CA1111750A - Laminated safety glass and a process for the production thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
The present invention relates to a process for the ma-nufacture of laminated safety glass comprising bonding one or more silicate glass sheets at a temperature of up to 200°C to a poly-vinylchloride foil, an ethylene and/or propylene foil, or a par-tially acetalised polyvinylalcohol foil, bonding being assisted by means of a silicon organo-functional silane and/or a silicon functional silane, with the provisos that when a said polyvinyl-chloride foil is employed, the silicon organo-functional silane and/or silicon functional silane is applied to the surface of a said foil and/or to a said glass sheet dispersed in a lacquer and that when a partially acetalised polyvinylalcohol foil is used, the silicon organo-functional silane and/or silicon functional silane is applied to the surface of said foil and/or to a said glass sheet dissolved in a solvent and/or dispersed in a lacquer, a solvent, when used, being removed after the application to the foil and/or glass sheet surface. The invention is also directed to the laminated safety glass as obtained from the above process.

Description

This lnvention relates to laminated salety cJlass and to a process for the productlon thereof.
The specification of our copending patent application No. 26S.075, filed November 4, 1976 describes and claims a process for the manufacture of laminated safety glass comprising bonding one or more silicate sheets at a temperature oE rom 120 to 200C to a plasticised polyvinylchloride, bonding being assisted by means of a silicon organo-Eunctional silane and/or a silicon functional silaneD
It has now been found that the novel use of the afore-said silicon oryano functional silane and/or silicon functional silane can be extended in a more general manner in the bonding of -`
silicate glass sheets to plastics foils. Thus, the process of the main patent application is also applicable to ethylene and/or propylene foils to be defined hereinafter. The process of the aforesaid patent application is preferably carried out by employing the silane(s) in solution in an organic solvent which may contain a lacquer binder. It has now been found that such a procedure can also be employed with plasticised partially acetalised poly-:
vinylalcohol, especially polyvinylbutyral foils, as well as with the~aforesaid ethylene and/or propylene polymer foils. Moreover, insofar as sil~ane-containing lacquers may be employed, it is not essential for the silane(s) to be in solution in the lacquer solvent; when using foils of any of the three aforesaid types, it is possible for the silane(s) to be suspended in the lacquer solvent.
Thus, according to the present invention, there is provided~a process for the manufacture of laminated~safety 31ass comprising bo;nding one or more silicate glass sheets at a tempera-ture of up to 200C to a polyvinylchloride foil, an ethylene ` ~ ~ and/or propylene foil, or a partially acetalised polyvinylalcohol ~foil, bonding being provided by means~of a si]icon organo-functiona - ~ .

silane and/or a si]icon or functional silane, with the provisos that when a said polyvinylchloride foil is employe~, the silicon organo-functional silane and/or silicon functional silane is applied to the surEace of said Eoil and/or to a said glass sheet dispersed in a lacquer and that when a partially acetalised polyvinylalcohol foil is used, the silicon organo-~unctional silane and/or silicon functional silane is applied to the surface of said foil and/or to a said glass sheet dissolved in a solvent and/or dispersed in a lacquer, a solvent, when used, being removed after the application to the foil and/or glass sheet surface.
The process of this invention can be carried out at autoclave temperatures as high as 1~5 to 200C. The minimum bond-ing temperature employed will usually be 120C and autoclave tem-peratures of 120 to 150 are preferably used, the autoclave temperatures being more preferably from 135 to 145C.
~ s is acknowledged in the specification of the aforesaid copending patent application, it has been known for some time to use bi-functional silanes for improving the bond strength obtained between synthetic resins and inorganic substrates. The silanes have been employed, inter alia, in filled or strengthened synthetic plastics materials, sealing compositions, cements and lacquers. With all the hitherto proposed systems~ the silane serves to improve or largely maintain an existing bond in such ;~ manner that it will be maintained even when subject to the action of molsture or when stored in water.
In contrast thereto~ silanes are used in the present invention to form a bond between a plastics foil and glass which would not exist but for the use of the silane.
Particularly insofar as the use of partially acetalised polyvinylalcohol foils is contemplated herein, it is of interest : ~: '' ' '.

~ 2 -. .
- ':

-7Si~

-that German Offenlegungsschrif-t No. ~,410,153 proposed the use of silanes in conjunction with polyvinyl butyral foi:Ls in the produc--tion of laminated safety glass~ In this case, however, the silane serves -to reduce the already high glass adhesion thereby making the foils easier -to work with and is employed in prede-termined ~uan-tities in the polyvinyl bu-tyral before or during the processing thereof to form a foil. The silane is adrnixed wi-th synthetic resin in a separate processing step~ It is found to be uniforn~y distri-bu-ted over the entire resin and accordingly relatively large amounts of silane have -to be employed. In contrast, as will be shown here-inafter, when using partially acetalised polyvinylalcohol foils, in the process of this invention, an at least equally good effect is produced if only the surface of the layers to be bonded are treated with -the silane(s), this treatment being carried out in solution or dispersion form using considerably smaller amount of silane(s) than those which are required when working in accordance with the procedure o~ German Offenlegungsschrift ~oO 2,410,153.
The use of silane(s) in solution or suspension applied to the surfaces to be bonded has a further advantage that the in-fluence of the water content of the acetalised polyvinylalcoholfoil no longer affects the adhesion of the foil to glass to any significant extent. It has been found, in general, that the adhe-sive capacity of acetalised polyvinylalcohol foils with respect to glass decreases as the water content of the foils increases. By reducing the water content, on the other hand, the adhesive capaci-ty is generally increased. By treating the surfaces of such foils with solutions or susperlsions Or silanes WlliCh incrcase t~le bond strength, reliable long-term adheslon is obtained over a wide range of water contents in the foil up to h~igh water con-tents~ In con-~rast, treatment with silanes which have the effect of reducing .
adhesive capaci-ty will result in the achievement of reliable long-term adhesion over a wide range down to low water con-ten-ts.

: ' Furthermore, the value of plasticised polyvinylbu-tyral foils in the building industry in connection with the production of glass panes for windows has been appreciated for a considerable time because of -the high adhes:ion of such foils -to glass. When sheets of laminated safe-ty glass are used as windscreens in motor vehicles, the adhesion of the foil to the glass mus-t, in contrast, be sui-tably reduced. If in fact the screen is destroyed by impac-t, then when high adhesion of foil to glass occurs, penetration at -the centre of impact occurs without much glass splintering. With poor adhesion, the impacting agent, for example a falling body, is in fact elasti-cally taken up by the foil, but the splintering or shattering is very great. In the event of a collision when the windscreen is des-troyed by impact of the head, the foil should undergo expansion to slowly break down the kinetic energy of the head -falling thereon and moreover the destroyed glass should still adhere sufficiently well to-the foll so that dangetous injury by cuts is av~ided. ~or ~his reason, -~
the power of adhesion in these cases must be adjusted to a defined pummel value ~see hereinafter) range, which is generally from 2 to 5. Such behaviour can readily be achieved when utilising partial-ly acetalised polyvinylalcohol foils in the process of the inven-tion.
Foils used in the process of this inven-tion will pre-ferably have Shore-A hardnesses, measured in accordance wit DI~
S3505 of from ~0 to 98, preferably from 50 to 95. The foils gene-rally achieve such softness b~ the plasticisation thereof,whether by internal plasticisation using plasticising comonomers in the production of the foil-forming polymers, or by use of separately - - added plasticisers. In general, some plas-ticisation is required ~and references herein to foils should always be Gonsidered to im-ply that~plasticisation thereof has occured.
The expression "ethylen and/or propylene foil" is usedherein ~o denote a foil formed ~rom a polymer which is a homopolymer of ethylene or propylene or a copol.ymer of ethylene and/or propy-lene with at least one comomer, the copolymer having a monomer con-tent of more than 30% by weight of ethylene and/or propylene, the remainder, up to 100%, being formed of comonomers which are copo-lymerisable with ethylene and/or propylene. A plasticising comono-mer which may be used with ethylene and/or propylene is vinyl ace-tate. As compared with t~e plasticised partially acetalised poly-vinylalcohol foils hi-therto employed as adhesive foils between glass shee-ts, such copolymers with vinyl acetate have the advantage that they are substantially more cold resistant with respect to impact.
Other co-monomers which may be employed in the produc-tion of ethylene and/or propylene copolymers are olefinically unsa-turated compounds, for example butadiene, alkylvinyl e-thers, vinyl-chloride, vinyl fluoride, acrylic acid, acrylic acid es-ters, for example ethylacrylate and bu-tylacrylate~, maleic anhydride, maleic ~ -.
acid esters and styrene which may be used singly or in admixture. .
Reaction products of these co-polymers, whi.ch are for example form-: ed by hydrolisis reactions or neutralisation reactions wi-th bases so that metal irons are introduced therein-to.
The term "polyvinylchloride" is used herein in a broad sense, unless otherwise indic.ated, to means homopolymers, copoly-me:rs with one or more olefinically unsaturated monomers and graft polymers of vinylchloride as well as reaction products thereof.
Preferred polyvinylchlorides for use in the proce~:s of thls i:nvention:are polyvinylchlorides with a K-value of from 50 ko 80, more~prefcrab:ly :~lom 60 to 75~.~ In addition to holnopolymers of vinylchloride, lt is possible -to use copolymers of v1nylchloride with othe~r ethylenically unsaturated hydrocarbons, for example ethyl-ene, propylene, isobutylene, 2-methyl-but-2-ene, butadiene and sty rene,;ethylenically unsaturated:halogenated hydrocarbons, for ex-ample vinyl fluoride, tetrafluoroethylene and other relatively high , fluorinated olefines, vin~liclene ch:Loride, trichlorethylene, 2-chloro-prop-l-ene and other chlorina-ted higher olefines, halogenated butadienes, halostyrenes, e-thylenically unsatura-ted alcohols and ethers, for example vinyl alcohol vinyl methyle e-ther, vinyl ethyl ether, vinyl isobutyl e-ther and other higher vinyl a~kyl ethers, allyl glycidyl ehters; ethylenically unsaturated acids and acid derivatives, for example vinyl acetate, vinyl s-tearate, vinyl olea-te and other vinyl esters of higher fat-ty acids, vinyl esters of alko-xy acids, allyl esters, methyl or ethylesters of acrylic ac~d, acry-lic es-ters of higher alcohols, acryloni-trile, methacrylic acid es-ters, olefine-dicarboxylic acids and their esters, and ethylenical-ly unsaturated compounds which contain hetero atoms such as nitro-gen, phosphorus, sulphur or tin. Copolymers of vinyl chloride and two or more such monomers can also be used~ It is also possible to use graft polymers of vinylchloride, reaction products, in particu-lar chlorination products,of homopolymerised vinylchloride or of the copolymers or graft polyrners of vinylchloride as aforesaid, one such reaction product bein~ post-chlorinated polyvinylchloride, or mixtures of such polymers derived from vinylchloride with each other or even with polyvinylidene chloride.
~ Especially suitable for use in the prac.tice of this in-vention are those foils which contain polyvinylchloride and which contain polymers miscible with the latter preferably present in an amount of not more than 50/O by wei~ht and not produced from vinyl-~ chloride. Examples of such polymers are polyvinyl acetate, copo-: Iymers of vinyl àcetate and ethylene, acrylonitrile-butadiene-sty-rene polymers and methacrylonitrile-butadiene styrene polymers.
~ Examples of external plasticisers which may be used in the ethylene and/or propylene foils or polyvinylchloride foils ; ~30 utilised i~ the process of this invention are esters of phtalic acid, more particular dioctyl phtalate, esters or aliphatlc dicarboxylic acids, especially of sebacic or adipic acids, esters oE phosphoric .~

.

acid, particularly trioc-tyl phosphate and polymer plas-tic.isers, in particular those based on bu-tadiene, acrylonitrile, s-tyrene arld po-lyesters.
In one working procedure emhodying this inven-tion appli-cable to the use of ethylene and/or propylene foils and ~artially acetalised polyvinyl alcohol foils, -the adhesi.on-promoting silanes are dissolved in solvents, and the solution which is obtained is applied by dipping spraying or similar simple me-thods, to at least one of the relevant boundary surfaces. ~fter -the application of the solution, the solvent is preferably removed prior to the brin~
ing together for bonding of the separate layers.
In a particular preferred procedure, the silanes are applied to at least one of the boundary surfaces of layers to be bonded, for example the plastics foil, by guiding the foil through a solution of the silane. The silane solution will contain the silane(s) in suitable concentration. Thereafter the solvent is evaporated off. When it is the foils which are treaded in this way, : they are not tacky and are capable of being handled in -the same way as untreated foils. It is, however, also posslble for the silica-te glass sheets to be treated with the silane solution. In such a :~ case, there is the.disadvantage that, after the vaporisation of the solvent, the silane(s) will remain as a moist film on the surface of the silicate glass. The silane(s) can be prevented from loss from -the glass surface by subjecting the glass surface to a suitable heat treatment. In a particularly preferred procedure, the silane solution applied to the glass surface additionally contains a lac-qucr-forming binder. The silane-containing lac~uer is thi.nly ap-plied~to the Sl licate glass sheet and an organo silicate glass surface ~ is formed on subsequent drying of this lacquer.
30 : It is also possible to apply such a silane~containing lac~uer to:the foil employed using one of the procedures referred .:
to above in connection wi-th the application of silanes dissolved . ~:
:

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' - .
. : : ,; ~ : ....

only in solveIlts. For exarnple, such appl.icati.on may be carr.ied out continuously in an immersion bath equipped with squeezing rollexs followed by drying in a continuous heating or pusher~type furnace.
The manufacture of -the foil can in this case also supply a ~ull.y prepared foil to the manufac-ture of the lami:nated glass~
Insofar as the use of silane-containing lacquers is con-templated, it is not even essential -that all the silane may be dis-solved in the lacquer solven-t. A dispersion of the silane(s) in a lacquer-forming material may be employed. In such case, the si-lane application procedure:is also applicable i.n accordance with the presen-t invention to polyvinylchloride foils. :
Examples of lacquer binders which can be used in the practice of this invention are non-hardening polymethacrylates and acrylates, solubles, non-reacted polyurethanes, post-chlorinated polyvinylchloride and vinylchloride/vinyl isobutyl ether copolymer.
Lacquer binders particularly effec-tive in achieving a g~od glass to foil bond are those which contain free -OH andjor --COOH groups. Examples of such preferred lacquer binders are par-tially hydrolysed copolymers of vinylchloride and vinyl acetate 20 vinylchloride-vinyl acetate-vinyl alcohol terpolymers, vinylchlo- :
ride-hydroxyalkyl acrylate copolymers, vinylchloride-vinyl acetate-unsaturated carboxylic acid (e.g. maleic, acrylic or methacrylic acid) terpolymers and vinylchloride - unsaturated carboxylic acid alkyl ester - unsaturated carboxylic acid terpolymers. These like the lacquer binders already mentioned herein are readily available commercially.
Since reactive groups, in particular carboxyl groups, will affect the light and thermal stability of the bonds produced -OH and -COOH group - containing lacquer binders are pre~erably .
used -together with less reactive bonding agents which must, of course, be compatible therewith. Examples of the less reactive . .~-bonding agents are copolymers of vinyl chloride and ~inyl acetate or unsa-turated carboxylic acid al~yl esters, as well as natural or synthetic rubber.
Irrespective of whether or no-t a reactive lacquer binder is employed in a silane containing lacquer, and whether separate plasticisers are employed, stabilisers and o-ther auxiliary ma-terials will usually be present, the total amount of involatile components in the silane-containing lacquer is preferably from 1.0 to 20% by weight, more preferably from 2.0 to 15% by weight. The volatile components ~of the lac~uers will be organic solvents which will be referred to hereinafter in connection with the use of silane-contain-ing solutions in general. ..
Insofat as the use of ethylene and/or propylene :Eoilsis contemplated herein, it is also possible to employ ethylene and/
or propylene foils which contain the silanes in a homogeneously dis-tributed form. In this case, the silanes are supplied either as such or dissolved in a solvent to the moulding compositions from which the foils are produced. When using this procedure, there is, of course, no need to provide silane surface coatings on:the pre-: pared foils or on thé silicate glass sheets. For producing a homo-

2~0 geneous distribution of the silanes in the foil, the silanes canalso be initially dissolved or finely dispersed in a plasticiser to be added to the foil-forming composition and added together with the plasticiser and possibly other conventional additives, for ex-ample stabilisers, light~protection ac~ents and dyestuffs to the ; compos1tion which is to be shaped. The mixing together of the c.om- ~ .
ponents:from which the foil is to be produced can be carried out -on conventlonaI equipment, for example, in co-kneaders. .~ :

The foils employed in the:process of this invention are :: :

preferably transparent, although opa~ue foils may be employed, de-pendlng on the purpose for which it lS lntended that the laminated :
:~ safety glass is to be used.

~ q'he choice of silanes employed in the practice of the 9 ::
::

present invention will be as follows:
a. silanes or silane mixtures which produce a strong adhesion of foil to glass, as required in -the build-ing indus-try and/or b. silanes or silane mixtures which produce a lesser s~trength of adhesion as may 'be used in laminated safety glass for motor vehicles.
In general, silicon organo-func-tional silanes tend to increase the bond strength obtained while silicon-functional silanes lower the bond strength and the silane or combination of silanes to be employed will generally be selected in accordance wi-th the intend-ed use of the product produced.
Silicon-functional silanes are compounds containing a functional group, for example a halogen or al}coxy group, directly linked to the silicon atom. Such groups are generally capable of being easily hydrolysed.
Silicon organo-functional silanes are essentially at least bi-functional. As well as containing at least one hydrolys- ~ -I able group, which is usually a halogen or alkoxy group, which is to 2a react in the bond with the glass surface, at least one functional ::
group is present which is bonded through one or more carbon atoms .
to silicon and is reactive, for example, because of the presence :
of amino or~epoxy groups therein or because of double bonds.
The silicon organo-functional silanes to be employe~ in the process of this~invention will gene~rally possess the general ~ -formula:- ~
~ :
Rn ~ Sl - A ~ z wherein R is a hydrolysable radical, for example halogen, especial-ly chloride, or 0~ wherein R denotes an alkyl radical containing Erom l to 18 carbon atoms, the carbon atoms of which w~en two or ~:

:

more are presen-t in -the radical being possibly interrup-ted by hetero atoms, for example O or S, or an acyl radical, Riii is an alkyl rad:ical containing from 1 -to 18 carbon a-toms, A is a s-traight-chain or b.ranched alkylene radical corl-taining from 1 to 10 carbon atoms, pre-ferably from 2 to 6 carbon atoms and which may be interrupted by hetero atoms;
A represen-ts a radical containing a functional group, for example CH-~H2, -C=C-, halogen,~(NR3i rn) or - N - C - Riv H2 ~ ~
~2 wherein Ri is hydrogen or a group of formula ~Rii-NH2 or -Rii -OH
wherein Rii is an alkylene radical containing from 2 to 8 carbon atoms': two radicals Ri when represent ,~belng the same or different, and RiV is methyl or ethyl, . m is 1, 2 or 3, n is 1, 2 or 3, and ~20 p lS 0 or 1 provided that Z is linked to -the silicon atom through at least one carbon atom forming par-t of A or Z.
The silicon organo-functional silanes utilised in -the practice of this invention are preferably alkylene-alkoxy silanes which contain amino and/or imino groups or:contain epoxy groups~
when the silane contains an amlno group, it is possible in this case for one or both hydrogen atoms of the amino group to be re-;: placed by an amino- or hydrosyalkyl radlcal or by a polyamino radi-cal.
One preferxed class o silicon organo-functional silane -for use in the process of -this invention to improve the bonding fo:~ce between the aforesaid plastics foils and silicate glass sheets consists of compounds of the general formula:
:

~(RO)n ~ Si - A 1 3-m _ 3-n m in which R is an alkyl radical containing from 1 -to 10 carbon atoms, the carbon atoms when -two or more are presne-t in ~he radical being possibly interrupted by he-tero atoms, Riii is an alky radical containing from 1 to 8 carbon atoms, A is a straight-chain or branched alkylene radical contairling from 1 to 8 carbon atoms, and which may be interrupted by hetero atoms, m is 1 or 2 or 3, n is 1 or 2 or 3, and in which Ri is a hydrogen atom, a group of formula -Rii -N~I2 or -Rii -OH

wherein Rii is an alkylene radical containing from 2 -to 4 carbon atoms or a polyaminoalkyl radical when m is 1, and Ri is a hydrogen atom or a group oE formula -Rll - NH-A Si (OR)n Riii '

3-n wherein Rii, Riii, A and n have the aforesaid meanings when m is 2.

Hetero atoms in R and A preferably oxygen.
~Another preferred class of silicon organo-functional ~ .:

20 silanes which:may be used consists of compounds of -the general ..
formula:

)n ~ C - RIV

Riii H2~
~: 3-n \ /

2 :~
wherein R, Riii, A and n have the aforesaid meaning and RiV is a hydrogen~ atom or a methy~ or ethyl group.
~ Partlcularly preferred aminosilanes are compounds of : general formula:

~30: MH2-(CH2)n-Si~(oRV)3 in which n is an integer of from 2 to 6 and RV is an alkyl radical containing from I to 8 carbon atoms. Alkyl radicals Rv can be : , .

.

branched or unbranched and possibly interrupted by hetero atoms when containing more than~one carbon atom, in for example -the radi--cal -CH2-CH2-0-CH3. Specific examples of these compounds are ~'-arnlnoe-th~l -trialkoxy silanes. In -the compounds of generaL formula III, the hydrogen atoms of the amino group may be replaced by an aminoalkyl or polyaminoalkyl radical (e,g. the radical L -CH2 -CH2 ~-ICH2)XCH2-~-NH2 wherei.n x is an integer of from 1 to ~. The ami-nosilane of -this sub-class which is most preferred for use in -the practice of this invention is ~--aminopropyl -triethoxy silane. O-ther aminosilanes of -this sub-class which can be used are ~-aminoethyl-~-oxypropyl methyl dialkoxy silanes and polyamino trialkoxy silanes, for example compounds of formula L(CH20)3Si(CH2)2 ~ I-CH2(CH2~I
CH2)X-CH2NH2 wherein x is an integer of from 1 to ~.
General formula I also includes within its ambit imino-silanes preferred examples of which are compounds of general for-mula:
H~[CH2-CH2--CH2--Si(OR)3~2 in which.RV has the aforesaid meaning.
A particularly preferred iminosilane is bis-triethoxy-silyl propylimine.
Examples of sllanes of general formula II which may be employed in the practice of this invention are the r-imidazolylpro-pyl trialkoxy silanes in which the alkyl moiety of the alkoxy group has the same meaning as the aforementioned radical RV. A particu-larly preferred compound of this class is ~-imidazolylpropyl trie-thoxy silane.
Use may also be made, as above-rnen-tioned, of silanes which contain epoxy groups. ~he epoxy group CH~-CH
c~

be bonded either by way of an ether grouping, (-CH2-0-) or an es-ter grouping, (-CH2-0-1-0-), to any alkylene silyl radical. However, - - .

. . - : ~ :
~ . . . : , -: :
.

7~

it is also possible for the epoxy ~roup -to be bonded directly or by way oE a cycloaliphatic rin~ to the alkylene radical, or for it -to be a consti-tuent of such a cycloaliphatic radical. The preparation of such silanes is described in German Paten-t Specification No.
1,061,321. The silanes mentioned therein and containiny epoxy groups may also be employed in the practice of this invention. Si-lanes which contain ether bridges and which are particularly suitable glycidyloxypropyl trime-thoxy or triethoxy silanes. ~ preferred example of epoxysilanes which con-tain es-ter bridges is -the compound C~ -CH2-0-1CI-O (CH2)3 3 3 An example of an epoxy silane in which the epoxy group is a cons-tituent of a cycloaliphatic ring is ~--3,4-epoxycyclohexyl-ethyltrimethoxysilane.
Of the compounds rnentioned above, the ~-imidazolylpro-pyltriethoxysilane and the r-glycidyloxypropyltrimethoxysilane are preferred for use as silicon organo-functional silanes which in-crease the bond s-trength. ~
As will be appreciated from the foregoing, it is also `' possible to employ silicon organo-functional silanes wi-th olefini-cally unsa-turated bonds, for example silanes which contain vinyl, propenyl, acryl or methacryl groups. These silanes can only be used to produce an increase in the bonding power when they are used together with radical formers. ~ot only is the bonding power no-t increased without addition of radical formers, b~-t it may under~
go a slight reduction.
li,xamplcs of radical formers which rnay be employed in-clude the compounds usually employed in the radical polymerisation of olefinically unsaturated compounds, especially peroxides, for example~ dicumyl peroxide. The radical formers are generally employ-e~ in quantities of from 0.01 to 1% by weight, preferably from 0.01 to 0.5~0 by weight, calculated'on the solvent or lacquer COmpOSitLQr '~ employed. Examples of these~

.

silanes are vinyl trialkoxy silanes, for example viny:L trimethc~xy silane, vinyl -trithoxy silane, r-methacryloxypropyl -trial]coxy sila-nes, for example the trimethoxy or trie-thoxy silanes, vinyl-tris-~-methoxyethoxy silane or vinyl triace-toxy silane.
In laminated safety glass produced according to this invention and wherein very good adhesion is required between sili-cate glass and foil, only silicon organo-functional silanes will generally be used. Such laminated safety glasses can be used, inter alia in the building industry, for example, as window panes, armoured glass or in partitions. Lamina-ted safety glass with a quali-ty of bonding lying in a middle region of the adhesion scale according to the pummel test are used in the vehicle industry, for example as glazing material in motor vehicles, rail vehicles, agri-cultural vehicles, ships and aircraft. In -these fields of applica-tion, the bonding power requirecl for the specific purpose of use can be adjusted by varylng the type and quantity of silane used.
Obviously, it is necessary to take into account, in addition, the bonding power of the plastics foil in -the absence of any silane at all. By the use of one or more silanes in varying proportions it is possible to obtain the bonding strength which is required.

If the bonding pGwer of a foil treated with a silicon organo-functional silane istoohigh for a particular purpose of use-then it is i~pos-sible to employ a silane or silane muxture which reduces the bondin~ pcwer as the only silane component; a silane-functional silane as herein defined -~
will generally be employed in such a case either alone or as a si~nificant component of a mixture thereof with a silicon organo~functional silane.
The bonding power of a glass sheets to a shaft foil used as an adhesive :eOil and ~ormed of one of the aforesaid plastics 30~ materlals is determined by the so-called "pummel" test. In this test, a test element, with a size of about 150 ~ 300 mm is chilled . .
for about 2 to 8 hours at say -18C + 0.5C, laid on a metal block ' ; ~ -15-., , , . . . , , , ~

7~i~

sloping at about 45 and hammered with a flat headed hamme.. until the silica-te glass disintegrates. The test surface has a si.ze of abou-t 100 x 150 nlm. The adhesion of the foil to the ylass i5 visual-ly evalua-ted in accordance with a scale of from 0 to 10 whose values represent:
% free film surface _ ~u~ne~ value 100 o 2 ~ 9 : The visual evaluation is facilitated by the fact that the indicated pummel values are also suitable for setting out to scal~e on diagrams. It has been found that this pummel test, which is not quan-titative, is fully adequate for practical purposes,and that the adhesion can be judged sufficiently ~ccurately by visual evaluation.
Silicon-functional silanes Eor use in the process of this invention include compounds of the general formula R - Si - R~i~ - n in which R xepresents a straight-chain or branched alkyl radical ~ containing from 1 to 18 carbon atoms, preferably from 1 to 10 car-: bon atoms, RVi represents a halogen atom, preferably a chlorine 30~ atom, or~an alkoxy group containing from 1 to 8 carbon atoms which, :: when containing a plurality of carbon atoms, may be in-terrupted by : one or more hetero atoms, such as oxygen or sulphur, or an acyl ~16--l7~3 r~dical, which is bonded th~ough an oxyg~n atom -to the silicon atom, and in which n is 1, 2 or 3, pre~erably 1. When a plurali ty of groups R and/or RVi is/are present, they may be the same or diEferen-t.
The following are exa~ples of silicon func-tiona~ silanes of the aforesaid general formula: propyltriethoxysi:Lane, propyl trimetho~ysilane, ispropyl dimethoxyethoxy silane and n-butyl or isobutyl-triethoxy or trime-tho~y silane~ ox isobutyl triacetoxy si~
lane, Solvents with whlch the silanes are utilised will be those within which the sila~es exhibit good solubility~ when silane solutions are to be employed~ The solvents should undergo ready vaporisation after the foils have been treated, In addition, the solvents should ha~e good wet-ting po~rer for -the plastics foils wi-th-out causing their dissolution, Such properties are possessed 9 for e~ample, by aromatic hydrocarbons" for`c~amole toluenes or x~lene, like petroleum ethers, as well as alk~l esters fo alipha-tic car~
boxylic acids, for example e-thyl ace-ta-te or butyl acetate, It is also possible to employ alcohols 9 ~or example isopropanol 9 or ke-tones for qxample msthylisobutyl ketoneO A comblnation of sol-vents may also be employed, The ~ount of silane employed will generally depend upon the bonding effect required, Insofar as solutions are to be employ-ed~ it will also depend upon the solubilit~ of the silane in the solvent~ In general, when silane solutions are employed 9 total si-lane concentrations of from 0,0001 to 10% by weight 9 preferably from 0,0005 to 7% by weight~ based on ~he solvent may be ernployedO When par-tially acetalised polyvin~lalcohol foils are being employed, the concentration of silane in solutlon will generally be from 0,0001 30 to 7~0~o by weight, preferably from 0O0005 to 5O0~ by we1~ht based on the solvent, Particularly~when employing ethylene ancl/or pro~
pylene foils9 the to-tal silane concentration in solutions thereof .. . . .
.
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iS preferably from O.O:L -to 10% by weight "nore preferably from 0.05 to 770 by wieght o~ the ~ol~en-li. Irrespec-tive of wh~ther th~y are dissol~ed in an organic sol~ent or dissolved or dispersed in a lacquer~ wh~n the foil i3 an ethylene a~d/or pro~-)ylen~ :foi:L~ -the silicon organo-func-tional silane is prefer~bly elllployed in ~n amounl of from 0.0001 to 7~to~ more pre~erably from C).0005 to 5%~ based on the weigh-t o~ sol~en~ present. Such values are also applicable to ~`
the case where a polyvinyl chloride film is employed and a suspen-sion or organo functîonal silane in a lacquer is used. When partial-ly acetalised polyvinylalcohol foils are employed, it is sufficient for a silicon organo~functional silane to be applied in an amount of from 0.0001 to 2%, preferably from O.OOOS to 1% by weight based on the weight of solvent present. In general, the silicon-functional sil~nes may be employed in amoun-ts of from 1 to 10, preferably from 2 to 7% by weight of the solvent present.
When using lacquers whose binders contain free hydro- ~`
xyl and/or carboxyl groups, the amount of silane employed will generally be less than otherwise as indicated herein. In such cases, :~ ~ when using silicon organo-functional silanes containing epoxide groups, it is sufficient for -the silanes to be employed in the . ~.
lacquer in amounts of from 0.001 to 5% by weight, preferably from 0.001 to 2% by weight based on the solvent. When silicon organo-functional silanes containing amino groups are employed, the silanes ~: are preferably employed in the lacquer in amounts of from 0.0001 ~:
~: to 2% by weight,~more preferably from 0.0005 to 1% by weight, based on the solvent.
When silanes are added directly to an e-thylene and/or : ~
. ~ propylene foil-forming composition prior to the thermoplastic de-~; : forming thereof into a foil, the silane quantity employed is pre-ferably from 0.1 to 5.0% by weight, more preferably from 0.5 to 3% by weight of the other components of the foil-forming composi-tion. When external plas-ticisation of foils is carried out, the : ' ` ~
~ -18-~ ~ .

total amount of plasticiser employed preferably amoun-ts -to from 10 to 65 par-ts by weight, calcula-ted on 100 parts by weight of the foil-forming polymer.
In addition to the various binde:rs indica-ted hereinabove, i-t is poin-ted ou-t -that when using par-tially acetalised polyvinyl-alcohol foils, a particularly suitable binde:r for use in a lacquer is a partially acetalised polyvinylalcohol which preferably corres-~onds in its composi-tion to tha-t of the foi.l. itself which is being employed. In principle, however, when using partially acetalised 10 polyvinylalcohol foils, it is also possible to employ other of the aforementioned film-forming binders, especially those which contain free hydroxyl and/or carboxyl groups.
In laminated glasses produced by the process of this invention and comprising at least one film l.ayer formed of a plas-tics material as aforesaid, the silicate glass used can be unharden-ed, or hardened, flat or curved, vapour-coated, printed, dyed, etch-: ed, or structurised. The glass can be provided with a wire insert.
In addition, it is possible to use colourless, coloured bu transpar~ :
ent or coloured and transl.ucent, foils which contain the particuIar . ~:
20 ~olymer and which may be printed. The foi1 may con-tain inlaid wires, wire meshed, woven fabrics or objects, for examplè solar cells.
The thicknesses of the silicate glasses and of the foils formed from the various polymers and modified or treated in : ~ accordance w.ith the invention can be selected as required. Like- ...
wise, the number of the separate layers of the laminated article .
can be selected as required. As a result, laminated glass can be : produced for use in the building indus-try in doors and door ins-tal~
:
lations, balconles or facades, ln ~artitlon walls for use as room : dlviders, balcony dividers or enclosures of premises, in roofs or ~ ~.
~: 3~ roof sections of terraces, light-transmissive canopies or green-houses, ln cornpartm~nts for telephone or computer installations, showcases, cash offices, prisons or rooms where there is danger of --19~
j : .
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explosion or implosion, as well as a safety ~lass for protection against burglary, larceny, firing of firearms, fire, sound, cold, warm-th, heat. It may be necessary in some of these cases for alarm or heatin~ wires to be incorporated.
Laminated glass may be produced by the process of this invention for use in the glazing of motor vehicles, rail vehicles, ships and aircraft, particularly as wind-shielding, stern or side windows, doors and partitions. In certain cases, the foils contain-ing the various polyrners and rnodified or treated in accordance with the invention may ~e used to produce a multiple lamination in com-bination with other transparent synthetic plastics materials. Ac-cordingly, other types of laminated structures become conceivable.
Such structures may contain, as well as silicate glass and foil, polymethyl methacrylate, polycarbonate, polyethylene terephtalate, hard polyvinylchloride, polyamide layers whlch are tough elastic materials or plasticised polyvinyl butyral, polyurethane, copolymers of ethylene, polyamides, polyepoxides, polysiloxanes and polymetha crylates as soft elastic adhering ma-terials.
~ The following Examples,in which all parts and percent-ages are expressed on a weight basis, unless otherwise indicated illustrate this invention. For succinctness many of the silanes mentioned in the Examples are identified frequently by abbreviations names identified in the Examples.

Foils having a thickness of 0.4 mm were produced from various copolymers of ethylene and vinyl acetate and treated with ~ .
sllane solutions by dipping or irnrnersion therein.
Toluene was chosen as solvent for the silane since this could be ~eadily vapourised before the further processing of the treated foils. The foils were thereafter placed between two glass sheets,~the assembly was passed through a pair of rubber rollers at ambient temperature to remove air therebetween and then heated in an autoclave at 12 bars and 170C for 1 :L/2 hours, 90 that a defect-free laminated glass was formed. The adhesion of -the foils to the glass was deter.mined by the pummel me-thod carried out at -20C, 23~C and -~90C.

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IME.O = Y-imldazolylpropyl -triethoxy silane GLYMO = ~-glycicyloxypropyl -trime-thoxy silane VTEO = vinyl triethoxy silane VTMO = vinyl trime-thoxy silane MEMO = ~'-me-thacryloxypropyl trimethoxy silane ) Shore-A hardness = 97 ) Shore-A hardness = 79 Examples 15 to 22 The procedure of Examples 1 -to 14 was repeated, but with the difference that the autoclave process was carriecL out at 12 bars and at 140C for 3 hours. The following results were ob-tained in the pummel test.
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Examples 23 to 27 The procedure of Examples 1 to 14 was again repeated but using the following foilso 1) Foils of a copolymer of ethylene and bu-tylacrylate (obtainable commercially under the name Lupolen A 2710 ~, made by BASF and having Shore-A hardness of 87).
2) Foils of a qua-ternary polymer of ethylene, and addi-tional olefine, acrylic acid and acrylates ~obtainable commercially under the name *
Lupolen A 2910 MX and having a Shore-A hardness of 94).

The pummel values of the produc-ts obtained were as follows:

TAB~E 3 __ _ _ Example Copolymer Silane % Pummel value at No. by wt. -20C ~23C +90~C
. . _ ~ - _ _.
23 A 2710 HX none O 1 7 24 ll 1% IMEO10 10 10 A 2910 MX none 10 10 10 :~
26 ll 1% ATAO10 10 10 . ..
20: : 5yO ATAO 1 5 IMEO = ~-imidazolylpropyl triethoxy silane -~
ATAO = isobutyl -trime-thoxy silane Examples 28 and 29 The basic working conditions of Examples 15 to 17 were utilised in further repetitions of the process of Examples 1 to ~4, but wi-th the fur-ther difference -that the silanes were not used in pure solv~nt, but in lacquers.
One lacquer (Lacquer 1~ contained, as binder, a partial- -ly hydrolysed copolymer of vinyl chlori:de and vinyl ace-tate contain-ing vinyl alcohol groups ~obtainable commercially under the name Vinylite VAGH of Union Carbide Corporation), 2S% by weight of diso-:~ : * Lupolen and Vinyli-te are trade marks.

~ 25 -~.--'~ .' ~ ,, .

decyl phtalate as plasticiser, hased on the weight of the copolymer,a stabiliser system for the copolymer and methyl isobutyl ketone as solvent. The lacquer contained 10% by weigh-t of binder composi tion, tha-t is copolymer ~ plasticiser -~ stabiliser, and 1% by weight of ~-imidazolylpropyl trie-thoxy silane (IME0).
A second lacquer (lacquer 2), was prepared, using the aforemen-tioned plasticised and stabiliser Vinylite VAGH copolymer and ano-ther copolymer, being a -terpolymer of vinyl chloride, vinyl acetate and maleic acid (obtainable commercially under the name Hos-taflex*M 133 from Hoechst AG). This latter polymer was plasti--cised and stabilised in the same manner, the rela-tive proportions by weight of the two copolymers VAGH and M 133 being 24:1, while the proportion of binder composition (copolymers ~ plasticiser +
stabiliser amounted to 15% by weight the lacquer also contained 1% by weight of r-glycidyloxypropyl trimethoxy silane (GLYM0)u Foils having a thickness of 0.4 mm and obtained from a copolymer of ethylene with 26% by weight of vinyl acetate were treated with these lacquers by dipping. After -the evaporation of the solvent, the treated foils were laid be-tween two glass sheets.
To extract the air entrapped in the assemblies, the assemblies were passed through a pair of rubber rollers and further processed in an autoclave at 12 bars and 140C over a period of 3 hours to pro-vide defect-free laminated glasses. The foil adhesion was establish-ed by the pummel method and gave the following values:

_ _ _.__ Example Lacquer Pummel values at No. No. -20C ~23~C -~90C
. __ .
28 1 10 10 ~0 2g 2 10 10 10 _ _ _ _ _ ~ _ xa~æ~

; Foils having a thickness of 0.4 mm were produced from * Trademark , .
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a copolymer of ethylene and 26% by welght of vinyl acetate and uti-lised in the production of laminated glass by the procedure of Example 16 using a 1% by weight solution o:E ~-imidazolylpropyl trie-thoxy silane (IME0) in -toluene.
In addition, plas-ticised polyvinyl butyral (PVB) foils with a thic~ness of 0.~ mm and showing good adhesion to glass (building glass quality) were air-conditioned to a moisture content of 0.45% by weigh-t and likewise processed to form a lamina-ted glass.
Both types of laminated glass were thereafter subjected to a ball~dropping test in accordance with DI~ 52 306, carried out at temperatures of +23C and -20C, using a steel ball weighing 227 g. The results obtained are set out in Table 5. As may be seen Table 5, when using -the external plasticiser-free foils of a copolymer of ethylene and 26% by weight vinyl acetate, laminated safety glasses were produced which, as compared with those consist-ing of plasticised polyvinyl butyral, were particularly resistant in the cold to the effect of impac-t. The safe droppi.ng height of .
he bal was about twice as high at a temperature of -20C.

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Examples 31 to 39 Plas-ticised polyvinyl butyral foil having a high glass adhesion (quali-ty fox building glass, pummel value 10) was coated with solutions consisting of toluene as solvent and various silanes in various concentra-tions by dipping or immersion. The solvent was thereafter removed by evapora-tion at room -temperature. The various-ly treated foils were air-conditioned to a wa-ter con-tent of 0.45%, placed between two glass plates and heated to such an extent that a temperature of 90C could be measured on the glass surfaces, The 10 warm sandwich obtained was passed through a pair of rubber rollers for air extraction. A preliminary bond was fo~ned which was improv-ed by treatment in an autoclve at 12 bars, 140C, for 3 hours, as a result of which a flawless laminated glass was formed. The glass adhesion of the foils was determined at -20C, using the pummel meth-od which gave the following results:
~ABLE 6 . . _ .
Example No. Silane % by weight Pummel value at ~20C
31 0 ATAo 10 32 0.5 " 10 20 33 1 ' 10 37 5.5 " 1 38 6 " 1 0.1 ~EM0 4 41~ 1 " 0 42 5 " 0 43 0.1 SIF0 1 ~4 5 " 0 0.1 GLFM0 3 46 1 " 0 30 47 0.1 ACTM0 3 48 1 " 1 ~9 5 " 0 :: ~ __ ,, . :: .

5~

ATAO - isobutyl trimethoxy silane MEMO = ~-m~thacryloxypLopyl trimethoxy si:Lane SIFO = 2-[triethoxys:ilyl~-ethyl phosphonic acid diethyl ester GLFMO = 4 me-thyl-3'l(-trimethoxilyl)-propoxy]¦-1,3-dioxolclne ACTMO = ll-polyethylène/propyleneglycol)-3-(trimethoxysilyl)-propyl]-aceta-te Examples 50 to 57 A plasticised polyvinyl butyral foil having high glass adhesion (building glass quality, pumrnel value lO) was treated with solutions of 3.0% by weight or 5.5% by weight respectively of iso-butyl trimethoxy silane (ATAO) in toluene, after evaporation of the .
solvent to different water contents, the silanised foll was air~
conditioned. :: :
The manufacture of the laminated glass was carried out by the procedures of Examples 31 to 49. ~or comparison purposes, laminated glass was prepared with an un-treated polyvinyl butyral foil of the same quality and of the same water content. The results obtained are apparent frorn the following Table.

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_xamples 58 to 6_ The procedure of Examples 31 to 49 was repeated, wi-th the difference tha-t petroleum ether and xylene were used in addi-tion to toluene for the prepara-tion of a 5% by welgh-t solution of isobutyl trime-thoxy s.ilane utilised solution. The following results were obtalned in -the pu~nel -tes-t~

_ _ Example No. Solvent Pummel values at =20C
untreated -foi.l ¦ treated foil _. _ . . _ _ ~0 58 toluene 10 3 59 petroleum 10 4 ether oO xylene 10 ¦ 4 Examples_61 to 79 A plasticised polyvinyl butyral foil with controlled glass adhesion (~uali-ty for windscreens, pumm~l value 2) was used in a repetition of the procedure of Examples 31 to 49. The foil was trea-t-ed as described in Examples I to 30 and processed to form laminated glass having the following pummel behaviour:

_ _ ~
Example No. Silane /O by weiqht Pwmrnel value at -20C

62 0.0005 " 2 63 ~ 0.001 " . 3 64 0.002 " 3 O.004 IME0 ~ 6 66 ~ 0.006 " 6 67 0~0~8 " . 7 ~3o 63 :: 0.01 " 10 69 0.02 " 10 ~:70 0.03 " 10 :: :
: :

, -~As~,~ 9 (continuecl) __ _ _ . __ Example No. Silane % by weight ) Pummel value at -20C

71 0 0~ - r~ - -lo ~-`----- ) 72 0.001 A~0 2 73 0.005 ' 1 7~ O.006 GLYM0 3 77 0.03 " 4 78 0.09 " 5 79 - 0.06_ ~~ 5 IME0 = r-imidazolylpropyl trithoxy silane AMEO = ~-aminopropyl trie-thoxy silane GLYM0 = r-glycicyloxypropyl -trimethoxy silane Examples 80 to 83 A plasticised polyvinyl butyral foil of the type used in Examples 61 to 79 having controlled glass adhesion was treated with a solution of 0.01% by weight of ~-imidazolylpropyl triethoxy silane (IME0) ln toluene and, after the evaporation of the solvent, was air-conditioned to differen-t water con-tents. The manufacture of the laminated glass was carried out as described in Examples 1 to 30 to yield products having the following pummel values:
~ BLE 10 :
- -- _ ~ Example No.Water content Pummel value at ~20C
; ~ ~ % by weight untreated foil trea-ted foil .. ::: -:: . _ . _ ._ 0.31 3 10 81 ~ 0.~1 3 10 82 0.6~ 3 10 : 33 _ 0~82 2 10 _ : _ Exa~ples 84 to 89 Plasticised polyvinyl butyral foil having high glass adhesion (~uality for building glass, pu~nel value 10~ was used ~' ~

in the manufac-ture of l.aminated safety glass. The ylass sheets used had a vaporised me-tal coating, the vapour-coa-ted sicles of the glass being disposed facing the polyvinyl butyral foil, i~e. on the inside. rrhe polyvinyl butyral foils were trea-ted beforehand wi-th a solu-tion of silane in toluene and were air-conditioned to a water-content o~ 0.45%. rrhe procluc-ts obtained showed the follow-ing pummel behaviour:

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Examp:Les 90 to 97 .
Plasticised polyvinyl butyra]. foil with high glass adhesion and glass surface-coa-ted. in the man:ner described in Examples 74 to 79 were used for the manufac-ture of laminated safety glass.
However, in place of a silane solution, a silane-con-taining lacquer was employed. For this purpose, a solution of 2% by weight of plas-ticised polyvinyl butyral foil as lacquer binder and 1% hy weight of silane was prepared. The solvent used was a 1:4 by volume mix-ture of dioxane and methyl isobutyl ketone. The polyvinyl butyral foil to be laminated (Examples 90.to 93~ or the coated glass (Exam-ples 94 to 97) were treated with this silane-containing lacquer.
Before preparaing the bond, the polyvinyl butyral foil to be laminat-ed was air-conditioned to a water content of 0.45%. The products obtained showed the following pummel behaviour.

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Claims (85)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the manufacture of laminated safety glass comprising bonding one or more silicate glass sheets at a temperature of up to 200°C to a foil selected from the group of foils consisting of polyvinylchloride foil, ethylene foil, propylene foil, ethylene-propylene foil and a partially acetalized polyvinylalcohol foil, enhanced bonding being provided by means of a silicon organo-functional silane and/or a silicon functional silane, with the provisos that when a said polyvinylchloride foil is employed, the silicon organo-functional silane and/or silicon functional silane is applied to the surface of a said foil and/or to a said glass sheet dispersed in a lacquer and that when a partially acetalised polyvinylalcohol foil is used, the silicon organo-functional silane and/or silicon functional silane is applied to the surface of said foil and/or to a said glass sheet dissolved in a solvent and/or dispersed in a lacquer, a solvent, when used, being removed after the application to the foil and/or glass sheet surface.

2. A process as claimed in claim 1, wherein bonding is assisted by means of a said silicon organo-functional silane.

3. A process as claimed in claim 2, wherein there is employed as said foil a foil selected from the group of foils consisting of ethylene foil, propylene foil, and ethylene-propylene foil.

4. A process as claimed in claim 3, wherein the foil has a Shore-A hardness measured in accordance with DIN
53505 of from 40 to 98.

5. A process as claimes in claim 4, wherein the foil has a Shore-A hardness measured in accordance with DIN 53505 of from 50 to 95.

6. A process as claimed in claim 3, wherein said foil is internally plasticised.

7. A process as claimes in claim 6, wherein said foil is formed of an ethylene or propylene copolymer which includes vinyl acetate as a comonomer.

8. A process as claimes in claim 3, wherein said foil is formed of an ethylene, propylene or ethylene-propylene copolymer which includes as a copolymer butadiene, an alkyl vinyl ester, vinylchloride, vinyl fluoride, acrylic acid, an acrylic acid ester, maleic anhydride, a maleic acid ester or styrene.

9. A process as claimed in claim 3, wherein the silane(s) is/are incorporated in a moulding composition from which said foil is produced.

10. A process as claimes in claim 3, wherein the silane(s) is/are applied to the surface of said foil and/or a said glass sheet in the form of a solution thereof in an organic solvent which is then removed.

11. A process as claimed in claim 3, wherein the silane(s) is/are applied to the surface of a said foil and/or a said glass sheet in the form of a dispersion thereof in a lacquer whose organic solvent is then removed.

12. A process as claimed in claim 2, wherein a said partially acetalised polyvinylalcohol foil is used, the silicon organo-functional silane and/or silicon functional silane being applied to a surface of said foil and/or to a said glass sheet dissolved in a solvent, the solvent being removed after the application to the foil and/or glass sheet surface.

13. A process as claimed in claim 2, wherein a said partially acetalised polyvinylalcohol foil is used, the silicon organo-functional silane and/or silicon functional silane being applied to a surface of a said foil and/or to a said glass sheet dispersed in a lacquer whose solvent is then removed.

14. A process as claimed in claim 12 or 13, wherein a polyvinylbutyryl foil is used as the partially acetalised polyvinylalcohol foil.

15. A process as claimed in claim 10 or 12, wherein the silicon organo-functional silane and/or silicon functional silane is/are dissolved in a solvent which additionally contains a lacquer binder.

16. A process as claimed in claim 2, wherein a poly-vinylchloride foil is used, the silicon organo-functional silane and/or silicon functional silane being applied to the surface of said foil and/or to a said glass sheet dispersed in a lacquer whose solvent is then removed.

17. A process as claimed in claim 16, wherein the polyvinylchloride has a K-value of from 50 to 80.

18. A process as claimed in claim 17, wherein the poly-vinylchloride has a K-value of from 60 to 75.

19. A process as claimed in any one of claims 16 to 18, wherein the polyvinylchloride is a homopolymer of vinylchlori-de.

20. A process as claimed in claim 16, wherein the poly-vinylchloride is a copolymer of vinylchloride with one or more monomers chosen from hydrocarbon monomers, halogenated hydrocar-bons, alcohols, ethers, acids and hetero compounds which contain in their molecules sites of ethylenic unsaturation.

21. A process as claimed in claim 20, wherein the polyvinylchloride is a terpolymer of vinylchloride ethylene and vinyl acetate.

22. A process as claimed in any one of claims 16 to 18, wherein the polyvinylchloride is a graft polymer of vinyl-chloride or a copolymer of ethylene and vinyl acetate.

23. A process as claimed in claim 16, wherein the poly-vinylchloride is a chlorination product of homopolymerised vinyl-chloride, a copolymer of vinylchloride and an ethylenically un-saturated monomer or a graft polymer of vinyl chloride.

24. A process as claimed in claim 16, wherein the poly-vinylchloride is present in the foil in admixture with a polymer not derived from vinylchloride and constituting not more than 50% by weight of the polymer blend thereby produced.

25. A process as claimed in claim 24, wherein the polymer is polyvinyl acetate, a copolymer of vinyl acetate and ethylene or acrylonitrile- or methacrylonitrile- butadiene sty-rene.

26. A process as claimed in claim 16, wherein the foil is plasticised with a phthalate, aliphatic dicarboxylic acid ester, phosphoric acid ester or polyester plasticiser.

27. A process as claimed in claim 16, wherein the foil has a Shore-A hardness measured in accordance with DIN 53505 of from 40 to 98.

28. A process as claimed in claim 27, wherein said Shore hardness is from 50 to 95.

29. A process as claimed in any one of claims 11, 13 and 16, wherein a lacquer containing the silicon organo-functional silane and/or silicon functional silane is applied to the foil and/or glass sheet, the lacquer containing a lacquer binder which is a non-hardening polymethacrylcate or polyacrylate, a polyure-thane, post-chlorinated polyvinyl chloride, or a copolymer of vinylchloride and vinyl isobutylether.

30. A process as claimed in claim 11, wherein a lacquer containing the silicon organo-functional silane and/or silicon functional silane is applied to the foil and/or glass sheet, the lacquer containing a lacquer binder which contains reactive OH- and/or -COOH groups.

31. A process as claimed in claim 30, wherein the lacquer binder is a vinylchloride-vinyl acetate-vinyl alcohol terpolymer.

32. A process as claimed in claim 30, wherein the lacquer binder is selected from the group consisting of a partially hydrolysed copolymer of vinyl chloride and vinyl acetate, a vinyl chloride-hydroxyalkyl acrylate copolymer, a vinylchloride-vinyl acetate-unsaturated carboxylic acid terpolymer and a vinyl chloride-unsaturated carboxylic acid alkyl ester-unsaturated carboxylic acid terpolymer.

33. A process as claimed in claim 32, wherein the lacquer binder is a vinylchloride-vinyl acetate-maleic acid terpolymer.

34. A process as claimed in claim 30, wherein bonding is assisted by means of a said organo-functional silane.

35. A process as claimed in claim 1, wherein bonding is assisted by means of a combination of a said silicon organo-functional silane and a said silicon functional silane.

36. A process as claimed in claim 1, wherein the silicon organo-functional silane prossesses the general formula:

wherein R° is a hydrolysable radical, Riii is an alkyl radical containing from 1 to 18 carbon atoms;
A is a straight chain or branched alkylene radical con-taining from 1 to 10 carbon atoms and which may be interrupted by hetero atoms;
Z represents a radical containing a functional group;
n is 1, 2 or 3 and p is 0 or 1, provided that Z is linked to the silicon atom through at least one carbon. atom form-ing part of A or Z.

37. A process as claimed in claim 36, wherein R0 is a halogen atom or a radical of formula OR wherein R denotes an acyl radical or an alkyl radical containing from 1 to 18 carbon atoms, the carbon atoms of which when two or more arc present in the radical being possibly interrupted by hetero atoms,

38. A process as claimed in claim 37, wherein Z denotes a halogen atom, an olefinically unsaturated group, or a group of formula , or wherein Ri is hydrogen or a group of formula - Rii - NH2 or - Rii - OH wherein Rii is an alkylene radical containing from 2 to 8 carbon atoms, two radicals Ri, when present, being the same or different, and Riv is methyl or ethyl and m is 1, 2 or 3.

39. A process as claimed in claim 38, wherein Z denotes an olefinically unsaturated group and the silicon organo-functio-nal silane is used in conjunction with a free radical former.

40. A process as claimed in claim 39, wherein the free radical former is used in an amount of from 0.01 to 1% by weight of the silane containing solution or lacquer.

41. A process as claimed in claim 40, wherein the si-licon organo-functional silane is a vinyl trialkoxy silane, a .gamma. -methacryloxy propyl trialkoxy silane, vinyl-tris - .beta. - methoxy-ethoxy silane or vinyl triacetoxy silane.

42. A process as claimed in claim 1, wherein the si-licon organo-functional silane contains at least one amino and/or imino group or at least one epoxy group

43. A process as claimed in claim 42, wherein one or both of the hydrogen atoms of the amino group is/are replaced by an amino- or hydroxyalkyl radical ox by a polyamine radical.

44. A process as claimed in claim 41, wherein the silicon organo-functional silane possesses the general formula:

in which R is an alkyl radical containing from 1 to 10 carbon atoms, the carbon atoms, when two or more are present being op-tionally interrupted by one or more hetero atoms, Riii is an alkyl radical containing from 1 to 8 carbon atoms, A is a straight-chain or branched alkylene radical containing from 1 to 8 carbon atoms and which may be interrupted by one or more hetero atoms, m is 1, 2 or 3, n is 1, 2 or 3 and in which: Ri is a hydrogen atom or a group of formula -Rii-OH or -Rii-NH2 wherein Rii is an alkylene radical containing from 2 to 4 carbon atoms when m is 1, and Ri is a hydrogen atom or a group of formula -Rii wherein Rii, Riii, A and n have the aforesaid meanings when m is 2.

45. A process as claimed in claim 41, wherein the silicon organo-functional silane possesses the general formula:
NH2-(CH2)n-Si-(ORv)3 in which n is an integer of from 2 to 6 and Rv is a branched or unbranched alkyl radical containing from 1 to 8 carbons which, when more than one carbon atom is present, may be interrupted by one or more hetero atoms.

46. A process as claimed in claim 42 or 43, wherein the hetero atom(s) is/are oxygen.

47. A process as claimed in claim 44, wherein the silicon organo-functional silane is a .gamma.-aminopropyl or .beta.- amino-ethyl trialkoxy silane.

48. A process as claimed in claim 44, wherein the amino group of the silicon organo-functional silane is substituted by an aminoalkyl or polyaminoalkyl radical.

49. A process as claimed in claim 45, wherein the amino group of the silicon organo-functional silane is substituted by an aminoalkyl or polyaminoalkyl radical.

50. A process as claimed in claim 48, wherein the polyaminoalkyl group possesses the general formula [-CH2(CH2NHCH2)xCH2-]-NH2 wherein x is an integer of from 1 to 8.

51. A process as claimed in claim 49, wherein the polyaminoalkyl group possesses the general formula [-CH2(CH2NHCH2)xCH2-]-NH2 wherein x is an integer of from 1 to 8.

52. A process as claimed in claim 41, wherein the silicon organo-functional silane is .gamma.-aminopropyl triethoxy silane or a .beta.-aminoethyl-.gamma.-oxypropyl methyl dialkoxysilane.

53. A process as claimed in claim 43, wherein the silicon organo-functional silane is a compound of general for-mula:
HN [CH2-CH2-CH2-Si(ORv)3]2 wherein Rv is a branched or unbranched alkyl radical containing from 1 to 8 carbons which, when more than one carbon atom is present, may be interrupted by one or more hetero atoms.

54. A process as claimed in claim 53, wherein the hetero atoms is/are oxygen.

55. A process as claimed in claim 53, wherein said compound is bis-triethoxysilylpropylimine.

56. A process as claimed in claim 44, wherein the silicon organo-functional silane is a compound of general formu-la:

wherein R, Riii, A and n have the meanings set out in claim 44 and Riv is a hydrogen atom or a methyl or ethyl group.

57. A process as claimed in claim 56, wherein said compound is a .gamma.-imidazolylpropyl trialkoxy silane.

58. A process as claimed in claim 57, wherein said compound is .gamma.-imidazolylpropyl triethoxy silane.

59. A process as claimed in claim 41, wherein the silicon organo-functional silane contains an epoxy group bonded by way of an ether grouping, an ester grouping or a cycloalipha-tic ring to an alkylene silyl radical.

60. A process as claimed in claim 41, wherein the silicon organo-functional silane contains a cycloaliphatic radical substituted by an alkylene silyl radical and having an epoxy group fused thereto.

61. A process as claimed in claim 59, wherein the silicon organo-functional silane is glycidyloxypropyl trimethoxy-silane, glycidyloxypropyl triethoxysilane or a compound of for-mula

62. A process as claimed in claim 60, wherein the silicon organo-functional silane is .beta.-3,4-epoxycyclohexyl-ethyltrimethoxysilane.

63. A process as claimed in claim 41, wherein the si-licon organo-functional silane contains epoxy groups and is pre-sent in said solution in an amount of from 0.0001 to 5% by weight.

64. A process as claimed in claim 63, wherein the silicon organo-functional silane is present in said solution in an amount of from 0.01 to 2% by weight.

65. A process as claimed in claim 41, wherein the silicon organo-functional silane containing amino and/or imino groups is present in said solution in an amount of from 0.0001 to 2% by weight.

66. A process as claimed in claim 65, wherein said silicon organo-functional silane is present in said solution in an amount of from 0.0005 to 1% by weight.

67. A process as claimed in claim 34, wherein the sili-con functional silane is a compound of general formula:

Rn - Si Rv4-n in which R represents a straight chain or branched alkyl radical containing from 1 to 10 carbon atomes, Rvi represents a halogen atom or an alkoxy group containing from 1 to 8 carbon atoms which, when containing a plurality of carbon atoms may be interrupted by one or more hereto atoms, and n is an integer from 1 to 3.

68. A process as claimed in claim 35, wherein the silicon functional silane is a compound of general formula:
Rn - Si Rv4-n in which R represents a straight chain or branched alkyl radical containing from 1 to 10 carbon atoms, Rvi represents a halogen atom or an alkoxy group containing from 1 to 8 carbon atoms which, when containing a plurality of carbon atoms may be interrupted by one or more hereto atoms, and n is an integer from 1 to 3.

69. A process as claimed in any one of claims 67 and 68, wherein said compound is selected from the group consisting of a propyl triethoxysilane, propyl trimethoxysilane, isopropyl dimethoxyethoxysilane and n-butyl or isobutyltriethoxy or trimethoxysilane.

70. A process as claimed in claim 12, wherein said solution has a total silane concentration of from 0.0001 to 1%
by weight of the solvent.

71. A process as claimed in claim 10, wherein. said solution has a total silane concentration of from 0.0001 to 1%
by weight of the solvent.

72. A process as claimed in claim 70, wherein said solution has a total silane concentration of from 0.0001 to 7%
by weight of the solvent.

73. A process as claimed in claim 72, wherein said solution has a total silane concentration of from 0.005 to 5.0% by weight of the solvent.

74. A process as claimed in claim 71, wherein said solution has a total silane concentration of from 0.01 to 10%
by weight of the solvent.

75. A process as claimed in claim 74, wherein said solution has a total silane concentration of from 0.05 to 7%
by weight of the solvent.

76. A process as claimed in claim 36, wherein the silicon organo-functional silane is applied in an amount of from 0.0001 to 7% based on the weight of solvent present.

77. A process as claimed in claim 76, wherein the silicon organo-functional silane is applied in an amount of from 0.0005 to 5% based on the weight of solvent present.

78. A process as claimed in claim 77, wherein the silicon organo-functional silane is applied in an amount of from 0.0001 to 2% based on the weight of solvent present.

79. A process as claimed in claim 78, wherein the silicon organo-functional silane is applied in an amount of from 0.0005 to 1% by weight based on the weight of solvent present.

80. A process as claimed in claim 76, wherein the silicon organo-functional silane is dispersed in a lacquer.

81. A process as claimed in any one of claims 10 and 11, wherein the silicon organo-functional silane and/or silicon functional silane is incorporated in a solvent selected from the group consisting of toluene, xylene, petroleum ether, ethyl acetate, butyl acetate, isopropanol, methyl isobutyl ketone and a combination of two or more such solvents.

82. A process as claimed in any one of claims 12 and 13, wherein the silicon organo-functional silane and/or silicon functional silane is incorporated in a solvent selected from the group consisting of toluene, xylene, petroleum ether, ethyl acetate, butyl acetate, isopropanol, methyl isobutyl ketone and a combination of two or more such solvents.

83. A process as claimed in claim 1, wherein the bonding is effected at a temperature of from 120 to 200°C.

84. A process as claimed in claim 83, wherein the bonding is effected at a temperature of from 120 to 150°C.

85. A process as claimed in claim 84, wherein the bonding is effected at a temperature of from 135 to 145°C.