CA1255067A - Process for covering plate glass edges using elastic polyisocyanate polyaddition products - Google Patents

Abstract

PROCESS FOR COVERING PANE GLASS
EDGES USING ELASTIC
POLYISOCYANATE POLYADDITION PRODUCTS
Abstract of the Disclosure The invention is a process for coating with an adhesion-improving agent and covering the edges of plate glass, to be fitted to vehicle compartments, with poly-urethane, polyurethane-polyurea, or polyurea elastomers.
The edges of the plate are coated with one or more layers of an adhesion-improving agent to achieve a good bond between the glass and the elastomer covering. A glass plate is positioned in a mold, the mold closed, and the cavity between the glass plate and mold filled with a reactable mixture of organic polyisocyantes, higher molecular weight compounds having at least two reactive hydrogen atoms, chain extenders and/or crosslinking agents, catalysts, and optionally auxiliaries and/or additives. The reaction mixture is allowed to cure and then the plate glass is removed.

Description

~L~55~;7 Case 1490 PROCESS YOR COVERING PLATE GLASS
EDGES USING ELASTIC
POLYISOCYANATE POLYADDITION PRODUCTS
Background of t_e Invention 1. Field of the Invention The invention relates to a proces~ for preparing plate qlass to be fitted, in a single mechanical step, to a vehicle. More particularly, the invention relate~ to a process for coating with an adhesion-improving ayent and covering, by reaction injection method, the edges of plate glass with polyurethane or polyurethane-polyurea or polyurea ela~tomers.
3esc~ption of the Prior_Art The present technology used to fit plate glass to the passenger compartment of a vehicle i~ a highly labor intensive and expenqive proce~s. A plate glass. vapor metalli~ed glasa plate and/or safety glass plate~ are coated with a transparent plastic film, for example, polyeqters or polyurethanes, and then bound by an adhesive material to the metal frames of the pas~enger compartment openings. After trimming the edges, the glass plates are cleaned. To prevent ultraviolet radiaticn from damaging the layer o~
adhesion-improving agent and adhe~ive between the plate and metal frame, the edges of the plate gla~s are printed with UV radiation absorbing inX. Subsequently the plate~ are I~D~ 7 spherically molded at eleva-ted temperatures to the specific shape of the particular vehicle model.
This invention overcomes the labor-intensive and ex-pensive process of the present technology by a simplified single step for processing and directly fastening, by mechanical means, panes of glass to the passenger compartment frame.

SUMMARY OF TH~ INVENTION

The objective of the invention is to simplify the present labor-intensive and expensive process of treating and fitting glass plates to a particular vehicle model. It has been found that objective may be unexpectedly accomplished by a pro-cess for covering, in a mold, the edges of the glass plates with polyurethane, polyurethane-polyurea or polyurea elasto-mers. As a result, a glass plate can be fitted to a vehicle frame in a single mechanical step.
The process according to the invention for coating with one or more adhesion-improving agents and covering an edge of plate glass with polyurethane or polyurethane-polyurea or polyurea elastomers comprises:
1) coating said ed~es of the plate glass with said adhesion-improving agent,

2) placing said plate glass in an open mold,

3) closing said mold,

4) charging a cavity formed between said glass plate and said mold with a reac-tive mixture comprising, a) an organic polyisocyanate, b) a higher molecular weight compound having at least 2 reactive hydrogen atoms and selected from a group consisting of polyether polyol, polyester polyol, polythioether polyol, polyes-ter amide, hydroxyl group-containing polyacetal and/or hydroxyl group-con~ining aliphatic poly carbonate.

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GENERAL DESCRIPTION OF l'HE INVEN'~'ION
_ In the process of the invention, plates of glass which have been cut to the dimensions required for a particular ~e-hicle model, which may optionally be spherically shaped, canbe covered by -the use of a reactive one-shot polyurethane-po-lyurea or polyurea elastomer systems with the aid of reaction injection molding techniques in a single processing step having short cycle times, e.g., mold residence times under 120 seconds, preferably from 5 to 60 seconds. The mold is adaptable to provi-de any desired geometry to the molding in covering the edge of the plate of glass and, therefore, can be matched to fit the metal frame of the vehicle compartment. It is also advanta-geous to select the initial components (a) through (d) in such a way that the polyurethane elastomer, polyurethane-polyurea elastomer, or polyu~ea elastomer, ~ ~e ~ ~ed //
/
/

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i~ .

~ZSS~)~7 a~ PUR elastomer, PUR-PU ela3tomer, and PU ela~tomer are produced with the required mechanical properties, in particular hardnes~, tenqile 3trength, and tear strength~
Gla~s plates of variou~ compo~itions may be covered around their edges. Preferably, ~ilicate gla~
u~ed for the glass plateq. However, mechanically or chemically treated glass plates, e.g., gla~s plate~ which have been vapor metallized or coated with tran~parent pla~tic films, for example polyamide, polycarbonate, or polyurethane films, a~ well as laminated glass may be u~ed. The plates of glass are generally from 3 to 20 mm thick, preferably from 3 to 8 mm thick.
To achieve a good adhe~ive bond between the gla~s and the elastomer covering, the edges of the plate glaq~ are - coated with one or more adhe~ion-improving agents prior to being covered with PUR, PUR-PU, or PU elastomer~. Suitable adhesion-improving agents are, for example, silane e~ters, organic polyisocyanate~, modified organic polyi~ocyanates, isocyanate end group-containing prepolymers, and polyfunc-tional epoxy compounds. Preferably used are y-aminopropyl-triethoxysilane, y-aminopropyltrimethoxysilane, N-~-amino-ethyl-y-aminopropyltriethoxysilane, N-~-aminoethyl-y-aminopropyltrimethoxy~ilane, y-mercaptopropyltrimethoxy-silane, and y~mercaptopropyltriethoxy~ilane. The agent i~
generally applied to a preferably degrea3ed plate of glaqs ~;SV67 in a qolution containin~ from 1 to 10 percent by weight adhe~ion-improving agent, preferably from 2 to 6 percent by weight, by known method3, for example by painting, spraying, rolling, immersing, etc., in such a way that when the solvent, preferably isopropanol, evaporates, the thickness of the adhesion-improving aqent layer is from 5 to 80~m, preferably from 10 to 40~m. The adhesion-improving layer, which may be comprised of one or more individual layers and one or more adhesion-improving agents, is generally applied in a ~ingle- or multiple-~tep process. It is generally best for the bottom layer to be cornprised of an aminoalkyltri-alkoxysilane, which, after the solvent haM evaporated, is coated with a different adhesion-improving agent containing non-reactive or, preferably, reactive groups. Such adhesion-improving agents with reactive group~ are, for exa~ple, organic, optionally modified polyisocyanates, for example carbodiimide group, isocyanurate group, urethane group, and/or uretonimine group~containing polyisocyanate~
based on diphenylmethane diisocyanates, mixtures of di-phenylmethane diisocyanates and polyphenyl polymethylanepolyi ocyanates having a low vapor pre~sure, i~ocyanate end group-containing prepolymers based on aromatic, aliphatic, and/or cycloaliphatic diisocyanates, and polyester and/or polyether polyols and polyepoxy compound~.

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The following ~hould be noted regarding the initial component (a~ through (e3 u~ed for preparing the noncellular PUR, PUR-PU, or PU elastomers of the proceq~ of the inventiono (a) Typical organic polyisocyanates which may be u~ed are the conventionally known aliphatic, cycloaliphatic, and preferably aromatic polyfunctional isocyanates.
Typical example3 are 1,6-hexamethylene dii~ocyanate, l-isocyanato-3,3,5-trimethyl-3-isocyanatomethylcyclo-hexane, 2,4- and 2,6- hexahydrotoluene diisocyanate, as well as the corresponding isomer mixtures, 4,4'-, 2,2'-, and 2,4'-dicyclohexylmethane diisocyanate, as well as the corresponding isomer mixtures; mixtures of 4,4'-, 2,2'-, and 2,4'-dicyclohexylmethane diisocyanate~, and polymethylene polycyclohexylene polyisocyanate~; 2,4-, and 2,6-toluenedii~ocyanates, and the corresp~nding isomer mixtures; 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate, and the corresponding isomer mixtures mixture~ of 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanates, and polyphenylpolymethylene polyisocya-nates (palymeric MDI), and mixtures of polymeric ~DI
and toluene diisocyanates.

~lZ~S~67 Frequently, modified polyisocyanates, ~uch a~ e~ter, urea, biuret, allophanate, and optionally carbodiimide, isocyanurate, and/or urethane group-containing di-and/or polyi~ocyanates, are also employed. Examples of resultant product~ include urethane group-containing aromatic polyiYocyanates having isocyanate contents of from 15 to 33.6 percent by weight, preferably from 21 to 31 percent by weight, for example, modified 4,4'-diphenylmethane diisocyanate or modified toluene diisocyanate~ The isocyanates are modified by reacting with low molecular weight diols, triols, dialkylene glycols, trialkylene glycols, or polyoxyalkylene glycols having molecular weight~ up to 800. Typical examples of the di- or polyoxyalkylene glycol~ which may be used individually or a~ mixtures are:
diethylene glycol, dipropylen~ glycol, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene polyoxyethylene glycol~. Isocyanate group-containing prepolymers having isocyanate contents from 9 to 21 percent by weight, preferably from 14 to 21 percent by weight, are also ~uitable. In addition, liquid carbodiimide group- and~or i~ocyanurate ring-containing polyisocyanates having i30cyanate content~ from lS to 33.6 percent by weight, preferably Prom 21 to 31 percent by weight, have al~o proven to be effective, ~LZS~ ;7 for example, those ba~ed on 4,4'-, 2,4'-, and/or 2,2' diphenylmethane diisocyanate and/or 2,4- and/or 2,6-toluene diiqocyanate, and preferably 2,4- and 2,6-toluene dii~ocyanate and the corresponding isomer mixture~, 4,4'-, 2,4'-, and 2,2'-diphenylmethane dii~ocyanate as well a~ the corre~ponding i~omer mixtures, for example, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanate~, mixtures of diphenyl-methane diisocyanate3 and polyphenyl polymethylene polyiqocyanates (polymerir MDI), and mixtures of toluene dii~ocyanates and polymeric MDI. Preferred are urethane group, carbodiimide group, and/or isocyanurate ring-containing polyi~ocyanates, for example, those based on diphenylmethane diisocyanate and/or toluene diisocyanate, toluene diisocy~nates, mixture~ of polymeric MDI and toluene diisocyanates, and, more preferably, mixtures of 4,4'- and 2,4'-diphenylmethane .:isocyanates or mixtures of diphenylmethane diiso-cyanate i~omer~ and polyphenyl polymethylene polyiso-cyanate~.

(b) For the higher molacular weight compounds, component (b), having at least two reactive hydrogen atoms, it has been found desirable to usa those having a func-tionality of ~rom 2 to 8, preferably from 2 to 4, and a ~LZS~

molecular weight of from 800 to 8000, preferably from 1200 to 6000. For example, polyether polyamines and/or, preferably, polyols such as polyether polyol~, polye~ter polyols, polythioether polyols, polye~ter amide~, hydroxyl group-containing polyacetals, and hydroxyl group-containing aliphatic polycarbonates or mixture~ of at least two of the cited polyol~ have proven to be effective. Preferably used are polyester polyols and/or polyether polyols. Suitable polyester polyols may be prepared, for example, from organic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyfunctional alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. Typical car-boxylic acids which may be used are: succinic acid, glutaric acid, adipic acid, 3uberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, maleic acid, and fumaric acid. The dicarboxylic acids may be used individually or as mixture~ with one another. Instead o~ the free dicarboxylic acids, the corresponding dicarboxlic acid derivatives may be used, for example the dicarboxylic acid esters of alcohols having from 1 to 4 carbon atoms or dicarboxylic anhydrides. Prefer-ably u~ed are dicarboxylic acid mixtures of succinic, .

~2S5Q67 glutaric, and adipic acid in quantitative ratio~ of, for example, 20-35:35-50:20-32 parts by weight, re~pectively. More preferably, adipic acid may be used alone. Typical example~ of di- and polyfunctional alcohols, preferably diol~, are, ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 decanediol, glycerine, and trimethylolpropane.
Preferably u~ed are ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures of at lea~t two of the cited diols, preferably mixture~ of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. In addition, polyester polyols of lac-tones, for example, ~-caprolactone, or hydroxylcar-- boxylic acid~, for example ~-hydroxycaproic acid may be used. Preferably, the polye~ter polyol have a functionality of ~p to 3 and a molecular weight of ~rom 800 to 3000, more preferably from 1800 to 2500.

Particularly preferred a~ polyolq are polyether polycls prepared by known method~, for example, the anionic polymeri~ation with alkali hydroxide~ quch a~ ~odium hydroxide or pota~ium hydroxide, or alkali alcoholate3 ~uch a~ ~odium methylate, ~odlum or pota~sium ethylate, or pota~ium i~opropylate a~ cataly~t~, or by the cationic ~2SS~:"7 polymerization with Lewis acids such a~ antimony penta-chloride, borofluoride etherate, etc., or bleaching earth as cataly~ts, from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical, and an initiator which contains fro~ 2 to 8, preferably from 2 to 4 reactive hydroyen atoms.
Suitable oxides are, for example, tetrahydrofuran, trimethylene oxide, 1,2-, and 2,3-butylene oxids, styrene oxide, epichlorohydrin, and preferably ethylene oxide and 1,2-propylene oxide. The oxides may be uqed individually, alternately one after another, or as mixture~. Typical intiator~ are, water, organic dicarboxylic acids such a3 succinic acid, adipic acid, phthalic acidl and terephthalic acid, aliphatic and aromatic, optionally N-mono, N,N- and N,N'-dialkyl-substituted diamines having from 1 to 4 carbon atoms in the alkyl radical such as optionally mono- and dialkyl-sub~tituted ethylenediamine, die~hylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- respec-tively 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-hexamethylenediamine, phenylenediamines, 2,4- and 2,6-toluenediamineJ and 4,4'-, 2,4'-, and 2,2'-diaminodi-pher~ylmethane .
Typical initiators are also alkanol amines such asethanolamine, diethanolamine, N-methyl- and N-ethylethanol-amine, N-methyl- and N-ethyldiethanolamine, and triethanol-~2SS~
amine, ammonia, hydrazine, and hydrazides. Pre~erably usedare polyfunctional, and more preferably di- and/or tri-functional alcoholq such a3 ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerine, trimethyolpropane, pentaery~hritol, sorbitol, and sucrose~.
The polyether polyols preferably have a func-tionality of from 2 to 4 and molecular weights from 800 to 8000, mora preferably from 1200 to 6000, and most preferably from 1~00 to 4000. As with the polyester polyols, they may be used individually or in the form of mixtures. They may al~o be mixed with the polyester polyolR a well a~ the hydroxyl group-containing polye~ter amides, polyacetal~, polycarbonates, and/or polyether polyamine~.
Typical hydroxyl group-containing polyacetals which may be u~ed are compound~ produced from glycols such as diethylene glycol, trSethylene glycol, 4,4'-dihydroxy-ethyoxydiphenyldimethylmethane, hexanediol, and formalde-hyde. Suitable polyacetals may also be prepared by polymer-izing cyclic acetal~r ~ ydroxyl group-containing polycarbonate~ which may be used are those of the essentially known type, which may be prepared, for example, through the reaction of diol~ ~uch a~ tl,3)-propanediol, (1,4)-butanediol, and/or (1,6)-hexanediol, diethylene glycol, triethylene glycol, or ll25501~ 7 tetraethylene glycol with diaryl carbonate~, for example diphenyl carbonate, or pho~gene. Among the polye~ter amides which may be used are those from polyfunctional saturated and~or unsaturated carboxylic acids or their anhydrides and polyfunctional saturated and/or unsaturated amino alcohol~
or mixtures of polyfunctional alcohols and amino alcohols and/or polyamines, preferably linear conden~ates.
Suitable polyether polyamines may be prepared from the polyether polyols cited above using known method~.
Typical examples are the cyanoalkylation of polyoxyalkylene polyols with the ~ub3equent hydrogenation of the nitrile which is formed (U.S. 3,267,050) or the amination of polyoxyalkylene polyols with amine~ or ammonia in the presence of hydrogen and cata~ysts ~Federal Republic of Germany Patent 12,15,373).

~c) Di-- to tetra~unctional, preferably difunctionall compounds having molecular weights ~rom 60 to 600, preferably from 60 to 300, from the group comprising the aliphatic, cycloaliphatic, or araliphatic diol~
and/or triols, the ~econdary diamines, and preferably the primary, un~ubstituted and/or more preferably substituted aromatic di- and/or higher funcationality polyamines are used as the chain extenders and/or crosslinking agents, component (c).

~;~55~367 Suitable diol~ or triol~ preferably have molacular weight~ les~ than 400, more preferably from 60 to 300.
Typical examples are aliphatic, cycloaliphatic, and/or araliphatic diols having from 2 to 14, preferably 4 to 10 carbon atom~, such as ethylene glycol, 1,3-propanediol, l,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, and more preferably l,4-butane-diol, 1,6-hexanediol, and bis(2-hydroxyethyl)hydroquinone, triols such as 1,2,4-, 1,3,5-trihydroxycyclohexane, glyc-erine, and trimethylolpropane, and low molecular weighthydroxyl group-containing polyalkylene oxides ba~ed on ethylene oxide and/or 1,2-propylene oxide, and the diols and~or triols cited above as initiators.
Typical secondary diamine~ which may be u~ed are: N,N'-dialkyl-substituted aromeltic diamines, which may optionally be substituted on the aromatic ring by alkyl : radical~, having from 1 to 20, preferably 1 to 4, carbon atom~ in the N-alkyl radical, ~uch a~ N~N'-diethyl-, N,N'-di-sec-pentyl-, N,N'-di-sec-hexyl-, N,N'-di-sec-decyl-, N,N'-dicyclohexyl-p-, m-phenylenediamine, N,N'-dimethyl-, N,N'--diethyl-~ N,N'-diisopropyl, N,N'-di-sec-butyl-, N,NI-dicyclohexyl-4,4'-diaminodiphenylmethane, and N,N'-di-sec-butylbenxidine.

~;25~

The following may be used as un~ubstituted primary aromatic diamine~ and/or higher functionality polyamine~:
1,2-, 1,3-, and 1,4-phenylenediamine, benzidine, 4,4'- and 2,4'-diaminodiphenylmethane, 4,4'- and 2,4'-diaminodimethyl-methane, 4,4'-diaminodiphenylether, 1,5-naphthalenediamine, 1,8-naphthalenediamine, and polyphenyl polymethylene polyamines a~ well a~ mixtures of diaminodiphenylmethane~
and polyphenylpolymethylenepoly~mine~. Al~o ~uitable are substituted primary aromatic diamines, preferably monoalkyl-substituted aromatic diamine~, in which the reactivity ofthe amino group i~ not significantly affected by the substituents, for example 3,4-, 2,4-, and 2,6-toluenedi-amine.
Substituted primary aromatic diamine~ and/or higher functionality polyamines which are preferably used are tho~e which are 3ubstituted in the ortho position relative to the amino group~ by at lea3t one alkyl group which reduce~ the activity oE the amino group due to stearic hinderance, which are liquid at room temperature, and which under the proces3ing conditions are at least partially mi~cible with component (b). Succe~s has been achieved, for example~ with alkyl-~ubstituted meta-phenylenediamine3 of formula~

~SSV67 R NE~ 2 R NH2 H2N- ~ -R and/or ~ -R

in which R3 and R~ are identical or different and are a methyl, ethyl, propyl, and isopropyl radical, and Rl i9 a linear or branched alkyl radical having from 1 to 10 carbon atoms, preferably from 4 to 6. Preferred are alkyl rad-icalq Rl in which the branching point i9 located at the cl carbon atom. Typical Rl radicals are the methyl, ethyl, isopropyl, l-methyloctyl, 2-ethyloctyl, l-methyl-hexyl, l,l-dimethylpentyl, 1,3,3-trimethylhexyl-, l-ethyl-pentyl-, 2-ethylpentyl-, and preerably the cyclohexyl-, ~ ~ l-methyl-n-propyl-, tert-butyl, l-ethyl-n-propyl~ methyl-: ~ n-butyl-, and l,l-dimethyl-n-propyl-~ radicals.
Typical alkyl-~ubstituted m-phenylenedia~ines which may be used are: 2,4-dimethyl-6-cyclohexyl-, 2-cyclohexyl-4,6-diethyl-, 2~cyclohe~yl-2,6-isopropyl-, 2,4-dimethyl-6-tl-ethyl-n-propyl)-, 2,4-dimethyl-6~ di-: methyl n-propyl)-, 2-(1-methyl-n-butyl)-4,6-dimethyl-1,3-: phenylenediamine. Preferably used are 1-methyl-3,5-diethyl-2,4- respec~ively 2,6-p~enylenediamines, 2,4-dimethyl-6-tertiary butyl-, 2,4-d~imethyl-6-isooctyl-, and 2,4-dimethyl-6~cyclohexyl-1,3-phenylenediamine.
: Also suitable are 3,3'-di- and/or 3,3l,5,5'-tetra-n-alkyl substituted 4,4'-diamino-diphenylmethanes such as ~S~ 7 3,3'-dimethyl, 3,3'-diethyl, 3,3' di-n-propyl, 3,3',5,5'-tetramethyl, 3,3',5,5'-tetraethyl and 3,3'5,5'-tetra-n-propyl-4,4'-diaminodiphenylmethane.
Preferably used a~ alkyl-~ubstituted 4,4'-diamino-diphenylmethane are those of formula ~ 2N- ~ -C~ ~ 2 in which R4, R5, R6, and R7 are identical or different and are a methyl, ethyl, propyl, isopropyl, sec-butyl, and tert-butyl radical. At least one of the radicals mu~t be an i~opropyl or a sec-butyl radical.

4,4'~Diaminodiphenylmethalle may also be used in mixture with iqomer~ of formulas R4- ~ 2 ~ N~2 and/or R - ~ -CH ~ 6 7 2 ~

wher~ R~, R5, R6, and R7 have the meaning given above.
Typic~l examples are: 3,3'/5-trimethyl-5'-isopropyl, 3,3',5-triethyl-5l-isopropyl, 3,3',5-trimethyl-5'-sec-butyl 3,3',5-triethyl-5'-sec-butyl-4,4'-dia~inodiphenylmethane, 3,3'-dimethyl-5,5'-diisopropyl, 3,3'-diethyl-5,5'~dii~o-propyl, 3,3'-dimethyl-5,5'-di-~ec-butyl, 3,3'-diethyl-5,5'-dii~opropyl, 3,3'-dimethyl-5,5'-di-~ec-butyl, 3,3'~diethyl-

5,5'-di-~ec-butyl, 3,5-dimethyl-3',5'-diisopropyl, 3,5-diethyl-3',5'-dii~opropyl, 3,5'-dimethyl-3',5-di-sec-butyl, 3,5-diethyl~3',5'-di-sec-butyl-4,4'-diaminodiphenylmethane, 3-methyl 3',5,5'-triisopropyl, 3-ethyl-3',5,5'-trii~opropyl, 3-methyl-3'5,5'-tri-sec-butyl, 3~ethyl-3',5,5'-tri~sec-butyl-4,4' diaminodiphenylmethane, 3,3'-dii~opropyl-5,5'-di-sec-butyl, 3,5-diisopropyl-3',5'-di-sec-butyl, 3-ethyl-5-sec-butyl-3',5'-dii~opropyl, 3-methyl 5 tert-butyl-3',5'-diisopropyl, 3-ethyl-5-3ec-butyl-3'-methyl-5'-tert-butyl, 3,3',5,5'-tertrai~opropyl and 3,3',5,5'-tetra-~ec-butyl-4,4'-diaminodiphenylmethane. Preferably u~ed are 3,5-dimethyl-3'05'-diisopropyl, and 3,31,5,5'-tetraisopropyl-4,4'-dia;ninodiphenylmethane. The dlaminodiphenylmethane~
may be u~ed individually or in the form of mixture~.
The cited chain extender~ and/or cros~linking agent~ of component (c) may be u~ed individually or a~
mixtures o~ identical or different type~. Succe~s ha~ been achieved, for example, with mixtures of 5 to 95 percent by weight of at lea~t one diol and/or triol and from 5 to 95 percent by weight of at lea~t one alkyl-substituted meta-phenylenediamine, 3,3'-dialkyl, and/or 3,3',5,5'-tetraalkyl-~SS~ '7 substituted 4,4'-diaminodiphenylmethane, or preerably alkyl~substituted meta-phenylenediamine. The percents by weight are based on the total weight of component (c), preferably~ mixtures of rom 50 to 80 percent by weight 2,4-dimethyl-6-tert-butyl-1,3-phenylanediamine, 2,4 diethyl-6-methyl, and/or 2-methyl-4,6-diethyl-1,3-phenylenediamine, and from 20 to 50 percent by weight 1,3-phenylenediamine, 2,4- and/or 2,6-toluenediamine.
The chain extender~ and/or crosslinking agents of component (c) as well as their mixtures may be used in the process of the invention in amounts from 2 to 60 percent by weight, preferably from 8 to 50 percent by weight, and more preferably from 10 to 40 percent by weight based on the weight of the (b) component.

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(d) Preferably used as the catalyst component (d) are tho~e cc~mpound~ which greatly accelerate the reaction of the hydroxyl group-containing compounds of the (b) and (c) components with the polyisocyanates. Organometallic ~ compounds may be used, preferably organic tin compounds ~uch as tin (II) salts of organic carboxylic acids such as tin (~I) acetate, tin (II) octoate, tin (II) ethylhexoate, and tin (II) borate, and the dialkyl tin (I~) salts o~ organic dicarboxylic acids. For example, dibutyl tin diacetate, dibuty~ tin dilaurate, dibutyl ~L~SS~ 7 tin maleate, and dioctyl tin diacetate. ~he organo metallic compounds are used alone or, preferably, in combination with highly basic amines. Typical examples are amidines such a~ 2,3-dimethyl-3,4,5,6-tetrahydro-pyrimidine, tertiary amines such a~ triethylamine, tributylamine, dimethylbenzylamine, N methyl, N-ethyl, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylene-diamine, N,N,N',N'-tetramethylbutan~diamine~ penta-methyldiethylenetri~mine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiper-azine, 1,2-dimethylimidazol, 1-azobicyclo(3,3,0)octane and preferably 1,4-diazabicyclo-(2,2,2)-octane, and alkanol compounds such as triethanolamine, triisopro-panolamine, N-methyl and N-ethyldiethanolamine and dimethylethanolamine.

The following may also be used as catalysts: tris(di-alkylaminoalkyl)-s-hexahydrotriazine3, more preferably tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine, tetraalkylammonium hydroxide~ such as tetramethyl ammonium hydroxide, alkali hydroxides such as sodium - hydroxide and alkali alcoholates auch a~ sodium methylate and potassium isopropylate, a~ well as alkali ~alts of long-chained fatty acids having from 10 to 20 carbon atoms and optionally hydroxyl groups on the side ~2SS~)~7 position~. Fro~ 0.001 to 5 percent by weight catalyst or catalyst combinatlon i~ used based on the weight of component (b), preferably from 0.05 to 2 percent by weight.

(e) Auxiliaries and/or additives, component (e), may also be incorporated in the reaction mixture. Typical examples are blowing agents, surfactant~, fillers, dyes, pigments, flame retardants, relea~e agents, agent~ to prevent hydrolysis, fungistats, and bacterio~
stat~.

Among the blowing agents which may optionally be used in the proces~ of the invention i~ water, which reacts with the isocyanate groups to form carbon dioxide. The amount~ of water which are mo~t effective range ~rom O.l to 2 percent ba~ed on the weight of the polyisocya-nate.

Other blowing agents which may be u~ed are low boiling polnt liquid~ which ~vaporate as a re~ult of the exothermic addition polymerization reaction. Suitable agen~ are liquids which are inert toward the organic polyi~ocyanate and which have boiling point~ les3 than lOO~C~ Examples of ~uch preferably use~ liquids are iSU~7 halogenated hydrocarbons such as methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichlorotetrafluoroethane, and 1,1,2-trichloro-1,2,2-trifluoroethane. Mixture~ of these low-boiling point liquids with one another and/or with other substituted or unsubstituted hydrocarbons may also be used. The most desirable amount of a low boiling point liquid to be used in preparing the cellular PUR, PUR PU, or PU elastomers depends on the de~ired density as well a~ on whether water i~ option-ally used~ In general, amounts from 1 to lS parts by weight, based on lOO parts by weight organic polyisocy-anate, produced satisfactory results.
Surfactants which may be u~ed are those which aid in homogenizing the initial materials. Typical example~ are emul~ifier~ such as the sodium salts of castor oil qulfates or o~ fatty acids as well as s~lts o~ fatty acids with amines. For example, oleic acid, diethylamine, or stearic acid diethanolamine, salts of sulfonic acids such as alkali or ammonium ~al~ of dodecylbenzenedi3ulfonic acid or dinaphthylmethanedisulfonic acid and ricinoleic acid. The surf-actants are generally u~ed in amounts from 0.1 to 5 parts by weight, baJed on 100 parts by weight of component tb).

3L2S;5~7 Among the filleral in partisular reinforcing fillers~ are ~he e~se~ially ~nown organic and inorganic fillerq, reinforcing subs~ance~, weight-increasing ~ub-stance~ and substances to i~prove the wear resistance of paint~ and coating~. Typical example~ of inorganic fillers are ~ilicate mineral~, for example, lamellar ~ilicate~ such a~ antigorite, ~erpentine, horn blend~, amphibole, chriso-tile, talcum, metal oxide ~uch aq kaolin, aluminum oxideq, titani~m oxide~, and iron oxides, metal salts such a~ chalk, heavy spar, and inorganic pig0ent~ 3uch as cadmium ~ulfide, zinc ~ulfide, as well a~ powdered a~besto~ Pre~erably used are kaolin tChina Clay), aluminum 3ilicate, and coprecipi-tate~ of barium sulfate and alu~inu~ silicate, a~ well as natural and synthetic fibrous mineral~ like asbe~tos and wolla~tonite. Typical organic fillers which may be used are coal, melamine, pine resin, cyclopentadienyl re~ins, and graft polymers based on styrene acrylonitrile prepared by ~n ~itu polymeriza~ion of acrylonitril~ styrene mixtures in polyether polyol~ a~ described in German patent~ 11 11 394, 12 22 G69 (U.S. 3,304,273, 3,383,351, 3,523,093); 11 52 536 (GB 1,040,452~, and 11 52 537 ~GB 987,618), which may then opt~onally be aminated. Other organic fillers which can be used include polyoxyalkylene polyol~ or filler polyolyoxy-alkylene polyamines~ where agueou~ polymer dispersion~ are converted to polyoxyalkylene polyol di~persions or polyoxy-alkylene polyamine di~perslons.

The inorganic and organic fillers may be used individually or in the ~orm of mixture~. Preferably, stable filler polyoxyalkylene polyol di~p2rsions are u~ed in which the filler~ are reduced to a particle size le~ than 7 ~m in situ in the presence of polyoxyalkylene polyol~ by means of high localized energy denqities and are dispersed at the same time.
The inorganic and/or organic fillers are incorpor-ated in the reaction mixture, preferably in amounts from 0.5 to 50 percent by wei~ht, more preferably from 1 to 40 percent by weight, based on the weight of components (a) through (c).
~urther information on the further auxiliaries and additive~ as cited above may be found in the technical literature, for example J.H Saunders and K.C. Frisch, Polyurethane~ Che _stry_and Technol Part II Technolo~y. High Polymer~, vol. 16, New York:
Inter~cience Publi~hers, 1962, 1964; or Polyurethane.
Kunststo~f Handbuch, volO VII, l~t ed., 2nd ed. Munich:
Carl Han~er Verlag, 1966, 1983.
To prepare the PIJR, PUR-PU, or PU elastomers, the organic polyisocyanate~, component ~a), the higher molecular weight compounds having at lea~t two reactive hydrogen atoms, component (b), and chain extenders and/or cro3s linking agents, component tc), are reacted in such amount ~ ;~ss~

that the equivalent ratio of isocyanate groups in the polyisocyanate, component (a), to the sum of reactive hydrogen atoms in components (b) and (c) is 1:0.85 to 1:1.25 and preferably 1:0.95 to 1:1.15, more preferably 1:0.98 to 1.05.
The encapsulation of glas~ plate edge~ using the process of the invention i~ pre~erably performed in tempera-ture-controlled metal mold~ such as molds con~tructed of steel, cast iron, aluminum, or in plastic molds con~tructed of epoxy resins, or unsaturated polyester resins. Gener-ally, ~ultiple-part molds having an upper and a lower molding plate are used. The area between the molding plates form~ a peripheral area for clamping the cut edge of the glass plate as well as a cavity fo~ holding the reactable PUR, PUR-PU, or PU elastomer mixture. In order to seal off the cavity, which is to be filled by ca~ting or preferably injection technique~, and to prevent the reactable ela~tomQr from creeping along the margin of the plate glas~ due to capillary action, it i3 de~irable to place a ga~ket con structed of an elastic material between the plate of glas~
and the mold. A gasket constructed of plastic polymer3 or products of cbnden~ation or addition polymerization, or some other sealing agent or device can be u~ed. Additional fa~tener~ may be positioned in ~he ca~ity so that they become connected to the plate glass in a single operation by S~ 7 mean~ of the PUR, PUR-PU, or PU ela~tomer~. For example, the ~urface in the cavity may be covered with release films or, preferably, decorative material~ ~uch as metallized or printed plastic ~ilms, or metal or plaatic decorative molding strips.
Preferably, the plate of glass i~ positioned horizontally in the mold~ However, other angles of inclina-tion between O and 90, preferably between O and 45, are possible. In addition, the clo~ed molds containing the plate of gla~s may be rotated as dèsired about the three normal spatial axes, or the reactable elastomer mixture may be injected from below, above, and/or from the sides.
The PUR, PUR-PU, or PU elastomer~ are prepared by ~means of the prepolymer process, or pre~erably in a one-shot proce~ For example by pouring the reaction mixture into the mold cavity, or preferably, by lnjecting the mixture with the aid o~ conventional reaction injection molding techniques (RIM). This proces~ is described, for example, by Piechota and Rohr, Inte~ralschaum~toff. Munich: Carl Hanser ~erlag, 1975, D.J. Prepelka and J.L. Wharton, Journal of Cellular_Plastics, (March/April 1975~: pgs. 87-98, and U. Knipp, Journal of Cellular Plastics, (March~April 1973):
_ _ , . _ . _ pg~. 76~
When u~ing a mixing chamber having several feed nozzles, the system component~ may be ~ed in individually '~2S~

and mixed inten~ively in the mixing chamber~ It has been found to be particularly desirable to use a two-component proces~ and to dis~olve the chain extender and/or cross-linking agent, component (c~, in the higher molecular weight compound, component (b), having at lea~t two reactive hydrogen atoms and to combine them with the catalysts as well a~ optional auxiliaries and additives in component (a) and to u~e the organic polyi~ocyanates a~ component (b).
One advantage of this is that components (a) and (b) may be stored separately and tran~ported in a space-saving man-ner. In proce~ing they then only need to be mixed together in the appropriate amount3.
The amount of reaction mixture fed into the mold is established such that the PUR, PUR-PU, or PU ela~tomer encapsulating moldings have a density of from 0.8 to 1.4 g/cm3, preferably from 0.9 to 1l.2 g/cm3. The optionally cellular elastomers may be ~ormed by gas es trapped in the reaction mixture, in particular air, through the u~e of ~oi3ture-contalning starting component~ (b) through (e) or through the carefully controlled addition of water and/or inert physic~l blowing agent~. The system component~ are mixed togethe~ at tempexatures from 15 to 80C, preferably from 20~ to 55~C, and fed into the mold. The de~ired mold ~emperature is from 20 to 90C, preferably from 30 to The PUR, PUR-PU, or PU elastomer encapsulated moldings of the invention po~se~s a hardness of from Shore A
40 to Shore D 60, preferably from Shore A 40 to ao, and more preferably from Shore A 40 to 60 in accordance with DXN
53,505, a tensile strength of from 5 to 27 N/mm2~ preferably from 5 to 16 N/mm2 in accordance with DIN 53,504, and a tear resistance of from 3.5 tc 30 N/mm, preferably fro~ 3.5 to 19 N/mm in accordance with DIN 53,507.
The plates of glass encapsulated with PUR, PUR-PU, or PU elastomers are preferably uqed in tran~portation vehicles, for example railroad vehicle~ and, in particular, automotive vehicles.
The part~ cited in the examples are based on weight.

~:~ss~

Example 1 (a) A 5.5 mm thick plate of silicata glass wa~ coated around the edges with a solution of 3 parts by weight y-aminopropyltrimethoxy~ilane in 97 part~ by weight isopropanol. The adhesion improving agent was applied using a felt applicator at a liquid layer thickness o 40~m. Then the plate of silicate glass was dried.

(b) A 5.5 mm thick plate of silicate glass was coated as described in Example l(a). After the isopropanol had evaporated, a solution of 5 part~ by weight of an isocyanate group-containing prepolymer of 4,4' di-phenylmethane dii~ocyanate and a polyester of 1,~-butanediol polyadipate havin~ an isocyanate content of 1.7 percent by weight, and 95 parts by weight methyl ethyl ketone was applied at a liquid layer thickness of 40 ~m, and the plate of silicate glass was dried.
Example 2 (a) Component-A mixture comprising 81.0 part~ by weight of a polyether polyol having a hydroxyl number of 26, prepared by the addition of 1,2-pxopylene oxide and the subsequent addition of ethylene oxide to trimethylolpropane, 12.6 part~
by weight 1,3-dimethyl-5-tert-butyl-2,4-diaminobenzene, 5.2 part~ ~y weight 1,3-phenylenediamine, 0.33 parts by t.~6~

weight 1,4-diazabicyclo-(2,2,2)-octane and 0.1 parts by weight dibutyltindilaurate~

(b ~ omponent:
A mixture of 48 parts by weight of polyoxy-propylene glycol and carbodiimide-modified 4,4'-diphenyl~
methane diisocyanate having an i~ocyanate content of 26.5 percent by weight.
A plate of silicate gla~ treated in accordance with Example l(a), but without the use of external release agent~, was placed horizontally in an aluminum mold. The (a) and (b) components were heated to 50C and injected by using a high-pres~ure Puromat~ 30 metering system from Ela~togran-Maschinenbau into the ca~ity of the closed mold and heated to 70C. The mold residence time was 30 ~econds.
The resulting PUR-PU ela~tomer had the following mechanical properties:

Den~ity per DIN 53,420 1.1 g/cm3 Shore D Hardness per DIN 53,505 61 Tensile Strength per DIN 53,S04 28.0 N/mm2 Tear Resistance per DI~ 53,507 28.7 N/mm2 ~255~67 Exam~le 3 (a) Component .

A mixture of 79.2 parts by weight of a polyether polyol having a hydroxyl number of 26 aq in Example 2, 8~23 part~ by weight ethylene glycol; 3.00 part~ by weight methylene chloride, 0.12 parts by weight dibutyl tin dilaurate, 0.15 parts by weight triethylenediamine in ethylene glycol (33 percent by weight solution), 5.8 parts by weight black paste, 3nd 2.5 parts by weight ~inc ~tearate.

.
(b) Component:
A mixture of 56 parts by weight of the modified polyisocyanate mixture of Example 2.
The glass plate coated on the edges was prepared as deqcribed in Example 2 except that the glass plate was pretreat~d per Example l(b~.
The resulting PUR elastomer had the following mechanical properties:

Density per DIN 53,420 l.OS g~cm3 Shore D Hardness per DIN 53,505 90 Tensile Strength per DIN 53,504 16 N/mm2 Tear Resistance per DIN 53,507 19 N/mm i5~

Exam~le 4 (a) Component:
A mixture of 68.37 part~ by weight of a polyether polyol having a hydroxyl number of 26 per Example 2; 18.78 part~ by weight ethylene glycol, 3.02 parts by weight methylene chloride, 0.01 parts by weight dibutyl tin dilaurate, 0.011 part~ by weight triethylenediamine in ethylene glycol (25 percent by weight solution), 1.76 parts by weight zinc qtearate, and 6.05 parts by weight black paste.

tb) Compone_t:
A mixture of 112 parts by weight of a mixture of polyoxypropylene glycol and carbodiimide-modified 4,4'-diphenylmethane dii~ocyanate having a~ isocyanate content of 28 percent by weight.
The coated glas~ plate wa~ pretreated per Example l(b) and prepared as de~qcribed in Example 3.
The resulting PUR elastomer had the following mechanical propertie~:

Density per DIN 53,420 1.05 gJcm3 Shore D Hardness per DIN 53,505 62 Tensile Strength per DIN 53,504 22.0 NJmm2 Tear Resistance per DIN 53,507 25.0 N~mm

Claims (16)

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

1. A process for coating with one or more adhesion-improving agents and covering an edge of plate glass with polyu-rethane or polyurethane-polyurea or polyurea elastomers compri-sing:
1) coating said edges of the plate glass with said adhesion-improving agent, 2) placing said plate glass in an open mold, 3) closing said mold, 4) charging a cavity formed between said glass plate and said mold with a reactive mixture comprising, a) an organic polyisocyanate, b) a higher molecular weight compound having at least 2 reactive hydrogen atoms and selected from a group consisting of polyether polyol, polyester polyol, polythioether polyol, polyes-ter amide, hydroxyl group-containing polyacetal and/or hydroxyl group-containing aliphatic poly-carbonate, c) a chain-extension agent and/or cross-linking agent selected from a group consisting of ali-phatic, cycloaliphatic or araliphatic diols and/or triols, a secondary aromatic diamine, and preferably a primary, unsubstituted and/or substituted aromatic di- and/or higher functio-nal polyamine, d) a catalyst, e) auxiliary and/or additive, and 5) curing the reaction mixture.

2. The process of claim 1 wherein said reactive mix-ture is reacted in a one-shot process.

3. The process of claim 1, wherein said reactive mix-ture is injected into the cavity formed between the plate glass and said mold by a reaction injection molding technique.

4. The process of claim 2 wherein said reaction pro-cess is a single step having a cycle time of under 120 seconds.

5. The process of claim 3 wherein said reaction pro-cess is a single step having a cycle time of under 120 seconds.

6. The process of claim 1, 2 or 3, wherein the higher molecular weight component (b) has a molecular weight of from 800 to 8000 and a functionality of from 2 to 8.

7. The process of claim 1, 2 or 3, wherein the chain-extension agent and/or cross-linking agent component (c) has a molecular weight of from 60 to 600 and a functionality of from 2 to 4.

8. The process of claim 1, 2 or 3, wherein said poly-urethane elastomer, or polyurethane-polyurea elastomer, or po-lyurea elastomer coating has a density of from 0.8 to 1.4 g/cm3, a hardness of Shore A 40 to Shore D 60, a tensile strength of from 5 to 27 N/mm2, and a tear strength of from 3.5 to 30 N/mm.

9. The process of claim 1, 2 or 3, wherein said plate glass is made of silicate glass from 3 to 20 mm thick, wherein said plate glass is mechanically or chemically treated.

10. The process of claim 1, wherein said plate glass is coated at its edges with said adhesion-improving agent befo-re said edges are covered with said elastomer.

11. The process of claim 1, 2 or 3, wherein said adhe-sion-improving agent is selected from a group consisting of a silane ester, an organic polyisocyanate, a modified organic polyisocyanate, an isocyanate end group containing prepolymer, and a polyfunctional epoxy compound.

12. The process of claim 1, 2 or 3, wherein said adhe-sion-improving agent is applied to a degreased glass plate in a solution containing from 1 to 10 percent by weight adhesion-improving agent.

13. The process of claim 1, 2 or 3, wherein an adhesion-improving layer is one or more individual layers of a single adhesion-improving agent or of different adhesion-improving agents.

14. The process of claim 10 wherein said adhesion-improving agent is selected from a group consisting of a silane ester, an organic polyisocyanate, a modified organic polyisocya-nate, an isocyanate end group-containing prepolymer, and a poly-functional epoxy compound.

15. The process of claim 10 wherein said adhesion-improving agent is applied to a degreased glass plate in a so-lution containing from 1 to 10 percent by weight adhesion-impro-ving agent.

16. The process of claim 10 wherein an adhesion-im-proving layer is one or more individual layers of a single adhesion-improving agent or of different adhesion-improving agents.