Note: Descriptions are shown in the official language in which they were submitted.
~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
-- 1 --
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.
1~2S5()~
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
//
/
/
/ / .
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
- 4 -
~;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~.
~lZS5Q~
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.
-- 6 --
~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
-- 10 --
~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-
-- 11 --
~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
- 12 -
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).
- 13 -
~;~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.
- 14 -
~;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~
15 -
~SSV67
R NE~ 2 R NH2
H2N- ~ -R and/or ~ -R
R3 R3 NH2
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
- 16 -
~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
R5 R6
~ 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
H2N R5 R6 HN2 R5
R4- ~ 2 ~ N~2 and/or R - ~ -CH ~ 6
7 2 ~
R R NH2
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
- 17 -
5C1 67
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-
18 -
~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.
.
(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
-- 19 --
~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
- 20 -
~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
- 21 -
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).
- 22 -
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.
- 23 -
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
- 24 -
~ ;~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
- 2S -
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
- 26 -
'~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
75C
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.
- 28
~:~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
- 29 -
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
- 30 -
~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
- 32 -
