Tintable, dyeable, curable coatings and coated articles

The invention disclosed in this application is the use of novel silanes in curable coatings to allow tinting or dyeing of the coatings after they are cured on certain substrates. An example of one such useful silane is ##STR1## The silanes and the curable coatings are also useful as antistat and antifog coatings.

BACKGROUND OF THE INVENTION 
The present invention relates to coating compositions which are curable and 
which can be used on transparent solid substrates. These coating 
compositions contain novel silanes which allow for dyeing and/or tinting 
(hereinafter "tintability") of such solid substrates. The curable coating 
compositions, containing the novel silanes, not only allow tintability, 
but these coating compositions also give excellent abrasion resistance, 
antifog and antistat properties to the coated article. In addition, the 
coatings described herein give very aesthetically pleasing, uniform, 
gel-free surfaces to the coated article. 
Plastic materials, especially clear, transparent plastic materials, have 
been used in increasing amounts for various applications where the user 
desired such properties as lightweightness and ease of handling. Further, 
plastics have been developed which are not only lightweight but are strong 
such that they have application in those uses where breaking, cracking or 
splintering are a problem, such as in eyewear. In the United States in 
1977, the sales of glass spectacle lenses was estimated at about 40 
million pairs as opposed to about 21 million pairs for plastic. It is 
predicted that in 1982, 30 million pairs of glass lenses will be sold as 
compared to 40 million pair of plastic lenses. 
A certain number of these lenses will be tinted in order to reduce the 
transmission of light through them. This tintability of the lenses does 
not seem to be a major problem, since there are a number of tints of 
varying colors which can be used to tint the lenses. Moreover, the 
plastics are readily receptive to these tints so that various intensities, 
as well as various colors of lenses, can be obtained. 
Plastic substrates have several major problems, however. Generally, 
polycarbonates and acrylics are soft, and articles prepared from these 
plastics scratch or abrade quite readily. Therefore, there has been a 
great deal of investigation into coatings for such articles in order to 
enhance the abrasion resistance of the surface of the plastic articles. 
This problem is particularly acute in plastic lenses and transparent 
plastic sheeting used in bus, airplane, and train windows and in 
architectural windows and panels. 
One premier coating that has found wide acceptance for such applications is 
the coating known as the Dow Corning abrasion resistant coating, which is 
a siloxane based, silica reacted, curable coating especially adapted to 
give hard surfaces when cured on plastic substrates. This material is 
disclosed in U.S. Pat. No. 3,986,997, issued Oct. 19, 1976. This material, 
however, even though having a hard, abrasion resistant surface, has a 
major drawback. It is not tintable! Therefore, it would be useful to 
develop an abrasion resistant coating which not only gave enhanced 
abrasion resistance to these plastic substrates, but it would be extremely 
useful if the coating was also tintable. 
Such coatings have been developed, but they too have some drawbacks. For 
example, U.S. Pat. No. 4,211,823, issued July 8, 1980, describes the 
preparation of a tintable coating for use on plastic substrates. The 
material comprises a hydrolyzate of a silane compound containing at least 
one epoxy group and not less than two alkoxy groups, fine silica particles 
and an aluminum chelate compound. This material is tintable but suffers 
from the fact that it is not exceptionally abrasion resistant, and it has 
a short resin pot life with a tendency to easily form gel specks. 
Another coating system for use on lenses is a material described in U.S. 
Pat. No. 4,073,967, issued Feb. 14, 1978, as a combination of a reactive 
silane and a metal cluster. This material is tintable but does not offer 
the ultimate in abrasion resistance and handleability. 
Furthermore, it would be desirable to have an additive for various resins 
in order to achieve tintability in resins which are not themselves 
ordinarily tintable. 
The silane adducts of this invention help overcome the problems associated 
with the prior art materials and, in addition, these silane adducts are 
not volatile under coating curing conditions or in use in the cured 
coating. As long as the silane adducts are compatible with the curable 
resin, the adduct will be useful and perform its function therein. 
THE INVENTION 
This invention therefore deals with a composition of matter which is a 
silane having the general formula (XO).sub.3 SiRSR' wherein X is an alkyl 
radical of 1-4 carbon atoms, R is a divalent aliphatic hyrdocarbon radical 
containing less than five carbon atoms and R' is selected from a group 
consisting of 
##STR2## 
wherein Q is a radical selected from a group consisting of --CH.sub.2 
CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, 
##STR3## 
wherein in groups (iii), and (iv), R" is hydrogen or the methyl group and 
in group (ii), R" is hydrogen, the methyl group or the isobutoxymethyl 
group. 
In this invention, X is an alkyl radical of 1-4 carbon atoms, and examples 
of such radicals include the methoxy, ethoxy, propoxy and butoxy radicals. 
It should be noted that there are always three such groups per molecule. 
It is believed that the presence of these groups allows for the 
non-volatility of the compound when heated during the cure reaction or 
when the cured coating is subjected to extreme temperatures when in use. 
R for purposes of this invention is a divalent aliphatic hydrocarbon 
radical containing less than five carbon atoms. The alkylene bridge in 
these silanes should be as small as possible, as the increased molecular 
size leads to the loss of abrasion resistance in the final cured resin. 
Therefore, the alkylene bridge is preferred to be three carbons or less in 
length. Thus, methylene, ethylene and propylene radicals are the preferred 
alkylene bridges in this invention. Most preferred is the propylene bridge 
because of the simplicity of manufacturing the silanes using the propylene 
bridge precursor, i.e. the allyl group. 
The letter S is a sulfur atom and R" is selected from a vary narrow group 
as set forth in the specification above as groups (i)-(v). Q in these 
groups is a radical selected from a group consisting of --CH.sub.2 
CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, 
##STR4## 
R" in these groups takes on a different meaning depending on which group, 
(ii), (iii) or (iv), is being considered. In groups (iii) and (iv), R" can 
be hydrogen or the methyl group, and in group (ii), R" can be hydrogen, 
the methyl group or the isobutoxymethyl group. No such groups are shown as 
required for groups (i) or (v) because of the nature of the molecules. 
The limitations on these groups, R", is only because of the unavailability 
of the precursor compounds. 
There are a number of methods by which these materials can be produced. It 
is known, for example, to add mercaptan groups to unsaturated organic 
groups under the influence of free radical catalysts or ultraviolet light. 
Thus, one can prepare these compounds by adding mercaptoalkyl-containing 
trialkoxy silanes to unsaturated organic amines and amides or, one can add 
mercapto containing organoamines or amides to unsaturated 
trialkoxysilanes. Conventional free radical catalysts or ultraviolet light 
will cause such reactions to be efficient; however, sometimes added 
catalysts are not necessarily required for these reactions. Sometimes 
solvents can be used, but they are not required in some cases. Generally, 
the materials to be reacted are mixed together and then catalyzed and then 
gently heated. Quite frequently, after gentle heating, the reaction 
exotherms to near completion of the reaction. Occasionally, the reaction 
is required to be refluxed for a period of time to ensure the completion 
of the addition reaction. 
The preferred method for this invention is the addition of commercially 
available mercaptoalkyl-containing trialkoxysilanes to unsaturated organic 
amines or amides under the influence of peroxides or 
axobisisobutyronitrile catalysts. The unsaturation on the organic 
precursors is preferred to be the allyl or vinyl groups. 
The examples clearly illustrate the methods and means preferred for the 
manufacture of the inventive silanes herein. 
A further aspect of this invention is the use of the above-mentioned 
silanes as additives to curable resins. This invention therefore also 
consists of a composition of matter which comprises 
(A) 1 to 50 weight percent, based on the weight of (A) and (B), of a silane 
having the general formula (XO).sub.3 SiRSR' wherein X is an alkyl radical 
of 1 to 4 carbon atoms, R is a divalent aliphatic hydrocarbon radical 
containing less than five carbon atoms and R' is selected from a group 
consisting of 
##STR5## 
wherein Q is a radical selected from a group consisting of --CH.sub.2 
CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, 
##STR6## 
wherein in groups (iii) and (iv), R" is hydrogen or the methyl group and 
in group (ii), R" is hydrogen, the methyl group or the isobutoxymethyl 
group and 
(B) 99 to 50 weight percent, based on the weight of (A) and (B), of a 
curable resin compatible with component (A). 
The curable resin and the silane additive must be compatible in order for 
the additive to function as it should, to give uniform tintability. 
Generally, from 1 to 50 weight percent of silane (A), based on the total 
weight of (A) and (B), will work properly in this invention. Generally, as 
the weight percent of the additive in the composition increases, the 
intensity of the tint increases. Also, as the weight percent of the 
additive in the composition increases, the abrasion resistance decreases. 
The abrasion resistance will decrease nominally at the lower amounts of 
additive, i.e. 1-25 weight percent, then the abrasion resistance will 
decrease dramatically with larger quantities of additive. The loss of 
abrasion resistance is dependent on the curable resin used and the amount 
of additive used in that resin. Normally, 15-35 weight percent of the 
additive gives the best tintability and the least amount of loss in 
abrasion resistance. 
The additive is useful in any curable resin in which it is compatible. 
Since the addition is a silane, it is quite compatible with silicone-based 
resins or silicone-organic resins. It is least compatible with organic 
resins. The additive is highly compatible with the resins described in 
U.S. Pat. Nos. 4,073,967, 4,211,823 and 3,986,997, and wide variations of 
such pigment-free coating compositions. Especially good resins, which are 
highly compatible with the additives of this invention, are these 
comprising 30 to 70 weight percent of colloidal silica; 0 to 25 weight 
percent of R""SiO.sub.3/2 as a partial hydrolyzate, wherein R"" has the 
meaning set forth for R in U.S. Pat. No. 3,986,997 and includes also the 
phenyl radical and the gamma mercaptopropyl radical and 15-35 weight 
percent of the silane additive, all based on the total weight of colloidal 
silica, R""SiO.sub.3/2 and silane additive in the mixture. This material 
is similar to the compositions described in U.S. Pat. No. 3,986,997, but 
the relative amounts of colloidal silica and partial hydrolyzate are 
changed to enhance the tintability of films prepared from this resin. The 
amount of partial hydrolyzate can be reduced to zero if the silane 
additive is cohydrolyzed into the system along with the colloidal silica. 
Small amounts of the partial hydrolyzate can be used with the colloidal 
silica, that is, up to 25 weight percent of the colloidal silica/partial 
hydrolyzate can be partial hydrolyzate. The solvents, catalysts and 
adjuncts set forth in U.S. Pat. No. 3,986,997 can also be used in this 
resin composition. 
It is possible to use solvents to enhance the compatibility of the silane 
additive in the resin systems. Solvents found to be useful herein are 
alcohols, glycols, glycol ethers, ketones and esters. 
Catalysts for these resin systems are dependent on which systems are used. 
The presence of the silane in the resin does not appear to affect 
catalysis. 
One further aspect of this invention is a solid substrate coated with the 
silane additive. Thus, the silane additive can be made curable and, in 
this form, it can be coated on a substrate, cured, and be tinted in the 
manner described in the examples. 
In addition, the invention consists of solid substrates coated with the 
resin composition containing the silane additive. This aspect of the 
invention is very important because of the fact that a storage stable, one 
coat, tintable, curable coating is needed in the marketplace for plastic 
spectacle lenses and plastic windows and decorative panels. 
Further, the resin compositions containing the silane additives are useful 
as coatings on various substrates as an antistatic coating. Thus, this 
material can be used on any substrate, transparent or non-transparent, if 
an antistatic coating is required. Further, this material can be used as 
an antifog coating on various substrates and, therefore, when an antifog 
coating is required, this material can be used. 
It should be noted that the silane additive can be cured through hydrolysis 
and then catalysis so that the silane additive itself can be used as an 
antistatic and/or antifog coating. 
Substrates that can be coated with the compositions of this invention 
include leather, plastic, wood, metal, rubber, paper and glass. 
Particularly, plastic lenses, sheets and art objects can be coated. Glass 
windows, for example aircraft windows, can be made antifog and antistatic. 
Metals can be coated with these compositions, especially aluminum, which 
when coated with these compositions, can be tinted with various tints and 
dyes. 
In the following examples, the apparatus and testing procedures used for 
the results shown therein are as follows: 
Vapor Degreasing 
Some of the plastic panels used herein were degreased by subjecting them to 
a five minute immersion in Freon.TM.TES (trichlorotrifluoroethane 
including 4% denatured ethanol and a stabilizer proprietary to DuPont, E. 
I. DuPont deNemours, Wilmington, Del., USA) in a Branson Ultrasonic 
Degreaser (Branson Cleaning Equipment Co., Shelton, CT, USA). 
Heat Cleaning 
After vapor degreasing, all plastic panels coated in the examples were heat 
annealed by subjecting the panels to at least two hours at 125.degree. C. 
for polycarbonate and two hours at 80.degree. C. for acrylic. The panels 
are always cooled to room temperature before coating. 
Tinting Materials 
All tinted samples were tinted using Sun Brown Molecular Catalytic.TM. dyes 
manufactured by Brain Power Inc., Miami, FL, USA. 
The samples were tinted in a hot aqueous bath at about 85.degree. C. for 15 
minutes. The length of time of tinting when varied is noted in the 
examples. 
Light Transmission 
The amount of tintability was determined by reading the amount of light 
transmitted through a coated panel. The difference in light transmission 
before and after the tinting was taken on a Gardner Haze Meter, Model UX10 
coupled to a P5500 Photometric Unit. The light transmission is reported in 
percent of total light transmitted through the sample. 
Adhesion Testing 
Adhesion was measured by crosscut adhesion. A series of scratches are made 
through the coating into the substrate in the pattern of a grid containing 
25 squares, each being about 1.5 mm square (1/16 in.). This surface is 
covered with No. 600 Scotch Brand adhesive tape (3M Co., USA) and pressed 
down firmly. The tape is withdrawn from the surface with one rapid motion 
at about a 90.degree. angle from the surface of the substrate. The number 
of squares remaining intact on the substrate are reported as a percentage 
of the total number of squares on the grid. 
Abrasion Resistance 
Abrasion resistance was determined according to ASTM Method D1044-56. The 
instrument was a Taber Abraser. A 500 gram test load was used with CS-10F 
abrasive wheels and the test panels were subjected to 500 revolutions on 
the abraser turntable. The percent change in haze which is the criterion 
for determining the abrasion resistance of the coating is determined by 
measuring the difference in haze of the unabrased and abrased coatings. 
Haze is defined as the percentage of transmitted light which, in passing 
through the specimen, deviates from the incident beam by forward 
scattering. In this method, only light flux that deviates more than 2.5 
degrees on the average is considered to be haze. The % .DELTA. Haze on the 
coatings was determined by ASTM Method D1003-61. A Hunter Haze Meter, 
manufactured by Gardner Laboratory, Inc., was used. The .DELTA. Haze was 
calculated by measuring the amount of diffused light, dividing by the 
amount of transmitted light and multiplying by one hundred.

EXAMPLE 1 
Preparation of 
##STR7## 
Vinylpyrrolidone, 55.6 gms. (0.5 mole) was weighed into a 500 ml., 
3-necked, round-bottomed glass flask. The flask was equipped with a 
water-cooled condenser, stirrer, thermometer, addition funnel and gas 
inlet tube. Mercaptopropyltrimethoxysilane, 107.8 gms. (0.55 mole) and 
Vazo.RTM. 64 catalyst (2,2'-azobis isobutyronitrile manufactured by E. I. 
DuPont deNemours and Co. Inc., Wilmington, Del., USA) (0.5 gm.) were mixed 
and placed in the addition funnel. Nitrogen flow was started to remove air 
from the flask and apparatus and nitrogen purge was used throughout the 
duration of the experiment. The flask was heated to about 82.degree. C. 
and the mixture from the addition funnel was added to the flask contents 
which were reddish-purple in color at the beginning of the addition. The 
color turned to clear brown and then to clear yellow. An exotherm was 
observed to about 90.degree. C. where it was controlled with an ice water 
bath and the flask temperature was maintained between 
85.degree.-90.degree. C. during the reaction. The addition took place over 
about 1 hour. The reaction was heated for about four hours after the 
addition had been made. An aliquot of the reaction product was titrated 
using standardized iodine to show that the anticipated reaction has 
proceeded to greater than 96% completion. Proton NMR analysis showed a 
structure consistant with the title compound. 
EXAMPLE 2 
Preparation of 
##STR8## 
Mercaptopropyltrimethoxysilane, 107.8 gms., was weighed into a flask 
equipped as in Example 1, above. Vazo 64, (0.5 gm.) was added and the 
solution stirred to dissolve the Vazo 64. The N,N-dimethylacrylamide 
(NNDA) was poured into the addition funnel and the flask was heated to 
80.degree. C. The addition was begun and was accompanied by an exotherm 
which was controlled between 82.degree.-90.degree. C. The addition was 
made in about 20 minutes. The pot temperature was maintained for about 
four additional hours after the addition was complete. Iodine titration 
showed the reaction had proceeded to about 97% conversion. Proton NMR 
analysis showed the structure consistent with the title compound. 
EXAMPLE 3 
Preparation of 
##STR9## 
Mercaptopropyltrimethoxysilane, 100 gms. (0.5 mole) was weighed into a 
flask and the flask was equipped as in Example 1 above. To this was added 
0.6 gm. of Vazo 64. Methacrylamide (MA) 42.6 gms. (0.5 mole) was dissolved 
in 150 gms. of methanol and placed in the addition funnel and added to the 
flask over a six-hour period while the flask was heated and maintained at 
about 85.degree. C. The heat was shut down and the remainder of the 
addition was carried out over a 14-16 hour period. A small amount of Vazo 
64 was added to the flask and reheating was started and the temperature 
was taken to about 100.degree. C. and held for about six hours. Another 
small amount of Vazo 64 was added and the temperature was raised to 
105.degree. C. for an additional seven hours. The reaction had proceeded 
about 86% as indicated by an iodine titration. The H'NMR analysis is 
consistent with the structure (CH.sub.3 O).sub.3 Si(CH.sub.2 ).sub.3 
SCH.sub.2 CH(CH.sub.3)C.dbd.ONH.sub.2. 
EXAMPLE 4 
Preparation of 
##STR10## 
Mercaptopropyltrimethoxysilane, 92 gms. was placed in a 500 ml flask which 
was equipped as in Example 1. Then, 15.8 gms. of the silane was placed in 
a glass vial and there was added 0.5 gm. of Vazo 64 catalyst. The catalyst 
did not completely dissolve and an additional 2 gms. of silane was added 
to the vial to help dissolve the catalyst. Thereafter, 58.1 gms. of allyl 
thiourea was added to the flask, in toto, and the catalyst/silane mixture 
was placed in an addition funnel. The flask was heated to about 85.degree. 
C. which caused the solid allylurea to melt. The Vazo/silane mixture was 
then added at a fast dropwise rate whereupon the temperature dropped 
rapidly and, at the end of the addition, the temperature began to increase 
and it finally reached 95.degree. C. The temperature was held at 
90.degree.-95.degree. C. for 5 hours. During this time, the reaction 
material colored from yellow to orange to brown. An iodine titration 
showed the reaction had progressed about 42%. Another 0.3 gm. of catalyst 
was added and the reaction was heated for another 8 hours at about 
90.degree.-95.degree. C. at which time a titration showed the reaction had 
gone to about 56% completion. 
EXAMPLE 5 
Preparation of 
##STR11## 
The reaction was carried out approximately as set forth in Example 1. 
Mercaptopropyltrimethoxysilane, 105 gms., was reacted with 78.6 gms. of 
isobutoxymethylacrylamide by adding the isobutoxymethylacrylamide to the 
silane at 100.degree. C. over a period of about 2 hours and then the 
reaction was heated an additional 5 hours. A titration indicated that the 
reaction was 86% complete. 
EXAMPLE 6 
Preparation of 
##STR12## 
One hundred grams of mercaptopropyltrimethoxysilane and 0.45 gm. of Vazo 64 
were placed in a flask equipped as in Example 1 above. The mixture was 
heated to 100.degree. C. and vinyl pyridine was added from an addition 
funnel (52.5 gms.). The temperature rose to 120.degree. C. whereupon the 
heating was discontinued and the temperature was reduced to about 
100.degree. C. The addition required about 45 minutes. After 21/2 hours of 
heating, the contents of the flask were golden brown in color. The 
reaction was heated at 100.degree. C. for about 6 hours. The reaction had 
proceeded to about 96% completion as indicated by a tiltration for the 
residual --SH. 
The reaction product was analyzed by H'NMR analysis and the analysis was 
consistent with the structure 
##STR13## 
EXAMPLE 7 
Preparation of 
##STR14## 
using a peroxide catalyst as a free radical source. 
Into a 500 ml., 3-necked flask equipped as in Example 1, there was added 
105 gms. of mercaptopropyltrimethoxysilane and 0.5 gm. of benzoyl 
peroxide. Into an addition funnel there was poured 55.6 gms. of vinyl 
pyrrolidone. The flask was heated to about 90.degree. C. and the addition 
was begun. The addition took about one hour and the contents of the flask 
colored from clear yellow to clear yellow brown. After the addition was 
complete, the contents were heated for four additional hours at about 
90.degree. C. and the contents continued to color a darker brown. An 
iodine titration indicated that the reaction had progressed to essentially 
100% completion. 
EXAMPLE 8 
The preparation of 
##STR15## 
without the addition of a free radical catalyst. 
Mercaptopropyltrimethoxysilane, 105 gms., was placed in a 500 ml., 3-necked 
flask and equipped as in Example 1. Vinyl pyrrolidone, 55.6 gms., was 
poured into the addition funnel. The silane was heated to 100.degree. C. 
and the pyrrolidone was added thereto with an exotherm which was 
controlled to 95.degree.-105.degree. C. over one hour. At the end of this 
time, an iodine titration indicated the reaction was about 95% complete. 
The reaction was heated for about 21/2 additional hours to ensure 
completion of the reaction. 
EXAMPLE 9 
Tintability of an abrasion resistant coating using 
##STR16## 
A commercial abrasion resistant coating resin prepared according to Example 
1 of U.S. Pat. No. 3,986,997 and available from Dow Corning Corporation, 
Midland, Mich., as Q9-6312 abrasion resistant coating resin, was used in 
the following manner with the tintable adduct prepared as in Example 1 
herein. The tintable adduct at 100% solids was diluted with 
isopropanol/butanol (50/50 weight percent) to 45 weight percent solids. 
One hundred grams of this diluted solution was added to 400 gms. of the 
Q9-6312 resin. The pH of the mixture was adjusted to 4.7 by the use of 
acetic acid. A trace of a surfactant was added to help the coating wet out 
on the surface. 
Three polycarbonate plastic panels (4".times.4") were vapor degreased to 
clean them, and then they were heat annealed at 125.degree. C. for two 
hours in an air circulating oven. The panels were then flow coated with 
the coating resin prepared above which contained the tintable adduct and 
cured in an air circulating oven at 125.degree. C. for 16 hours. The 
panels were cooled and one panel was tested for adhesion of the coating 
and for abrasion resistance. Two of the panels were tinted by using a 
brown dye manufactured by Brain Power, Inc., Miami, Fla., USA, and named 
Sun Brown. 
The dye bath was heated to 95.degree. C. and the panels were immersed in 
the bath for 15 minutes and removed. The coating dyed a greenish-brown 
color. Polycarbonate panels coated with the adduct-modified Q9-6312 
without tinting have a light transmission of 90.4%. The tinted panel 
(average of two panels) light transmission was 80.5% or a reduction of 10% 
in light transmission. A sample of the Q9-6312 without the adduct would 
not tint at all, even on prolonged immersion in the heated dye bath. The 
adhesion of the coating containing the adduct, before tinting, was 100% 
and after tinting, the adhesion was still 100%. The % .DELTA. Haze 
abrasion reading was 5.5%. 
EXAMPLE 10 
An abrasion resistant coating resin was prepared according to the general 
procedure set forth in U.S. Pat. No. 3,986,997. This resin composition was 
combined in various proportions with various adducts set forth in Table I 
such that the final resin composition was about 34% solids, wherein the 
solids consisted of about 54 weight percent SiO.sub.2, 16 weight percent 
CH.sub.3 SiO.sub.3/2 and 30 weight percent adduct as the silsesquioxane 
i.e. RSiO.sub.3/2. The pH of all of the resin samples was adjusted to 4.7 
prior to curing on the panels. Polycarbonate panels (4".times.4") were 
flow coated with the resin compositions and cured at 125.degree. C. for 16 
hours in an air circulating oven. When removed from the oven and cooled, 
Sample 4 panels crazed badly. 
The panels were then tinted using the brown dye bath, as in Example 9, for 
15 minutes. 
The results are on Table I. 
TABLE I 
__________________________________________________________________________ 
Results of Tinting on Coated Polycarbonate Panels 
Tintability 
Abrasion Resistance 
ASiO.sub.3/2 where % Transmission 
% .DELTA. Haze 
% Adhesion 
Sample No. 
A is -- Pretint 
Posttint 
Pretint 
Posttint 
Pretint 
Posttint 
__________________________________________________________________________ 
1 No adduct 90.4 
90.4 2.0 2.0 100 100 
(No tint- 
ability) 
##STR17## 89.4 
50.2 8.4 9.5 100 100 
3 
##STR18## 89.4 
68.3 4.9 4.0 0 0 
4 
##STR19## 88.9 
67.3 5.5 3.5 0 0 
5 
##STR20## 89.5 
43.9 11.3 6.1 100 100 
__________________________________________________________________________ 
EXAMPLE 11 
This example illustrates the versatility of utility of the adducts of this 
invention in various siloxane resins containing SiO.sub.2. In this case, R 
in the RSiO.sub.3/2 is changed to change the type of resin obtained. 
The colloidal silica used in this example is a basic colloidal dispersion 
of 13-14 millimicrons silica (pH 9.8, Na.sub.2 O content of 0.32%). The 
adducts were added as 100% solids reaction products. Sodium acetate 
catalyst was also added to the final composition before curing the resin 
on the panels. 
A base resin is prepared by adding each silane to colloidal silica at 
weight ratios of 78.5:21.5 SiO.sub.2 to silane. This material is then 
diluted with isopropanol/butanol (IPA/BuOH) solvent (1:1 weight ratio) to 
obtain the final composition. One sample will illustrate the procedure. 
The silane, in the trialkoxy form, is combined with the aqueous colloidal 
silica and mixed while hydrolysis takes place for about 90 minutes. The 
composition is then diluted with IPA/BuOH (2:1 weight ratio), and the 
adduct was added with stirring which was continued for two hours after the 
addition. The catalyst was then added. Each resin was flow coated onto 
4".times.4" polycarbonate panels, air dried and cured 16 hours at 
125.degree. C. Three panels were coated with each resin. The adduct used 
in each case was that prepared as in Example 1. (See Table II for resin 
compositions and Table III for results of adhesion and tinting.) The dye 
procedure and bath was the same as used in Example 9. 
TABLE II 
__________________________________________________________________________ 
Composition Data for Resin Compositions 
SiO.sub.2 / 
CH.sub.3 COOH/ 
Adduct/ 
Solvent/ 
Catalyst/ 
Ref. 
Silane Type/gms. gms. 
gms. gms. gms. gms. 
__________________________________________________________________________ 
A Vinyltrimethoxysilane 
(11.8) 
67.9 
1.6 16.8 39.0 1.29 
##STR21## (8.7) 
67.9 
1.5 16.8 43.0 1.29 
C (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.3 Cl 
(9.7) 
67.9 
1.6 16.8 42.0 1.29 
D (CH.sub.3 O).sub.3 SiCH.sub.3 
(12.8) 
67.9 
1.7 16.8 39.0 1.29 
__________________________________________________________________________ 
TABLE III 
______________________________________ 
Results on Tintability and Adhesion of Various 
Siloxane/SiO.sub.2 Resins 
Tintability Abrasion Resistance 
% Adhesion 
Ref. % Transmission 
% .DELTA. Haze Pretint 
Posttint 
______________________________________ 
A 46.9 19.0 100 0 
B 10.4 25.4 100 -- 
C 23.6 27.6 100 -- 
D 65.0 6.5 100 90 
______________________________________ 
EXAMPLE 12 
The effects on adhesion and tintability while varying the quantity of an 
inventive adduct 
Inventive adduct was prepared as in Example 1. This adduct was diluted with 
IPA/BuOH (1:1) to 35 weight percent solids. This material was labeled 
"Component A". "Component B" is the commercial abrasion resistant coating 
referred to earlier in this application as Q9-6312 and is also 35 weight 
percent solids. These resins were blended to give varying ratios of A to 
B. The blends were then coated on polycarbonate plastic panels and tinted. 
Adhesion, tintability, and abrasion resistance were tested. A mixture of 
CH.sub.3 COOH and NaOOCCH.sub.3, 50:50 weight ratio, was added to adjust 
pH to 4.7. 
______________________________________ 
CH.sub.3 COOH + 
Ref.Sample 
gms.Component A 
gms.Component B 
##STR22## 
______________________________________ 
1 10 90 0.2 
2 20 80 0.4 
3 30 70 0.6 
4 40 60 0.8 
5 50 50 1.0 
______________________________________ 
See Table IV for test results on these materials. 
TABLE IV 
______________________________________ 
Results of Adhesion/Tintability/Abrasion Resistance of 
Example 12 Resin Compositions 
Sam- 
ple Abrasion Resistance/ 
% Adhesion Tintability 
Ref. % .DELTA. Haze Pretint Posttint 
% Transmission 
______________________________________ 
1 3.7 100 100 89.0 
2 7.0 100 100 84.0 
3 13.8 100 100 64.6 
4 20.5 100 100 46.4 
5 37.5 100 100 37.0 
______________________________________ 
EXAMPLE 13 
Preparation of 
EQU (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.3 SCH.sub.2 CH.sub.2 CH.sub.2 
NHCONH.sub.2 
70 grams of mercaptopropyltrimethoxy silane and 35.5 gms. of allylurea were 
weighed into a flask equipped as in Example 1. The contents of the flask 
were heated to about 90.degree. C. and 0.3 gm. of Vazo 64 was added. The 
temperature indicated an exotherm to about 145.degree. C. which was 
controlled back down to about 100.degree. C. for a total of 61/2 hours and 
it was then cooled. Titration of a sample showed about 71% reaction of the 
mercaptan. The material was filtered. The proton NMR analysis showed a 
structure consistant with the title compound. There was unreacted 
allylurea present at less than 25%. 
EXAMPLE 14 
The following base resin was prepared. Eighty and eight-tenths grams of 
colloidal SiO.sub.2 (as in Example 1); 15.2 grams of CH.sub.3 
Si(OCH.sub.3).sub.3 and 2 grams of CH.sub.3 COOH were stirred together for 
one hour. 86.9 grams of isopropyl alcohol was added thereto along with 
43.4 gms. of butanol. This material was stirred to homogenize and was then 
split into two equal quantities. One-half of this resin was combined with 
9.8 gms. of the material from Example 13. The second one-half was combined 
with 9.2 gms. of the material from Example 6 and after stirring it gelled. 
A new resin was prepared and combined with ten gms. of the material from 
Example 6. About 630 ppm of sodium acetate in an isopropanol solution was 
added to each combination. The combination using the material from Example 
13 was labeled A. The second combination using the material of Example 6 
was labeled B. 
A and B were flow coated on separate polycarbonate 4".times.4" plastic 
panels which had been previously vapor degreased and heat annealed for two 
hours at 125.degree. C. and cooled. After coating, the panels were air 
dried for about 15 minutes and then cured in an air circulating oven at 
125.degree. C. overnight. The panels were dyed using BPI Sun Brown dye at 
90.degree.-95.degree. C. for 15 minutes. The results were as follows. A 
vinyl pyrrolidone adduct in the base resin of this example was prepared 
and was tested as Reference C. 
______________________________________ 
% Adhesion % Light 
Ref. Pretint Posttint % .DELTA. Haze 
Transmission 
______________________________________ 
A 100 100 18.2 74.0 (30 min. 
immersion) 
B 100 100 44.2 51.0 
C 100 100 30.0 73.6 
______________________________________ 
Example 15 
The use of the inventive adduct in a commercial tintable coating to further 
reduce the light transmission 
A coating resin was prepared as shown in Example 2 of U.S. Pat. No. 
4,073,967. This resin was divided into two equal portions. The portion 
that was used "as prepared" was designated A. The other half of the resin 
was combined with an adduct analogous to and prepared as in Example 1 in a 
quantity of 16 weight percent adduct. 
These resins were coated on separate 4".times.4" polycarbonate panels and 
air dried about 15 minutes and then cured overnight (about 16 hours) at 
85.degree. C. The panels were tinted as in Example 14 above. The Panel A 
had a light transmission of 35%. Panel B had a light transmission of less 
than 1%. 
Example 16 
Effect of variation in the SiO.sub.2 content of the coating resin on 
dyeability/tintability 
Five resins were prepared in which the SiO.sub.2 content was varied. The 
resins were prepared by mixing methyltrimethoxysilane, colloidal silica 
(as in Example 1), acetic acid and water. After these materials were mixed 
and homogenized with stirring, a 50/50 weight ratio of isopropanol and 
butanol solvent was added to the resin. After continued stirring for a few 
minutes, the resins cleared and they were then stirred for three hours and 
there was added thereto an adduct prepared as in Example 1 and having the 
same chemical formula. The resins were allowed to stand overnight and 
about 600 ppm sodium acetate was added to each resin as a curing catalyst. 
The resin formulations can be found in the following table. 
EXAMPLE 16 
______________________________________ 
The Resin Formulations 
gms. gms. gms. 
gms. gms. Acetic 
gms. Sol- Ad- Wt. % 
Ref. CH.sub.3 Si(OCH.sub.3).sub.3 
SiO.sub.2 
Acid H.sub.2 O 
vent duct SiO.sub.2 
______________________________________ 
A 60.8 14.7 1.9 21.0 100 20 10 
B 40.6 44.1 1.7 0.0 91.5 20 30 
C 20.3 73.4 1.7 0.0 82.6 20 50 
D 5.1 95.6 2.0 0.0 73.3 20 65 
E 0.0 102.3 2.0 0.0 73.7 20 70 
______________________________________ 
These resins were flow coated on separate polycarbonate 4".times.4" panels 
which had been vapor degreased and heat annealed at 125.degree. C. and 
cooled before coating. The panels were cured about 16 hours in an air 
convection oven at 125.degree. C. 
The panels were tinted using the BPI Sun Brown for 15 minutes at 85.degree. 
C. The results can be found in Table V. 
TABLE V 
______________________________________ 
Results of the Variability of the 
SiO.sub.2 Content of the Base Resin 
Average 
Coating % % Transmission 
Ref. Thickness/.mu. 
% .DELTA. Haze 
Adhesion 
Pretint 
Posttint 
______________________________________ 
A 5.0 15.5 100 89.1 85.4 
B 4.6 9.5 100 89.0 82.3 
C 4.2 7.4 100 89.0 76.6 
D 2.9 20.8 100 88.7 64.2 
E 2.0 23.7 100 88.5 25.0 
______________________________________ 
In base resin coatings which contain colloidal silica, it is apparent that 
greater dyeability can be achieved by increasing the amount of SiO.sub.2 
in the base resin, but it should be observed that at about 65 weight 
percent the coatings start to soften. 
EXAMPLE 17 
Use of the inventive adducts in a commercial silicone resin 
Three resins were prepared according to Japanese Patent Publication Sho 51 
(1976)-123280, Example 3 and Comparison Example 1, page 9 of the 
publication. The formulations were prepared by simple mixing as shown in 
the publication and they had the following formulations: 
______________________________________ 
(A) Methyltrimethoxysilane (MTM) 
27 gms. 
Vinyltrimethoxysilane (VTM) 
38 gms. 
CH.sub.3 COOH 8 gms. 
0.02 N HCl 21 gms. 
Na Acetate 0.4 gms. 
(B) MTM 27 gms. 
VTM 38 gms. 
0.02 N HCl 21 gms. 
CH.sub.3 COOH 8 gms. 
Na Acetate 0.4 gms. 
##STR23## 2.8 gms. 
(C) MTM 27 gms. 
VTM 25 gms. 
CH.sub.3 COOH 8 gms. 
0.02 N HCl 21 gms. 
Na Acetate 0.4 gms. 
*Adduct 13 gms. 
______________________________________ 
*The adduct had the same chemical structure as that prepared in Example 1 
of this application. 
Polycarbonate panels (4".times.4") were vapor degreased and heat annealed 
at 125.degree. C. and cooled before coating. Both acrylic plastic panels 
(Plexiglas.RTM. G product of Rohm and Haas, Philadelphia, PA, USA) and 
polycarbonate panels (Lexan.RTM. General Electric Co., Plastic Division, 
Pittfield, Mass., USA) (4".times.4") were flow coated, air dried for 25 
minutes and then cured in an air convection oven, the acrylic panels at 
80.degree. C. for 16 hours and the polycarbonate panels at 125.degree. C. 
for 16 hours. The panels were all dyed using BPI Sun Brown at 85.degree. 
C. for 15 minutes. The results are on Table VI. 
TABLE VI 
______________________________________ 
Results from Example 17 
% .DELTA. Haze % Trans- % 
Acrylic mission Adhesion 
Ref. Polycarbonate (PC) 
(AC) PC AC PC AC 
______________________________________ 
A Crazed Badly 25 -- 75 0 100 
B Crazed Badly 25 -- 72 0 100 
C Crazed About 20% 
20 -- 59 100 100 
of Surface Area 
______________________________________