Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
- 1 15~7~
There are many applications where it is desirable
to form thin metallic films or coatings on various solid
substrates. An example of such an application is the
formation of silvered mirrors wherein very thin films or
coatings of silver metal are deposited from chemical
solution onto glass or similar substrates. Also, large
reflectors for solar applications have been formed from
~ vapor deposited silver or aluminum on solid substrates.
Some of the problems associated with prior art
methods of forming thin metallic coatings on solid
substrates have been the cumbersome application methods,
for example, in producing silvered mirrors from chemical
solution and, the inability to retain the metallic coating
on the solid substrate for long periods of time. Also, in
vapor deposition, vacuum metallizing, ion plating,
spraying and similar methods, the metallized surface can
only retain its aesthetic value if the substrate has been
pre-treated with some composition which can mask or
eliminate the scratches, pits and voids in the solid
substrate. Such materials are generally curable organic
coatings which are first coated onto the solid substrates
at such thicknesses that they will physically fill the
scratches, pits and voids, and are then
cured. The metallizing is then carried out on the surface
of the organic coating. Unfortunately, because of the
presence of these organic "basecoats", the manufacturer is
; faced with a variety of adhesion problems between the
basecoats and the solid substrate and the basecoat and the
thin metallic film or coating. This problem is enhanced
~ ' . ; .
` 11~9729
considerably when the manufactured item is intended to be
used outdoors and is subject to the ravages of the
weather.
What is needed therefore is an improved method of
forming adherent metallic films or coatings on solid
substrates and improved metallic coated materials.
According to the present invention there is
disclosed an improved method of adhering a thin metallic
film or coating to a solid substrate. The improved method
utilizes a specific sllane or mixtures of silanes to
strongly adhere the thin metallic film or coating to solid
substrates.
It has been known for a number of years that
silanes are useful for bonding many materials to many
various suraces. It is generally recognized that silane
coupling agents are not universal coupling agents such
that any given silane will bond all materials to all
substrates. Instead, it is generally accepted that
specific silanes can be used for adhesion of specific
materials to specific substrates, that is, the silane must
be matched to the application and it cannot be assumed
that all silanes will work in all applications.
In a recent British patent, Number 1,550,532,
issued August 15, 1979, it is disclosed that thin films or
coatings of metals can be adhered to plastic substrates by
the use of a combination of alkoxysilanes, alkylsilicates
~ and copolymers of alkyl acrylate or a'kyl methacrylate
~::
with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
This patent discloses that the inventive composition
therein serves two purposes i.e. the polymeric material is
...
,",~.~
' . ' , ~ -
~ 1597~-~
a film former and the silane enhances adhesion of metal
overcoat. The alkoxy silanes shown there are of the
formula RnSi(OR')4-n wherein n is 1, 2 or 3, R is a Cl-C6
hydrocarbon group and R' is a Cl-C4 alkyl group. This
prior art material and method appears to work quite well
as long as articles for use indoors are contemplated. It
has been observed that this material does not have
adequate adhesion of the deposited metal to the polymeric
film which results in loss of adhesion of the thin
metallic film.
It has now been found that the adhesion of thin
metal films to various substrates can be enhanced by the
use of certain silanes and silane mixtures on certain
substrates such that the articles prepared using the
inventive method are durable, weatherable and have
brilliance and enhanced specularity.
What i5 disclosed herein is a method of forming
an adherent continuous thin metal surface on a substrate
and the articles prepared thereby.
Thus, what is disclosed is a method of forming an
adherent metal surface on a substrate by (I) treating a
solid substrate with at least one organofunctional silane,
or the partial hydrolyzate thereof, having the general
formula
(RO)aSiR'X
Rc
or a mixture of such an organofunctional silane or the
; partial hydrolyzate thereof with a second silane, or the
partial hydrolyzate thereof, which has the general formula
(RO)bsiRn4~b in which formulae R is an al~yl radical of
;`, 3
~ 15972~
1-4 carbon atoms, R' is a difunctional hydrocarbon radical
having from 1-12 carbon atoms or a
-CH2CH2CH2NHcH2cH2
radical, X is an -NH2,
-NHCH2 <~ CH=CH2 Cl
-SH, OH or Cl radical, R" is a phenyl radical, or an alkyl
radical of 1-4 carbon atoms and a and b each have a value
of 2 or 3, c has a value of 0 or 1 and a + c =3; (II)
drying the silane treated surface until the majority of
volatile materials have been removed and thereafter, (III)
depositing a metal on the silane treated surface to form a
thin continuous film or coating thereon.
The organofunctionalsilanes used in step I have
the general formula
)asiRlx
c
wherein R is an alkyl radical of 1-4 carbon atoms, R' is a
difunctional hydrocarbon radical having from 1-12 carbon
atoms or a
-CH2CH2CH2NHCH2cH2
radical, X is an -NH2,
-NHCH2 ~ CH=CH2 Cl
~ -SH, OH or Cl radical. R is preferably the methyl
, ,.
~ radical. a has a value of 2 or 3. c has a value of 0 or
~: ~ : : ,
. ~ 4
: .: ~
~;f'~: . ' , ,
, ,~
, ::
, , ,
. . ,
~ ~9729
1 and a + c = 3 Thus, contemplated within the scope of
the formula
(R)al R'X
are such organofunctional silanes as
(cH3o)3si(cH2)3NH(cH2)2NH2~
(cH3o)3si(cH2)3NH2(cH2)2NHcH2 ~ CH=CH2 Cl ~ ,
(CH30)3si(cH2)3sH~ (CH30)3Si(CH2)3Cl, (CH30)3Si(cH2)30H~
CH3(cH3o)2si(cH2)3NH(cH2)2NH2
CH3(cH3o)2si(cH2)3NH2(cH2)2NHcH2 ~ CH=CH2 Cl ~ ,
CH3(CH30)2Si(CH2)3SH, CH3(CH30)2Si(CH2)3Cl and
CH3(CH30)2si(cH2)3oH-
It should be noted that contemplated within the
scope of this invention are the partial hydrolyzates of
these organofunctional silanes. By "partial hydrolyzate",
the inventor herein means the water soluble or water
miscible product formed when the organofunctional silane
is treated with water to hydrolyze all or a part of the
alkoxy groups on the molecule. Sometimes, in order to
effect the hydrolysis, a small amount of acid is required
along with the water. Whenever "hydrolyzate" or "partial
hydrolyzate" is used herein, it shall mean that it
contains the hydrolyzed silane or silanes, water for
: : hydrolysis and the alcohol solvent formed by the cleavage
of the alkoxy groups from the silane.
The treatment of the substrate can be carried out
with the organofunctional silane or its partial
hydrolyzate alone but contemplated within the scope of
this invention is a mixture of the organofunctional silane
`, 30
~.. ... .. . . . . . . . .. . ..
1 159~2~
or its partial hydrolyzate with an organosilane having the
general formula (RO)bSiRI'4_b wherein R has the same
meaning as R above, R" can be a phenyl radical, or an
alkyl radical of 1-4 carbon atoms and b has a value of 2
or 3. As indicated above for the formula
(RO)aSiR'X,
the partial hydrolyzates of (RO)bSiR"4_b are also part of
this invention. R is preferably methyl.
The organofunctional silanes and the
organosilanes are well-known commercial silanes and it is
believed that their manufacture is adequately set out in
the art and need not be repeated herein.
Whenever it is required to use a mixture of the
silanes, it is done by a simple mixing technique. The
neat silanes can be mixed first then cohydrolyzed or they
can be hydrolyzed separately and the hydrolyzates mixed
thereafter.
For purposes of this invention, whenever a
mixture of silanes is required, it is generally preferred
that they be mixed in a ratio of 1:10 to 10:1
organofunctional silane to organosilane on a weight basis.
The ratio applies to the weight of the silanes before
hydrolysis.
As indicated above, some of the silanes require
the presence of a small amount of acid to enhance
hydrolysis. Such acids are, for example, hydrochloric and
acetic. This acid requirement is well-known in the silane
hydrolysis art.
':
i -~ 6
', :
, . .. .
.
.
: . . .-:
~ ~ ~9729
It is generally preferred that the silanes be
hydrolyzed prior to mixing. After the silanes are
hydrolyzed, simple hand shaking of the hydrolysis vessel
i.e. a bottle or flask will suffice to force the
hydrolysis reaction. Generally, the hydrolysis mixture is
used at this point without further modification or
purification.
The amount of total silane in the hydrolysis
mixture can be from 0.01 to 35 weight percent.
Whenever the silanes are to be used neat, they
can be dissolved in solvents which are soluble with or
miscible with water such as isopropanol, methanol,
butanol, methylcellosolve or the like. Mixtures of such
types of solvents are contemplated within the scope of
this invention. These solvents can alqo be used with the
hydrolyzed silanes to enhance film forming abilities, etc.
The silanes or silane solutions can be applied to
the substrate by any method which is convenient for the
user. Such methods as dipping, flowing and spraying are
most satisfactory for this invention.
The substrates useful in this invention are those
which are solid substrates~ Thus, most every useful solid
substance which makes up an article can be the substrate
of this invention. Such substrates can be, for example,
plastics such as acrylonitrile-butadiene-styrene
copolymers, Sioplas~ crosslinked polyethylene (Dow Corning
Corporation, Midland, Michigan), polycarbonates,
;, polyethylene terephthalates such as Mylar~ (E. I. DuPont,
Wilmington, Delaware), polyimides such as Kapton~,
~ ! 7
~'
,
: ~ '
.
~ 1~9~29
(E. I. DuPont), polyphenylene oxides such as Noryl~
(General Electric Co., Pittsfield, Massachusetts3,
polyphenylene sulfides such as Ryton~ (Phillips Chemical
Co., Chicago, Illinois) and mineral filled nylons such as
Minlon~ (E. I. DuPont), acrylics, urethanes, epoxys and
polyesters, just to name a few. Wood, cardboard, glass,
metals, silicone rubbers and resins, urethane foams and
polyvinylchloride foams are examples of other useful
substrates.
One method taught herein consists of treating a
solid substrate with an organofunctional silane or a
mixture of an organofunctional silane and an organosilane
and then allowing the silane treated surface to dry until
the majority of the volatile materials have been removed
from the treated surface. What is meant by volatile
materials are the solvents, water and low molecular weight
products that have been formed upon hydrolysis. What is
meant by the "majority" of volatile materials is that the
surface should be tack free or nearly tack free to the
finger touch. This can be accomplished in a number of
ways. For example, the treated surfaces can be left at
room temperature for a period of time, perhaps days, to
allow slow evaporation of the volatile materials into the
atmosphere. Since time is usually a factor in commercial
manufacture, however, the articles can be heated to remove
volatiles. Vacuum can be applied to reduce the pressure
and enhance volatization. The inventor herein has used a
number of methods to cause the removal of volatiles in a
short period of time, such as 1-5 seconds, by heating and
applying vacuum simultaneously.
.,
,,
,~ ,
~ 159`~29
Any method of volatile material removal that fits
the manufacturers mode of manufacture is contemplated
herein.
After the volatile materials are removed, the
thin metal coating is applied. Generally, any method by
which thin, continuous metal coatings can be applied will
suffice for this invention. Methods such as vapor
deposition, electroplating, sputtering, ion plating and
spraying are preferred. However, applying the thin,
continuous metal coating can be accomplished from current
methods of chemical solution application without
detrimental affects on the adhesion promoting coating.
Metals that are useful in this invention are any
metals that can be vapor deposited, electroplated,
sputtered, ion plated, sprayed or applied from chemical
solution. Such metals as copper, nickel, tin, silver,
silver solder, gold, aluminum, platinum, titanium, zinc
and chrome are preferred.
For purposes of this invention, "thin" means the
thickness of the metal film that is required to give a
continuous, coherent film or coating. Generally, these
coatings are less than 30 microns thick.
The articles prepared in this invention can be
covered by clear protective coatings such as the silicone
resins set forth in U.S. Patent 3,986,997. These
materials are generally referred to as "topcoats" and are
well-known in the art.
' As indicated earlier, the surfaces of some
substrates are soft enough that they are blemished by
gouges or scratches during the manufacture of the article
.j ~
" 9
59729 3
and in order to end up with a product that is
aesthetically pleasing, the blemishes must be eliminated
since simple metal plating over them with thin coatings or
films allows the blemishes to show through.
A common method of covering over the blemishes is
to basecoat the substrate with a material such as curable
organic polymers. The organic polymer fills the blemishes
and gives a smooth, flat, blemish free surface over which
the thin metal coating can be a~plied.
Another invention herein therefore contemplates
the use of such basecoat materials in conjunction with the
method of, and materials of, this invention. Thus, this
invention also deals with the treatment of a substrate
with a basecoat and the application of the silane or
silanes of this invention to said basecoat. The metal is
then applied to the silane treated basecoat. Preferred
for this invention are certain silicone basecoats. More
specifically, the preferred basecoat is one that is
selected from the siloxane coatings disclosed in U.S.
Patent Number 3,986,99i issued to Harold A. Clark October
19, 1976.
In using a base coat, the substrate is cleaned by
any conventional process and then the basecoat is applied
and cured. Generally, for the Clark coating, 6-8 hours at
lS0C is required. Some basecoats require only a few
minutes air dry time. In certain circumstances, depending
on the substrate and the basecoat, a primer may be
required. The silanes of this invention, for example,
could be used as such primers. The cured basecoat is then
B
..
~ ,.. - - : :
.
~ 1597~9
top treated with the silane or mixtures of silanes, dried,
then overcoated with the metal of choice. Thus,
contemplated within the scope of the claims of this
invention are substrates named herein overcoated with
organic or silicone basecoats and then treated with the
inventive silanes or silane mixtures.
A third aspect of this inVentiQn is the use of
the silanes of this invention in conjunction with certain
curable coatings to enhance the adhesion of the thin metal
films or coatings. Whereas, the essence of this invention
where first presented herein is the treatment of certain
substrates or the treatment of certain substrates
basecoated with organic or silicone curable coatings, this
further aspect of this invention deals with the metal
coating of curable organic or silicone basecoats which
have included in them, before cure, the inventive silane
or silanes disclosed herein.
This invention therefore also consists of
incorporating in the curable basecoat, the silanes of this
invention and then depositing metals to form films or
coatings thereon. The invention therefore also consists
of a method of forming an adherent metal surface on a
substrate by (I) treating a solid substrate with a curable
organic or silicone basecoat which contains at least one
organofunctional silane, or the partial hydrolyzate
thereof, having the general formula
(RO)aliR'X
Rc
or a mixture of such an organofunctional silane, or the
partial hydrolyzate thereof, with a second silane, or the
, 11
~ ~59~29
partial hydrolyzate thereof, which has the general formula
(RO)bSiR"4_b in which formulae R is an alkyl radical of
1-4 carbon atoms, R' is a difunctional hydrocarbon radical
having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2-
radical, X is an -NH2,
-NHCH2 ~ CH=CH2 Cl ~ ,
-SH, OH or Cl radical, R" is a phenyl radical, or an alkyl
radical of 1-4 carbon atoms and a and b each have a value
of 2 or 3, c has a value of 0 or 1 and a + c = 3; (II)
drying the basecoat until the majority of volatiles have
been removed and thereafter; (III) depositing a metal on
the basecoat to form a thin continuous film or coating
thereon.
The organic basecoats useful herein are those
currently being used as basecoats for metal deposition on
solid articles. These.material~ are air dry acrylics or
urethanes which can be used with or without heat cure.
Such a material, for example, is EB-1, the tradename for
an acrylic polymer manufactured by Red Spot Paint and
Varnish Co., Inc, Evansville, Indiana.
The amount of silane or silanes incorporated in
the basecoat is 0.1 to 10 weight percent based on the
weight of silane(s) and basecoat. Simple mixing of the
silane into the basecoat is all that is required. It
~; should be noted that such mixing need not be done under
anhydrous conditions as the adhesive effect is enjoyed
whether the silanes are used neat or in the pre-hydrolyzed
condition. The basecoat is dried and/or cured, depending
on the application where it is being used, and then the
12
~ ' ' , '' ' , .
,
~ 1~97.~9
meta} top coat is applied by one of the methods indicated
earlier.
Articles which are manufactured by the methods of
the inventions herein have enhanced adhesion, weathering,
durability and enhanced efficiency and specularity
whenever the metal surface is a mirrored surface.
The following examples are not to be construed as
limiting the invention which is set forth in the claims.
Several silanes were evaluated in this invention
by observing the adhesion of the metal coating. An
appearance determination was made which was subjective and
was based upon such characteristics as continuum of film,
brilliance, specularity and the presence or absence of
voids, pockmarks and the like. An excellent film is one
which is continuous, without voids and/or po~kmarks and
has brilliance and high specularity. Specularity is a
term used in the mirrored surfaces art which means the
degree of light transmitted from the surface of a mirror
i.e. how good are the mirror properties. Adhesion was
measured subjectively by rubbing the metal surface with a
cloth saturated with acetone, methanol or isopropanol
using moderate pressure unless a different method is
indicated~ The degree to which the metal surface survived
this treatment is reported. No removal of the coating is
considered "excellentn. "Good" is when some slight
abrasion occurred. "Fair" means noticeable removal of
metal. "Poor" means the removal of essentially all of the
metallic coating. "None" means all the coating was
removed.
13
',,.. : ~ , '
.
1 1~97~9
Example 1
The following samples were prepared to observe
which silanes or combinations of silanes would give the
best enhanced adhesion between a given substrate and
certain metals. Silanes or combinations of silanes were
made at the concentrations shown by a method which
involved the hydrolysis of each silane and the eventual
combinations of the silanes to give the adhesion promoter
used on the substrate. Table I in this example shows the
various silanes tested.
Silane A is (CH30)3Si(CH2)3NH(CH2)2NH2. Silane B
is ~CH3O)3Si(CH2)3SH. Silane C is
(cH3o)3si(cH2)3NH2(cH2)2NHcH2 ~ CH=CH2 Cl ,
Silane D is (CH3O~3Si(CH2)3Cl, Silane E is
phenylSi(OCH3)3, Silane F is propylSi(OCH3)3, Silane G is
C~2=CHSi(OCH3)3 and Silane H is HO(CH2)3Si(OCH3)3.
Results are on Table II. IPA is isopropanol.
MeOH is methanol. gms is grams.
Primer PreParation - Silane A (8 gms), IPA (8
gms) ard 1.12 gms of water were mixed with agitation in a
small 1 ounce glass bottle with a screw-top lid. The
bottle was allowed to stand overnight (about 16-20 hrs).
The material was then diluted with 800 gms of IPA upon
transferring to a larger bottle.
Silane B (12.35 gms), IPA (717.65 gms), Glacial
acetic acid (30 gms) and 40 gms of water were mixed
~ together in the order given herein.
.: :
14
.
-
~1~9,~9
Silane C (24 gms) and 1.2 gms of water were mixedtogether and allowed to stand overnight (16-20 hrs). The
material was then diluted by 800 gms of MeOH.
Silanes D, E, F and G were all handled the same.
Three gms of the silane were treated with 27 gms of MeOH
and then a small amount of acetic acid and enough water
for complete hydrolysis was added, the mixture was shaken
until clear and then was used without extensive aging~
H was used at 20 weight % in MeOH by using the
same method as for D, E, F and G.
All primers were filtered before use.
All samples were hand dipped in the primer
solutions and the excess material was allowed to drip off.
The samples were then dried as shown in the tables.
Table I shows the silanes or combination of
silanes that were used in the examples. "Sample #" is the
reference number for the runs that were carried out for
these examples. "Silane #l" is the organofunctional
silane used in the sample. "Silane #2" is the
organosilane used in the sample. ~Acid added" and "H2O
added" means that the material was used as a hydrolyzate,
in the hydrolysis water, with the alcohol by-produced upon
hydrolysis. In those cases where the silane was used
neat, that is without prior hydrolysis, it is so
indicated.
In Table II, the sample # from Table I indicates
the silane(s) used in that particular run. If more than
one run was made using the same silane but a different
substrate or deposited metal, the run was designated a, b,
c, etc. For example, from Table I, sample 4 is a primer
)
- - , .
1 1~9~9
made up of silanes C and B. Table II, sample 4a shows
that the silanes were used in a ratio of 2.4:1, there was
present 1.3 weight percent total silane in the primer, the
substrate in the run was glass and the deposited metal was
silver solder. Sample 4b of Table II shows the primer of
sample 4 of Table I, having the same ratio of silanes at
the same weight percent solids but the substrate is now
acrylic sheet and the deposited metal is aluminum.
All samples in Table II were vapor deposited
using a Mikros Vacuum Evaporator ~odel VE-10 manufactured
by Thermionics Laboratories, Hayward, CA.
Example 2
In order to compare the material of British
Patent 1,550,532 against the present invention, the
following material was prepared. One hundred eighty gms
of a silicate ba~ed polymer containing
methyltrimethoxysilane was mixed with 20 gms of Acryloid
OL-42 (Rohm & Haas Co., Philadelphia, PA). Acryloid OL-42
is an acrylic p~lymer similar to that found in the British
patent in Example 1. The Acryloid is 80% solids in
cellosolve acetate. One gram of hexamethylenetetramine
catalyst was also added with agitation.
A primer (P~ was prepared for use herein which
consisted of 8 gms of HS(CH2)3Si(OCH3)3 diluted with 800
gms of IPA, 24 gms of 40% in MeOH of
(CH3O)3Si(CH2)3NH2(CH2)2NHCH2 ~ CH-CH2 Cl diluted
; with 800 gms of additional MeOH. Seventy-five gms of the
dilute HS(CH2)3Si(OCH3)3 was mixed with 25 gms of the
16
,,
. ..
.
. . . .
- , ':
~ 159729
dilute (CH3O)3Si(CH2)3NH2(CH2)2N~cH2 ~ CH=CH2 Cl
and a small amount of acetic acid and water and the
mixture was stirred until clear.
A Lexan~ (General Electric Co., Schenectady, NY)
polycarbonate slide was abraded with emery paper to
simulate an abused article from manufacturing. After the
- slide was cleaned, it was measured off in 4 equal sections
and marked and one section was dipped in the solution of
primer (P) from above and then allowed to air dry for 20
minutes at room temperature.
The solution of acrylate polymer, silicate and
alkoxysilane analogous to that found in Example 1 of
British patent 1,550,532 was then applied to 3/4 of the
slide and the 1/4 primed area was overcoated thereby and
air dried. The coating was then cured 15 min. @ 70C and
20 min. @ 100C. Next, 1/2 of the slide was dipped in a
solution of P and allowed to air dry for 10 minutes at
room temperature. Finally, the whole slide was vapor
deposited with silver metal and cured for 15 min. @ 100C.
If one were to lay the slide on its edge and note the
coatings or layers on the top of the slide, the left-most
1/4 section (denoted A) would have a silver coating only.
Moving to the right, the next 1/4 section (denoted 8)
would have a top layer of silver covering a layer of the
1,550,532 polymer which in turn covers the polycarbonate
slide. The third 1/4 section ~denoted C) would have a top
layer of siIver covering a layer of P primer which in turn
covers the 1,S50,532 polymer which in turn covers the
,~: . ,
polycarbonate slide. The last 1/4 section (denoted D)
, ~ ,
,:
~ ~ 30 17
:~ : , .. ... .
.~ .. . .. . . . . .
. ~
~ : ~ . . . . . .
,, . . ~ . . - . - -
, ~
3 1 59~
consists of a top layer of silver, a second layer of the
primer P, a third layer of the 1,550,532 polymer and
finally a fourth layer of primer P.
Sections B, C, and D were scored into
crosshatched squares by a sharp instrument to give 25
equal squares. Scotch Brand adhesive tape #650 (3M Co.,
St. Paul, Minnesota) was then pressed onto the
crosshatched squares and removed forcibly. Recognizing
that the most optimum conditions were not observed, the
test was deemed to have been passed if at least 50~ or
more of the silver metal remained intact. Table III shows
the results.
ExamPle 3
A silicone resin was prepared according to
Example 2 of U.S. Patent 4,173,553 with the exception that
the HS(CH2)3Si(OCH3)3 was present at 10 weight percent
CH3Si~OCH3)3 at 40 weight percent and colloidal silica at
50 weight percent based on the weight of all three
components. This material is shown herein as "A".
Another sample of silicone resin was prepared as shown in
Example 1 of U.S. patent 3,986,997, that is, the same
material as above but without HS(CH)2Si(OCH3)3 and this
was designated "B". The two materials were compared
side-by-side for their ability to accept and adhere metals
which were depo~ited thereon. Both materials were diluted
to approximately lOX solids with isopropanol.
A clean square of Lexan~ polycar~onate was dipped
1/2 into "A". The remaining 1/2 was dipped in "Bn. The
sample was then air dried for 40 minutes at 25C. The
sample was then vapor deposited with silver. The sample
18
' . .' , '
~; : ~-. - .-
..
.~
~`~59729
then cured 1 hour at 125C. The samples both had
excellent specularity. The samples were subjected to a
methanol rub to test the adhesion of the silver. The
material "A" was clearly superior in retaining the silver
metal.
Example 4
The silicone resin designated "B" in Example 3
above, was coated onto a clean Lexan~ polycarbonate square
and cured 25 minutes at 100C. One-half of the coated
slide was then dipped into a primer designated earlier as
primer P of Example 2 and this was allowed to dry for 2
minutes at 25C. The square was then vapor deposited with
silver and cured 1 hour at 125C. The 1/2 side of the
slide that had been primed with primer P of Example 2
showed superior retention of the silver deposited thereon.
The means of metal deposition described in this
specification and claims are conventional means for
depositing metals and it is believed that elaborate
descriptions of such methods are not required by those
skilled in the art.
19
... . ,, , .. , ... , . ., . ., ~ , ~ , . .
:: `
. , ,:
.
~ 1597~
~ Z
Iv~ ~ I ~ ~ ~ ~ ~ ~ ~ ~ I
O ~ u~
,.
I,'~ooo~oooo
H O O I I I W H
O U~i
E~ J~
~1 ~ ~ O O ~ ~ ~ O
U~ W H W W W W I I I O
c I I I m ~ ~ c~ m ~ ~ c~
~ lll
c ~ ~ u c~ m m m ,~c 11 1l ¦ 11
~.: ~,q
:,
!
,' #
~1 ~ o ,~ ~
~ .
-
~ C C ~) .C ~ .C ~ .C ~ S ~ S ~ s ~) S ~
o ~
~ ~ '~ O ~ C '~
~ 0 U~ e ~ ~ o~E z ~ ~ o ~ o e o
,. o ~ o o ~ U'~ ~ o ~ o ~ o ~ o
_ ~ ~ ~ ~ ~ 7 r~QJ ~ ~ ~ ,,~
I ~c~" ~n ~e c c c
~,~ ~ e e
~r~
I~ o~ ~ ~ D ~ Z
'~ ~ _
'~ : ~
E i --I C`l ~ ~ ~ ~r ~ er 'r
cn
., ,
il ': : ~
21
:3 ~
1 ~597
I
.~ _
3 C
_1 ~ ~ 1 o
E~
# ~
. l l I
1~ 1
O .~
l ~
)-~
~ O h --I ~ 5 o O
O
#~ 0
U 11
U ~ ~ er 1111 1
. ` ,
`~' 22
/
.~,.. ,,...... ` .
~ 1~9 ~29
~ e eS ~ ~ .e ~ S ~ S C~
u~ .C o ~ o E~ o o E~ o
a~ c: o o u~u~ O In In
O ,~ o o r-o r~ o o ao r~
u e U ~e u 'E U e u e u è u ~u
r~ aaJ o ~u~ ~ o ~ o ~
~ tq o ~ ~ C C ~ ~ ~
D1~ ~ ~ U~
a~
Q)
~ ~ ~ ~ ~ C
.~ D C ~ 1 S ~ e
~ ~ o o u~ x u o
.: tq ~ O ~ 3 Q~
t~
~ #
~ I ~ S er
i~ :
. ~ ~
.,1
4;
23
`:`i; :
1 1597
_
U~
.~
3.-1 U~
~ U~ ~ _l ~ _l ~
0~
~1 #
O ~ .. .. .. .. .. .. ..
~1 ~ c~
,~'11 ~ ~ O O
~C ~
O ' O 1:: C C C C
H S t~ O
~ ~ W~ W ~ W
C
a) ~ o
~1 tl~ H ~
s ~ ~ x ~ e
. ~: 24
1 1~9729
e = U .= U = U ." U = U E u
~r o~r o~o oo oo~ o~ o-n
O ~ ~ ~ ~ ~ ~ ~ _1 ~9 ~ ~ ~ a~
~ I \\ \ \\ \ \
U rl U S U r~ U r~ U ~ U
O E~ ~ E~ E~ E~ E3 ~
o~ o~ ~ o~ o~ o~ o~
~O ~ D ~ a!) ~ ~ ~ oe) ~ ~ ~ oe~
1-1 0 ¦ ~ E ~, ,e ~ E
~_1 u~
E~
,
:, ~ O
3 o ~ o ~ o ~
~ ~ ~ 5~ ~ rl O J~ ~ O a
.Q ~ u
', : ~n .
;~
~ : 25
IJ~
~ 1 1~9729
S
.~ I U~ U.
3 ~ ~
1~ ~n
~JP
O I ~
c o q .. .. .. .. .. .. ..
c~ , a~ ~
l (~ O O O o o o o
U~
~C
cO C C ~ C
.q ~ I o
~ 3 Z
:: a~
' ~ ~ I :)~O
: ~ a ~ o Q. 8~
', ~ ~
:
:!
,~
'
~'
',:
2 6
:,,!;
:: ' : ` ;"
1 ~97
~ ~ ~ C ~ C
a) 2 o ~ o o o o o o o o ~ o ~ o
S~ O r~ _I ~D ~ ~ ~ ~ _I _I ~ ~ ~ _~ ~1 ~ ~
`,.~ ~ ,~, ~ U ~C~ ~ ~ ~
a o ~ ~ U~ ~ ~ ~ 6 n ~
O ~ O ~ O ~O ~ O ~O N O ~ O ~
V ~r
l ~
U t) ''~ ~ O
, 1 O ~
.a ~_~ s~
~:
~n ~n bq tn u~u~ u3 u~
u~
, ~ ~
.4 ~ 3
e
*
O ~ 3 x
~ i ~
: ~n
~'
,:
i
, 27
'
:
1 15972
, U~ U~
~_ ~ , ~~ o o ~o
.,, aJ .. . . .o
a) c~1 ~ O--I O O
3 a -I .
,1 ,~
t~
4~ _I
O#
O U~ .. . I
. .~ a)o o~ o
~J ~J C
O 0
H ~ '¢
~ JJ V ~JJ ~
E~ ~ C CC C
O~ O ~
.~~ I o ~~a
U7
O U O
~: WG3~ E~~3 h
a~
a~ c
O
# *
~ ** O
_1 ~ 3 X ~1 R o ~ n5H~
~n
. 28
,... ... ... . .. . .
- ,
'
~: , - , - .
~ ~5972~
~ U rl U r~ U '~ V '1 U r~ U rl ~ ~ C~
~n ~ o ~ O ~ O ~ O ~ o ~ O ~ O
~ ~ o~ o~ o~ o~ o~ o~ o~ oo
SJ O ~
V' ~ U ~ ~ .C U ~ U .C U ,C U ,C U
C~ U ~ ~ ~ ~ ~ P o ~ o
o ~ o ~ o ~ o ~ o ~ o ~ o ~ _I
h
~ O
~-I 1~ ' '~
~:
,
t,q 0
U~ bq 0 U~
8 ~ 3
0 0
:: :
# * * *~ *~ N n~
~ O
:
29
. ~ ~
~ ~ , . .. . . .
I 159729
su
~_
~ ~ ~
~ C o o o ,~ o~ I o
3 n~
_l o o ,~ o
.-t-~ o _I
~ cn _i
E~
W _
01~- IIIII~
~ ~ a~
O J- ~ ~ ~ I I I
C) p;~a ~ o
~ tn
E~ 4
r~
O O O ~ C ~ O
I ~ ~ 2 z z ~
C
; ~ ~ o
N
U~
E . C
~ 159729
C C C C ~ C
~ ) ~ E~ o ~ o ~ o~ o
a)O oo oo oo oo oo oo oo
C~ C C ~ .C C~ ,C L~'E ~E ~E ~ E ",
~) ~ ~ In ~ ~ <~I o ~ o ~ o ~ I
~ .o
C
V C . C
0 ~ ~
¦ ~ ~ ~ ~ ~ ~ O
~: ~ ~ a~ -.
O
~ V I ~ ~ ~ ~ ~ ~ ~
~; `
;~ 31
'
,..... .
: ~. ` ' .
~ 1~972
.,,_
e I o o o o o o o
a ~ ~ _, ,, _,
C~l o
~I
~ # a)
~1 o~ >
* ~ o
E~ ~Q
~y 2 ,~ z o
a~
:: C C
:: # * * .,~ ~ ~ o
a ~ co *a~ o
~ ~ *~ ~ *
::
59729
C
a) c
~,.,, _,
~ C ~ , ~
.~.,, ~ , .~ .,,
, s~ ,~
, ,
,, ,
~ o o
~ tn
a~
O SJ
_I
.~
_, ~ ,~
tn . ~ o
:~ :
o
: ~ ~ ~J a o
:,
3 3
,
: ~ ~ . .,