 4 KV. The distance between the source and the surface of the substrate was 120 mm and the vapor deposition time was about 1 minute, It was difficult to determine the presence of one on the PVA surface the coating film composed of individual particles. The thickness of the coating film was 1,5oo 1 and the percentage The area of the openings was 80 #. If that coated When the substrate was subjected to the abrasion test, no scratches were found even after being painted over with the brush 500 times observed, and it was confirmed that the haze is not impaired as by fogging after about 23 seconds of treatment in a misting test was indicated.

Example 8

On the surface of a 5o mm χ 5o mm χ 3 mm glass plate was a 2-hydroxyethyl methacrylate polymer (Hydron) in one Thickness of 5 microns was applied and after drying the surface coated with the hydrophilic polymer (Hydron) densely covered with a stainless steel mask, the numerous 500 micron wide slits 7oo microns apart

exhibited. The plate was evaporated with silicon monoxide in the same manner as in Example 1, whereby a coating film having a thickness of 3,000 K and a percentage area of the openings of about 30 $ was formed on the plate. The results of the haze test and the abrasion test conducted on the sample are shown in Table 4.

Tabel 4th Abrasion test sample Freedom from
Secondary education ( lake) 5 ο
> 1.ooo not covered
overdrawn 18th
6th
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example

A layered sheet of glass measuring 100 mm by 100 mm, commonly used as safety glass for automobile windshields, was coated with a 2-hydroxyethyl methacrylate polymer (hydron) to form a coating film with a dry thickness of about 7 microns. ' After drying, the plate was placed in a sputtering device as an anode. A tin plate was attached to a cathode as a catch plate. Two masks, each of which openings 5o of microns in diameter at a distance of microns had loo, and f at an angle of 45 ° to each other via bearings ^ ^e were densely arranged thereon. After evacuating the apparatus to 1 χ Io "^ Torr, a gas mixture consisting of 95 $> argon and 5 i ° oxygen was introduced, was adjusted until the pressure to 2 χ lo ~ Torr. A DC sputtering was for about 4 minutes using a direct voltage source with a direct voltage of 5 KV and 2oo mA, a film of stannous oxide having a thickness of about 2,000 K. By supplying gaseous oxygen and not just the inert gas argon, a reactive gas was A sputtering process was achieved in which the vapor emitted from the plate was converted from metallic tin to stannous dioxide. The percentage opening area of the resulting stannous dioxide coating was about 75 #. The 2-hydroxyethyl methacrylate polymer surface and the SnOp-coated surface of the same polymer had the following properties :

Table 5

Freedom from
Sample fogging (see) abrasion test

not overdone 6o 5o

overdrawn 55 > l.ooo

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- 4ο -

Example Io

A commercially available eyeglass lens for myopia, made of glass 63 mm in diameter, was coated with a hydrophilic Acrylic resin, a polymer of 2-hydroxymethacrylate (hydron) coated to a thickness of about 16 microns and after drying densely covered with a stainless steel mask, the circular holes 25 microns in diameter in that shown in FIG Had patterns at a pitch of Ho microns. The lens was placed in a vacuum chamber and a silicon monoxide containing molybdenum boat v / urde below the

• -5

Lens arranged. After the vacuum chamber was evacuated to 2 χ Io Torr, electrical current was applied to the molybdenum boat, and silicon monoxide was deposited on the lens to a thickness of about 1200 and 3500 K. The percentage area of openings was 79 ⁰ I ". The results obtained in the test j the turbidity freedom and the abrasion test are summarized in the following Table 6.

Tabel

not overdone
coated, 1,2oo Ä
covered, 3 · 5οο Ά

Freedom from
Nebelbildune (lake) Abrasion test 4oo gauze Celite .000 > 1 loo loo , ooo> 3 . 000 about 14o > 5, .000 about 95 > Io,

Thus, as indicated in the above table, the protective films of the present invention improved the surface hardness to a great extent and moreover improved the property of freedom from haze.

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Example 11

In place of the 25 micron diameter mask used in Example Io with an aperture spacing of Ho microns, a mask was used which had circular holes 15 microns in diameter in an arrangement shown in FIG. 9 with a spacing of 80 microns. A protective film was obtained whose percentage surface area of the openings, determined by microphotography, was 92 ° /> . When the obtained sample was tested together with a sample without a protective film, the results shown in Table 7 below were obtained.

Table 7 Sample Fogging Test Abrasion Test

T / To (#) Celite Cazc

not overdrawn loo - 4oo loo overdrawn 13o> 3.ooo ? l.ooo

Example 12

Instead of the mask described in Example Io with holes of 25 microns in diameter and spaced apart by Ho microns, a mask was used which had circular holes of 15 microns in diameter in the arrangement shown in FIG. 9 at a spacing of 100 microns. A film of stannous oxide consisting of individual islands with a thickness of about 1,000 K with a percentage area of the openings of $ 95> was deposited. The results obtained when the sample was tested in the fog formation test and in the abrasion test are summarized in Table 8 below.

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23100Λ6

Table 8

sample Secondary education test Abrasion test gauze T / To (%) Celite 8o not covered loo 35o loo overdrawn Io5 • * 1. ooo

Example 13

On a 3 ram thick polycarbonate plate measuring 50 mm χ A hydrophilic resin (hydron) was applied to a thickness of about 7 microns 50 mm and after drying the plate was * covered with a nickel mask, the circular holes with a radius of 35 microns arranged in that shown in FIG Pattern, spaced llo microns apart. This mask was placed close to the coated plate. Thereafter, the plate provided with the mask was placed in a vacuum deposition chamber brought. An electron gun and a block of ordinary sheet glass were placed in the vacuum evaporation chamber arranged opposite the electron gun as a collecting plate. The chamber was evacuated to 5 x Io Torr and a Electric current of 4 KV and 30 mA was applied to the electron gun, whereby the glass block melted and evaporated became. By evaporation for about 5 minutes, a coating film consisting of individual islands and a thickness of about 1.81 / Iikron and a percentage of the surface area of the openings of 61, o # is formed on the surface of the substrate plate.

Table 9

sample Fog formation test Abrasion test gauze T / To (#) Celite loo not covered loo 4oo > lo.ooo overdrawn 113 > 50.00c 309836/1130

Example 14

A hydrophilic resin (hydron) was applied to a thickness of about 5 microns on a surface of a 5 mm thick glass plate measuring 8o mm χ loo mm and, after drying, the plate was densely covered with a nickel mask, the circular holes with a radius of 40 microns arranged in the pattern shown in Figure 9, spaced 15o microns apart, and the plate covered by the mask was placed in a sputtering chamber. The back of the substrate plate was applied to a cooled high-frequency anode (earthed) with the aid of a thin layer of silicone grease in order to produce a cooling effect. A silicon plate (silicon pericle) of 150 mm × 150 mm × 5 mm was placed on the opposite cathode and the chamber was then set to 2 ×

-5
Io Torr evacuated. Then, gaseous nitrogen was introduced into the chamber to adjust the pressure to 3 x lo "-. Discontinue ⁵ Torr Sputtering was then during Io minutes at a voltage of 3, o KV carried out with an anode current of 25o mA, wherein an overcoat film of silicon nitride a Thickness of about 2,000 K. The percentage surface area of the openings of the film was 90 #.

Table Io Probe Fogging Test Abrasion Test

T / To (#) Gelite gauze

not excessive loo 4oo loo

overdrawn 13o > 3.ooo> 1.5oo

Example 15

A cleaned? Oly (methyl methacrylate) plate from Io cn χ

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Io cm χ 3 mm was placed in a vacuum deposition chamber and metallic chromium was evaporated onto the surface of the plate through a nickel mask with circular holes 15 microns in diameter spaced 85 microns apart, with a coating layer about 1.0 microns thick was formed. On the other hand, on a substrate of the same quality, silica was applied to form a coating film. Thickness of about 1.0 microns evaporated through the same mask. The percentage area of openings of the sample A (covered with chrome) and the sample B (with Siliciumdioxid'überzogen) were both times 96.5 ° ß> and the light transmittance of each element itself of the sample A was about 7 $> and the sample B was about 92 fi. Fogging in sample A was, as determined by ASTM D-loo3 o, 62 ° / o and the sample B ^ 2.3. The total permeability for visible radiation was 87.6 $> for sample A and 91, ο ^c / o for sample B, with no difference in light permeability being observed between the two samples with the unprotected eye.

Example 16

A cleaned polycarbonate sheet with the dimensions Io cm χ Io cm 3 mm was placed in a vacuum vapor deposition chamber and a silicon monoxide film 0.8 microns thick was passed through a nickel mask with circular holes of 15 microns in diameter evaporated onto the surface of the plate at a distance of 85 microns. After that it was on this Coating film evaporated an approximately 0.2 micron thick film of metallic nickel, whereby Sample A was formed. on the other hand became only a silicon monoxide film of a thickness of about Evaporated 1.0 microns onto a polycarbonate plate of the same dimensions to form Sample B. The percentage

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The area of the coating in both samples was about 3½. The light transmittance of each element itself of the sample A was about 15 #, while the fog of Sample A o, io 83 and that of Sample B 2.6 ^a / o, respectively. The Gesarat light transmittance of the sample A was 88.5 $> and that of the sample 3 9o, 5 ° / o, thereby indicating that there is practically no difference in the light transmittance consisted of both samples.

Example 17

On the surface of a cleaned glass plate with the dimensions Io cm χ Io xm χ 3 mm, an approximately 5 micron thick PiIm of a hydrophilic resin, namely poly (2-hydroxyethyl methacrylate) (Hydron) was applied and, after the coating film had dried, the plate was arranged in a vacuum vapor deposition chamber. Alumina AlpO and metallic aluminum from separate evaporation sources were simultaneously vapor-deposited onto the coated surface through a rust-free steel mask, which had circular holes 30 microns in diameter, evenly distributed at a distance of 200 microns, with one Protective film about 0.6 microns thick was formed (Sample A). On the other hand, similarly, only alumina was evaporated on a cleaned glass plate of the same dimensions to form an alumina film about 0.6 microns thick (sample B). The percent area of coating on Sample A and Sample B was about 3 ^c / ° in both cases, and the haze of Sample A was about 0.53 and that of Sample B was about 2.7 96.

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Example 18

As the substrate, a polarizing plate was used, the dyed a yellow between two poly (roethylmethacrylat) plates embedded polarizing film consisted and a light transmittance of et v / a 8o ° / o had. After cleaning, the substrate was covered with a mask having circular holes 80 microns in diameter spaced 25o microns apart in the pattern shown in Figure 9. The entire assembly was mounted in a high-frequency sputtering chamber and subjected to reactive sputtering in a gaseous nitrogen atmosphere, with a protective film of silicon nitride Si, N, consisting of individual particles. was formed to a thickness of 3,000 K. on the substrate surface (sample A). On the other hand, a film consisting of individual islands and having a thickness of 3 · οοο λ made of chromium nitride was formed on another substrate of the same nature in the same manner (sample B). The silicon nitride was very transparent, but the green was colored brown. The visible radiation transmittance of the Si, N. film itself ( 3,000K thickness) was about 90 $> and that of the CrN film was about 25 #. The haze of Sample A was 1.65 % and that of Sample B was 0.45%.

Example 19

A vapor deposition mask A was produced by creating a basic pattern which consisted of a regular hexagon which had 5 rectangular holes of 40 microns χ 12 microns in an irregular distribution, the side length of the hexagon being 124 microns. On the basis of this basic pattern

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a block pattern was produced in the manner described with reference to FIG. 1b, and the block pattern was rotated twice. On the other hand, a vapor deposition mask B was prepared which had circular holes 25 microns in diameter arranged in a regular pattern at intervals of 100 microns. On separate substrates, silicon dioxide was applied through mask A or B to form a coating film about 3 · 4οο Κ thick. Coated Samples A and B were thus obtained, both of which had an area area of openings of about 92%. Samples A and B and a sample C made of an uncoated substrate were subjected to the abrasion test and the test of response to moisture absorption and desorption. The abrasion test was carried out using a rotary abrasion tester fitted with a silicone rubber, gauze-covered abrasive tip. The abrasion resistance was determined by measuring the time it took for a noticeable scratch to be formed by abrasive action under a load of 500 g / cm at a rotation speed of 30 rpm. The response to moisture absorption and desorption was determined by measuring the amount of transmitted light using a He-Ne laser beam while water vapor at 40 ° C. was applied to the surface of a sample at a flow rate of 1,000 ml / min , was applied. The change in the amount of transmitted light corresponding to points Q and U in the curve shown in Fig. 8 was given as a relative value with respect to the value of the sample B, which was determined to be 1.0. The moisture desorption (drying) response was expressed by the time it took for the light transmittance of a sample to reach 99 # of the original value (before feeding

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of steam) returned after the supply of steam was interrupted. The supply of steam was carried out for the same duration for all samples. The Claimant. the moisture desorption was also given as a relative value, the value of sample C being viewed as I ₁ o.

Tabel

11

Sample abrasion test. (Min) Change in response to d esorpti on

9o - loo

3o - 4o

5 - Io

about o, 25 l, oo

approximately 1 , 15 approximately 1 , 5o 1 , 00

The table above indicates that both samples A and B have far higher surface hardness than sample C, and that sample A is harder than sample B, while the above said sample shows less change in light transmittance due to the protective coating film than the last-mentioned sample and, moreover, is better with regard to the desorption behavior, i.e. that the inventive Method as a method of improving surface hardness of a substrate leads to superior results.

Example 2o

A 46o micron square that had 6 irregularly spaced rectangular holes 50 microns χ 157 microns as Basic pattern, was rotated 90 ° three times to form a block pattern, which consisted of 4 basic patterns. The block pattern

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was turned over twice to form an enlarged pattern, thus forming an image mask D. On the other hand, a vapor deposition mask E having circular holes of 100 microns in diameter in a pattern shown in Fig. 9 at intervals of 200 microns was formed. A silicon monoxide film with a thickness of about 96 ° was evaporated onto a substrate through mask D or E, samples being obtained which each showed a percentage area of the openings of about 92 °. Samples D and E and a sample of an uncoated substrate were subjected to the same test as in Example 19, and the results summarized in Table 12 below were obtained.

Table 12 Sample abrasion test (min) Change in response to desorption

o.3o about 1.5o l, oo about 4.5o

l, oo

The table above shows that one of the individual Islands of protective coating film consisting of non-circular elements, both in terms of surface hardness as well as the moisture absorption and desorption properties is better than one of the single Elements consisting of coating film, the circular elements even if both films have the same percentage area of the openings.

D. approximately 12o Io E. approximately 6o F. 5 -

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Claims (1)

DA-10392 PATENT CLAIMS 1. Cover film made of inorganic material, characterized in that it has a thickness of 400 Å to 5 microns and consists of separate elements, between which openings remain with an extension of 5 to 99 % of the total area of the film. 2. Coating film according to claim 1, characterized in that it consists of separate transparent elements consists. 3 coating film according to claim 1, characterized in that it consists of individual elements which have a IiichtdurchläBSigkeit of at most 50%, preferably of at most 30 $>. 4-coating film according to claim 1, characterized in that it consists of individual, multi-layer elements comprising layers of a transparent substance and / or layers of a substance with a permeability of at most 50 $ or at most 30 ° C. - 2 300836/1130 5. coating film according to claim 3, characterized in that it comprises elements consisting of a or more oxides, nitrides, fluorides and / or sulfides are formed by metals. 6. Coating film according to claim 3, characterized in that the elements are formed with a light transmission of at most 50 $ from a mixture of at least one silicide, boride, nitride or carbide and at least one metal, colored metal oxide or a scliv.'erechmelzbaren material. 7. Coating film according to claim 3, characterized in that the elements having a light transmission of a maximum of $ 30 are formed from metals, colored metal oxides or refractory substances. 8. Coating film according to one of claims 1 to 7, characterized characterized in that the individual elements are arranged in a regular pattern. 9. Coating film according to one of claims 1 to 7, characterized. that the elements in irregular Distribution are arranged. 10. Coating film according to one of claims 1 to 9, characterized 309836/1130 ft.U) characterized in that it consists of individual elements that have a ratio of short axis to long axis of 0.1 to 1. 11. Coating film according to claim 10, characterized in that it consists of circular elements. .12. Coating film NaOH claim 10, characterized ge ke η η - is characterized in that it consists of oval, rectangular or ellipMenförmigen elements. 13. Coating film according to one of claims 1 to 12, characterized in that it comprises a surface area of the openings of 5 to 70 %. Η · Cover film according to one of Claims 1 to 12, characterized in that it comprises a surface area of the openings from 30 to 99 #, in particular from 60 to 99 i> . 15. überzugefiln according to any one of claims 1 to 14, characterized ' characterized in that each individual element has a Has an area of no more than 3 x 10 square microns. 16. A method for producing a coating film according to egg nem of claims 1 to 15 on a molded body, the at least 309836/1130 received on has a surface consisting of a 'plastic, characterized in that with the aid of a Vapor deposition process on the plastic surface one from one ·? its elements consisting of a film of an inorganic material with a thickness of 400 S to 5 microns is applied through a vapor deposition mask, which is formed in such a way that numerous individual islands or elements with an area of no more than 7 x 10 square microns each are formed, between which openings remain, in which the surface of the forra body lies. '17. Process according to Claim 16, characterized in that the vapor deposition is then carried out with the aid of the resistance heating process, the electron beam process or the atomization process. 18. The method according to claim 16 or 17, characterized in that a vapor deposition mask is used which consists of one? perforated plate. 19. The method according to claim 18, characterized in that a perforated plate is used which has regularly or irregularly arranged openings. 20. The method according to claim 16 or 17, characterized in that can ale vapor deposition mask from a stack multiple perforated plates or slotted plates are used. '- 5 -309138/1130 received ohlJ & Ü 21. The method according to claim 16 or 17; thereby geke η η -s -e leans that ale vapor-deposition mask uses a perforated plate with a pattern which, using a regular polygon, which has numerous irregular through holes of elongated shape or elliptical shape, as a basic pattern, n- turn the polygon by (56O / n) °, where η means the number of corners of the polygon, forming a block pattern, and repeat the blocker, was formed. .22. With a coating film according to any one of claims 1 to provided molded body which has at least one surface made of a plastic as a substrate for the coating film. 23. Pormkörper according to claim 22, characterized in that it consists of a plastic or a material coated with plastic. 24. Pormkörper according to claim 22 or 23, characterized in that it contains a hydrophobic polymer as the plastic. 25. Pormkfirper according to claim 24, characterized g e k e η η - «• rejects that the percentage opening area in the overtaking film is £ 5 to £ 70. 26th A molded body according to claim 24 or 25 »characterized in that the · hydrophobic · polymer ·« in polycarbonite, 301131/1130 received on. Poly (ethyl methacrylate), polyvinyl chloride, polystyrene, polypropylene, Polyethylene or an unsaturated polyester resin let. 27. Shaped body according to claim 24, characterized in that it is a door panel or a spectacle lens represents. 28. Shaped body according to claim 22 or 23Y, characterized in that it is a hydrophilic polymer as a plastic contains. 29 Shaped body according to claim 28, characterized in that the percentage opening area of the coating film is 30 to 99 ^, preferably 60 bic 99 $> . 30. Shaped body according to claim 28 or 29, characterized in that it is a hydrophilic polymer as the hydrophilic polymer Acrylic or methacrylic polymer, polyvinyl alcohol, polyvinyl acetate, Polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, hydridxyethyl cellulose or regenerated cellulose contains. 31. Shaped body according to claim 30, characterized in that it is used as a hydrophilic acrylate or methacrylate poly. meres a polymer of a hydroxy-lower alkyl acrylate, hydroxy-lower alkyl) methacrylate, hydroxy-lower-alkoxy-lower-alkyl) -acrylate or hydroxy (lower-alkoxy-lower-alkyl) methacrylate . 309836/1130 «Went out - Shaped body according to claim 30 or 31, characterized in that it consists of a glass coated with a hydrophilic polymer, preferably one coated with a hydrophilic acrylate or methacrylate polymer. 33. Shaped body according to claim 32, characterized in that AaD he the lens of glasses, a window glass or a windshield of an automobile. 34. Shaped body according to claim 27, characterized in that it is polyvinyl as the hydrophilic polymer contains alcohol. 309836/1130