DE2650120A1 - Manufacture of laminated security glass for windscreens etc. - using silane(s) to bind olefin polymer(s) to glass - Google Patents

Abstract

Parent patent describes the mfr. of laminated security glass by combining, on one or both faces of >=1 sheets of silicate glass, leaves of plasticised PVC with the aid of silanes. In this addn., ethylene and/or propylene polymers or partly acetylated PV alcohol (esp. poly(vinyl butyral)) replace the PVC; lamination is done under pressure at 120-200 degrees C. The polymer sheets have Shore A hardness of 40-98 (pref. 50-95). The silanes have formula RnSi(Y)3-nApZ (where R is hydrolysable gp., e.g. Cl or OX, X is 1-8C alkyl, opt. contg. -O- or -S-, or is acyl; Y is 1-18C alkyl; A is 1-10C alkylene, opt. branched. Z is radical contg. epoxy, -C=C-, halogen, -NR1R2 or (R' is H or 2-8C aminoalkyl; R2 is H or R1, R3 is H, CH3 or C2H5); N=1-3; p=o or 1. of Z contains -C=C- the cpds. are used together with a radical former. Depending on the degree of adhesion between the various layers (which depends on the type and amt. of silanes used), the materials can be used in window glass and in other constructional used, in glass for testing projectiles, or in the windscreens of motor cars, railed vehicles, boats, aeroplanes, etc. Replacement of PVC by ethylene and/or propylene polymers gives an improved security glass.

Description

Process for the production of laminated safety glass

Subject of the German patent specification ........

(Patent application P 25 49 474.0) is a method for production of laminated safety glass by joining one or more of them on one or both sides Silicate glass panes with plasticized plastic films at elevated temperatures with the help of silanes, which is characterized in that it is used as a plastic film plasticized polyvinyl chloride containing film made of high molecular weight vinyl chloride homo- and / or copolymers or graft polymers and, as silanes, silicon-orgamofunctional Silanes, optionally in a mixture with one or more silicon-functional ones Silanes, used and the Verbumd produces at 120 to 200 ° C.

According to a special implementation form, the silanes in one Solvent dissolved used in such a way that one of these silane solutions at least one of the interfaces to be connected of the layers to be connected to one another applies, the solvent evaporates and then the bond is established.

This form of implementation also includes the method of operation which the silane is used in a lacquer, and the silane in this lacquer either present dissolved or dispersed.

It has now been modified in the procedure of the German patent specification ... (patent application P 25 49 474.0) a process for the production of laminated safety glass by joining one or more silicate glass panes on one or both sides with | plasticized plastic films with the help of silanes, these being silanes be used dissolved in a solvent or in a lacquer in such a way, that one of these silane solutions or the silane-containing paint on at least one of the to be connected interfaces of the layers to be connected to each other applies, the solvent evaporates and then creates the bond, found that characterized in that the plastic film is polyvinyl butyral film begins.

It is already known from DT-AS 24 10 153, the liability between plasticizer-containing partially acetalized polyvinyl alcohol films and inorganic ones Set glasses in a targeted manner that the partially acetalized resin before or adds predetermined amounts of a silane during processing into a film. In this procedure, the silane from the resin is in a separate process step mixed in; it is located evenly across the entire resin in these: distributed, In this way of working, relatively large amounts of the Silane used.

It has now been shown that an effect is at least as good achieved if only the surface of the layers to be bonded is made with the silane treated, this treatment being carried out in the form of a solution. It is in this way possible to use considerably smaller amounts of silane than with the procedure of DT-AS 24 10 153 are necessary.

The method of operation according to the invention surprisingly also shows the advantage that the influence of the water content of the plasticized polyvinyl butyral film on the desired glass adhesion is practically irrelevant. It's bekazat that the higher the adhesiveness of polyvinyl butyral films to glass, the lower their water content is. If the water content is reduced, however, the adhesiveness decreases .E.a. By treating the surfaces of the polyvinyl butyral films with solutions of Adhesive strength-increasing silanes achieve a constant adhesion value over a wide range up to high water contents; conversely, one achieves through treatment with adhesive force-reducing silanes a constant adhesion value over a wide area Range down to low water contents.

It is also known that plasticized polyvinyl butyral films generally have a very high adhesion to the glass, which when used in the construction sector, z. B. as a building glass window pane, is desirable * For composite safety panes, those used as windshields are used in motor vehicles, on the other hand, the adhesive force of the film on the glass must be reduced in a controlled manner. If namely the disc is destroyed by impact; is done at very high adhesion, a breakdown in the center of the impact without a lot of glass splintering. If the adhesion is very poor, the impact tool, e.g. a Pall body, will be used by the film is elastically intercepted, but the splintering effect is very great. At a Rear-end collision with destruction of the pane by impact of the head should the film On the one hand, slowly reduce the kinetic energy by stretching, | on the other hand but should the destroyed glass still adhere so well to the film that dangerous cuts be avoided. For this reason, the adhesive force must be optimal in these cases a defined pummel value, which is generally between 2 and 5, is set be.

According to the invention, the silanes are used in solvents such as in which they are readily soluble and which evaporate easily after the film treatment permit. Furthermore, the solvents must use the plasticized polyvinyl butyral films wet well without loosening them. Such properties have z. Bo aromatic Hydrocarbons such as toluene or xylene, light gasoline or lower alkyl esters of lower aliphatic 1 carboxylic acids, such as ethyl or butyl acetate.

An advantageous form of use of the silane is that in which the Silane is dissolved or dispersed in a paint.

Plasticized polyvinyl butyral, for example, is suitable as a binder, that advantageously the recipe of the plasticized polyvinyl butyral film used is equivalent to. In principle, however, other film-forming binders are also included settable, it being advantageous if these contain free OH or COOH groups.

The concentration of the silanes depends on the type of application to be selected away. If they are used dissolved in a solvent, the concentration can be between 0.0001 and 7.0 parts by weight, preferably between 0.0005 and 5.0 parts by weight, be based on 100 parts by weight of solvent. If, on the other hand, the silane is in a Paint is used, the concentrations range between 0.0001 and 2.0 parts by weight, preferably 0.0005 and 1.0 parts by weight: based on the silane-containing paint.

The silanes which can be used according to the invention are characterized by | a) silicon-organofunctional silanes or mixtures which increase the adhesive force organofunctional silicon silanes or b) silicon-functional ones that reduce the adhesive force Silanes or mixtures of different silicon-functional silanes or c) Mixtures of at least one silicon-functional silane with at least one silicon-organofunctional Silane.

The organofunctional silicon used according to the invention are amino and / or irino or epoxy groups containing alkylenalkoxysilanes. One or both H atoms of the amino group can be replaced by an amino or hydroxyalkyl or a polyamino radical can be replaced. They are referred to below as organofunctional silicon Designated silanes because they contain both functional groups, such as, for. B. alkoxy groups, that are directly linked to the silicon atom (i.e. silicon functional groups) as well as the organofunctional groups mentioned, which have an or several carbon atoms are bonded to silicon.

In a preferred embodiment according to the invention it is therefore provided that the organofunctional silicon-functional silanes which increase the adhesive force are preferably those of the general formula uses, in which R is a C1 to C8-alkyl radical, which is optionally interrupted by oxygen atoms, such as. B. the -CH2-CH2-O-CH3 radical, R '''is an alkyl radical with 1 - 8 carbon atoms, A is a straight-chain or branched alkylene radical with 1 - 8 carbon atoms, which is optionally interrupted by oxygen bridges, m = 1 or 2 or 3, n = 1 or 2 or 3 R ', if m = 1, H and / or R ″ - NH2 or R ″ - OH (R ″ = alkylene residue with 2 to 4 Carbon atoms) and R ', when m = 2, is H or R "-NH-A Si (OR) n R"' 3-n.

Furthermore, according to the invention, organofunctional silicon silanes of the general formula are used preferably used. In formula II, R, R ''', A and n have the same meaning as in formula I. R' is H or CH3 or C2H54. in which the hydrogen atoms of the amino group are optionally replaced by an amino or polyaminoalkyl radical, e.g. B. the radical [-CH2 (CH2NHCH2) xCH2-] NH2 (x = 1 to 8) are replaced.

The aminosilane preferred according to the invention is # -aminopropyltriethoxysilane, But are suitable, for. B. also f3-Aminoäthyl - # - oxypropylmethyldialkoxysilane or Polyaminotrialkoxysilanes, e.g. B. [(CH3O) 3Si- (CH2) 2] -NH-CH2 (CH2NHCH2) x -CH2NH2 (x = 1 - 8th).

The iminosilane which is preferably used is bistriethoxysilylpropylimine.

Of the imidazolylalkyltrialkoxysilanes falling under the formula II # -Imidazolylpropyltriäthoxysilan may be mentioned in particular. The alkoxy groups the substances mentioned above have the same meaning as those of the formula I.

Amino- or iminosilanes or their mixtures.

In the case of the silanes containing epoxy groups, the epoxy group is either via an ether (-cH2-o-) or an ester Grouping connected to the alkylenesilyl radical. But it is also possible that it is connected to the alkylene radical directly or via a cycloaliphatic ring, or it is part of such a cycloaliphatic radical. The preparation of such silanes is described in DBP 1,061,321. The silanes containing epoxy groups mentioned there can also be used according to the invention. Particularly suitable silanes containing ether bridges are the glycidyloxropyltrimethoxy or triethoxy silanes. Of the epoxysilanes containing ester bridges is the compound particularly mentioned and of the epoxy silanes in which the epoxy group is part of a cycloaliphatic ring, the B-3,4-epoxy-cyclohexyl-ethyltrimethoxy-silane should be mentioned in particular.

According to the invention, silicon-infused silanes which reduce the adhesion force are used those of the general formula Rn - - R'4 - n are used, in which R are identical or different, saturated, straight or branched alkyl radicals with preferably 1 to 10 carbon atoms, R'-halogen, preferably Cl, or identical or different saturated alkoxy groups with 1 to 8 carbon atoms, which may be interrupted by heteroatoms, such as -O- are or an acyl radical, which is connected to the Si.licium atom via an oxygen atom and n = 1 to 3. Preferably | n = 1.

Examples include: propyl-triethoxysilane, propyltrimethoxysilane, Isopropyl dimethoxy -ethoxysilane, n-butyl- or isobutyltriethoxy- respectively.

trimethoxysilane, 4- (3'-trimethoxysilylpropoxymethyl) -1,3-dioxolane, 4- (3'-trimethoxysilylpropoxymethyl) -2-oxo-1,3-dioxolane [1-polyethylene / propylene glycol) -3- (trimethoxysilyl) propyl] acetate or 2 | triäthoxisilyl] -äthylphosphonsäurediethylester.

The alkyl radical R can therefore be of any length and by Sauer.Dtoffatome interrupted or connected ines-position to a heterocyclic ring. It can also contain a carboxyl, sulfonic acid or phosphoric acid residue at the end. Such compounds are e.g. B. in DT-PS 10 69 148, 11 13 455 and 10 90 210 described.

In the case of laminated safety glass, where there is very good adhesion between Silicate glass and plasticized polyvinyl butyral film are desirable in accordance with the present invention only solutions of organofunctional silicon silanes are used. Such laminated safety glasses can include in the construction sector B. as window panes bulletproof glass or in partition walls be used.

On the other hand, the type and the effective solution of the organofunctional silicon Silane or silane mixture is vital when considering laminated safety glass with controlled adhesion in a medium range of the adhesion scale. Laminated safety glass with controlled adhesion can be used in the vehicle sector, zs 3. as glazing material for motor vehicles, rail vehicles, agricultural vehicles, Ships, airplanes etc. can be used.

The method according to the invention has the advantage that the HafJ force a polyvinyl butyral film on inorganic glasses a optimum adhesion value adapted to the respective application can be set can. So z. B. a polyvinyl butyral film, based on a preliminary test it was found that it would become a composite safety pane for the building sector and does not result in an automobile windshield by use a silicon-functional one that has been determined in a preliminary test and reduces the adhesive force Silane can be converted into a "windshield quality".

Conversely, a "windshield grade" polyvinyl butyral film into one with "construction sector quality" by using one determined in a preliminary test organofunctional silicon silane.

Foil waste from the composite pane industry is usually taken from taken back by the film manufacturers and put together after a reprocessing process processed into new film with fresh goods in the extruder.

However, this makes the quality of the new film more uncontrollable Way influenced. In most cases, the waste is not strictly followed beforehand Windshield and construction sheet film quality delivered sorted. An indefinable one A mixture of waste therefore leads to films with undefined adhesion to the glass. According to the invention it is now possible to process unsorted waste into foils and to do so afterwards by means of a suitable combination of the silane types to be used according to the invention to bring the desired value of the glass adhesion.

Experiments with various polyvinyl butyral films of unknown and Ultimately, different quality in terms of liability values have shown that one can achieve the desired goal if one can provide them with solutions, if necessary from a mixture of a silicon-organofunctional that increases the adhesive strength Silane and a silicon-functional silane that reduces the adhesive force.

The concentration of the 511 to be used in the solution or the The type of silane to be used depends on the intended use of the composite panes as well as the properties of the polyvinyl butyral film to be modified. she depends on the adhesion value of the unmodified polyvinyl butyral film.

The adhesion of a pane of glass to a plasticized polyvinyl butyral film is determined after the so-called "fumble test". A laminated glass pane (glass / polyvinylbutyralfoliy ' Glass) with a size of approx. 150 x 300 mm will take approx. 2 to 8 hours at -18 ° C + 0.50 C chilled. It is then placed on an approx. 450 inclined metal block and with hammered with a flat head hammer until the glass is pulverized. The test area is approx. 100 x 150 mm. The adhesion is assessed on a scale from 0 to 10. These values mean: % free film area Pummel value 100 0 95 1 90 2.

85 3 60 4 40 5 20 6 10 7 5 8 2 9 0 10 The visual assessment is facilitated by the fact that in addition to the specified Pummol values on the scale also Images are attached next to the respective Almmelwert. It has shown, that this - not quantitative - pummel test is completely sufficient for practice and that based on the visual assessment, the setting of the can make the desired adhesive force.

A practical embodiment of the method according to the invention consists in that one d.ie silane solutions on at least one of the respective interfaces of the individual layers is applied by removing the plasticized polyvinyl butyral films for example, be guided directly from the role through the solution in which the Silane is present in a given concentration, then the solvent evaporates. These foils treated in this way are not tacky and can also be used handle like untreated foils.

Furthermore, in the method according to the invention there is also the possibility of the silicate glass panes instead of the foils in the same or similar To be treated wisely, however, has the disadvantage that the silane is after evaporation of the solvent is located as a moist film on the silicate surface. In this If necessary, the silane can be stoved by means of a suitable heat treatment.

In this case, however, it is advantageous to proceed in such a way that an in uses a solvent dissolved silane together with a paint binder. The silane-containing lacquer is applied thinly to the silicate glass pane, whereby an organophilic silicate glass surface when this lacquer is then dried arises. The paint application can be done continuously, for. B.

by spraying, squeegeeing or printing and by subsequent Drying in a conveyor oven.

After applying the silane solutions or the silane-containing varnish on the surface of one of the layers to be bonded and the removal of the solvent the foils to be connected are placed on top of each other in the desired order, optionally at elevated temperature in a manner known per se in a pre-composite brought, the laminate is expediently vented. I) afterwards this becomes Pre-composite brought into the final composite under the action of temperature and pressure, e.g. in an autoclave at pressures of about 10 to 15 kp / cm2 and temperatures between about 130 to 150 OC.

A special form of application of the silanes which can be used according to the invention is the production of laminated safety glass using surface-treated Silicate glass panes.

According to the chemical structure of the top layer.

the surface-treated silicate glass panes are to be taken into account the adhesive strength of the film to be used and, if applicable, of the lacquer used The suitable silanes, expediently on the basis of preliminary tests, decide. The laminated glasses, in which the plasticized polyvinyl butyral films treated according to the invention are used will consist of at least one layer of plasticized material treated according to the invention Polyvinyl butyral film. You can use unhardened, hardened, flat, curved, vaporized, printed, colored, etched, structured silicate sheet glass that possibly has a wire insert, as well as colorless, colored, transparent, colored covered, printed, plasticized polyvinyl butyral film treated according to the invention, any inserted wires, wire nets, fabrics or objects, such as Solar cells, included, are produced. The thickness of the silicate glasses or the Plasticized polyvinyl butyral films treated according to the invention are correspondingly The intended use can be selected as required, as can the number of individual layers d.of the composite item. This results in the possibility of application in the construction sector for door and door systems, for window and window systems, for parapets of Railings, balconies or facades, with partition walls as room dividers, balcony partitions or property enclosures, on roofs or roof parts of terraces, light roofs or greenhouse, with cells for telephone or computer systems, showcases, cash registers, Prisons or rooms at risk of explosion or implosion each as safety glass for protection against puncturing, burglary, Shelling, fire, sound, Cold, warmth, heat if necessary with alarm or

Heating wires.

In the vehicle sector, the glazing of motor vehicles, rail vehicles, Ships and airplanes with windscreens, stern or side windows, doors, partition walls etc. in question.

If appropriate, plasticized with those treated according to the invention can be used Polyvinyl butyral films are a multiple composite in combination with other transparent ones Plastics are made.

So are z. B. visual construction types possible, in which in addition to silicate glass and plasticized polyvinyl butyral film as tough elastic materials polymethyl methacrylate, Polycarbonate, polyethylene terephthalate, rigid PVC, polyamide, etc. and as flexible ones adhesive materials Polyurethanes, copolymers of ethylene, polyamides, polyepoxides, Polysiloxanes, polymethacrylates, etc. can be used.

: The examples listed below for the production of the laminated safety glasses according to the invention serve to illustrate and do not represent any restriction with regard to the subject matter according to the invention: Examples 1-19 Plasticized polyvinyl butyral film with high glass adhesion (quality for building glass, Pummel value 10) with solutions was made from Toluene as a solvent and various silanes in various concentrations treated by immersion. The solvent was then removed by evaporation at room temperature. The variously treated films were conditioned to a water content of 0.45%, placed between two glass plates and heated so that a temperature of 900 ° C. could be measured on the glass surfaces. The warm sandwich was passed through a pair of rubber rollers for ventilation. The resulting pre-lamination was then treated in an autoclave at 12 bar, 1400 ° C. for 3 hours, which resulted in flawless laminated glass. The glass adhesion of the films was determined at -20 ° C using the Pummel method: Example Silane Pummel- Example Silane Pummel- worth worth No. % By weight at - 20 ° C No. % By weight at - 20 ° C 1 0 ATAO 10 10 0.1 MEMO 4 2 0.5 "10 11 1" 0 3 1 n 10 I 12 5 "0 4 2 "7 13 0.1 SIFO 1 5 3 "5 14 5" 0 6 5 "3 15 0.1 GLFMO 3 7 5.5 "1 16 1" 0 8 6 "1 17 0.1 ACTMO 3 9 7 "1 18 1" 1 19 5 "0 ATAO = isobutyltrimethoxysilane MEMO = γ - methacryloxypropyltrimethoxysilane SIFO = 2- [triethoxysilyl] ethylphosphonic acid diethyl ester GLFMO = 4 [methyl - 3 '(trimethoxysilyl) -propoxy] -1,3 - dioxolane ACTMOylene = [1- (poly-ethylene) -3- (Trimethoxysilyl) propyl] acetate Examples 20-27 A plasticized polyvinyl butyral film with high glass adhesion (building glass quality, Pummel value 10) was treated with a solution of 3.0 or 5.5% by weight of isobutyltrimethoxysilane (ATAO) in toluene; After the solvent had evaporated to different water contents, the silanized film was air-conditioned.

The laminated glass was produced as in Examples 1-19.

For comparison, laminated glass was produced with an untreated polyvinyl butyral film of the same quality and the same water content. The results are shown in the table below. Example ATAO water pummel value at -20 ° C content untreated treated No. Wt.% Wt.% Film film 20 5.5 0.31 10 1 21 5.5 0.41 10 1 22 5.5 0.64 7 1 23 5.5 0.82 4 1 24 3.0 0.32 10 5 25 3.0 0.41 10 5 26 3.0 0.61 7 2 27 3> 0 0.82 4 1 Examples 28-30 Examples 1-19 were repeated with the difference that instead of toluene, gasoline and xylene were used to prepare a 5% strength by weight solution with isobutyltrimethoxysilane (ATAO). Example solution pump values at -20 ° C medium untreated @ treated No. Slide slide 28 toluene 10 3 29 petrol 10 4 30 xylene 10 4 Analogously to Examples 1 - 30, a plasticized polyvinyl butyral film with controlled glass adhesion (quality for windshields, Pummel value 2) was used and this was treated as described in Examples 1 - 3 [and processed into laminated glass: Example Silane Pummel- Example Silane Pummel- worth worth No. % By weight at -20 ° C No. % By weight at -20 ° C 31 0 IMEO 2 42 0.001 AMEO 2 32 0.0005 "2 43 0.005" 6 33 0.001 "3 44 0.01" 6 34 0.002 "3 45 0.05" 10 35 0.004 "6 46 0.006 GLYMO 3 36 0.006 "6 47 0.03" 4 37 0.008 "7 48 0.09" 5 38 0.01 "10 49 0.6" 5 39 0.02 10 40 0.03 "10 41 0.04 1 10 IMEO = # - Imidazolylpropyltriäthoxysilan AMEO = # - Aminopropyltriäthoxysilen GLYMO = # - Glycidyloxypropyltrimethoxysilan Examples 50-53 A plasticized polyvinylbutyral film used in Examples 31-49 was used with controlled glass adhesion (#pro-imid% IMoxysilane with a solution of 0.01% imide weight IMEO). treated in toluene and conditioned to different water contents after evaporation of the solvent.

The laminated glass was produced as described in Examples 1 - 30: Example water content Pumm @ lw @ rt at -20 ° C untreated @@ treated No. % By weight film film 50 U, 31 3. 10 51 0.41 3 1Q 52 0.64 3 10 53 0.82 2 Examples 54-59 Plasticized polyvinyl butyral film with high glass adhesion (quality for building glass, pummel value 10) was used for the production of laminated safety glass using metal-coated glasses, the vapor-coated glass sides being laid towards the polyvinyl butyral film, ie on the inside. The polyvinyl butyral films had previously been treated with a solution of silane in toluene and conditioned to a water content of 0.45%. Example Glasbeschich- Silan Pummelw @ rte at -20 ° C tung untreated treated No wt% foil foil 54 Auresin # 50/36 5 AMEO 1 7 55 Auresin # 55/42 5 "1 5 56 Metallic 50/47 5 :: 1 2 57 auresin # 50/36 5 GLYMO 1 3 58 auresin # 55/42 5 GLYMO 1 4 59 M @ tallic 50/47 5 GLYMO 1 3 AMEO = -Aminopropyl triethoxysilane GLYMO = # -Glycidyloxypropyltrimethoxysilane Examples 60-67 Plasticized polyvinylbutyral film with high glass adhesion and surface-coated glass as in Examples 54-59 were used to produce laminated safety glass, but a silane-containing lacquer was used. For this purpose, a solution of 2% by weight of plasticized polyvinyl butyral film and 1% by weight of silane was produced. A 1: 4 mixture of dioxane and methyl isobutyl ketone was used as the solvent. The polyvinyl butyral film (Examples 60-63) or the coated glass (Examples 64-67) were treated with this silane-containing lacquer. Before the composite production, the polyvinyl butyral film was conditioned to a water content of 0.45%. Example glass coating silane pummel values at -20 ° C Not treated untreated Slide slide 60 Calorex # IMEO 6 10 61 Parelio # IMEO 6 10 62 Calorex # GLYMO 6 10 63 Parelio # GLYMO 6 10 untreated treated Glass glass 64 Calorex # IMEO 6 10 65 Parelio ## IMEO 6 10 66 Calorex GLYMO 6 10 . 67 Parelio # GLYMO 6 10 IMEO = # - imidazolylpropyltriethoxysilane GLYMO = # - glycidyloxypropyltrimethoxysilane

Claims (4)

P a t e n t a n s p r ü C h e 1. Modification of the manufacturing process of laminated safety glass by joining one or more of them on one or both sides Silicate glass panes with plasticized plastic films with the help of silanes being the silanes dissolved in a solvent are used in the catfish that one these silane solutions on at least one of the interfaces to be connected to one another layers to be connected, the solvent evaporated and then produces the composite, according to patent specification .......... (patent application P 25 49 474. 0), d u r c h e k e n n n z e i c h n e t that one as a plastic film a partially acetalized polyvinyl alcohol film is used. 2. The method according to claim 1, characterized in that the partially acetalized Polyvinyl alcohol film is a polyvinyl butyral film. 3. The method according to any one of claims 1 or 2, characterized in that that the silanes are dissolved in solvent. in quantities | between 0.0001 and 7.0, preferably 0.0005 to 5.0 wt.% Are present 4. The method according to any one of the claims 1 or 2, characterized in that the silanes are dissolved in a lacquer, the amount of silanes in the silane-containing paint being 0.0001 to 2.0% by weight, preferably Is 0.0005 to 1.0 wt%.