CA1238997A - One component detergent resistant compositions - Google Patents

Abstract

ONE COMPONENT DETERGENT
RESISTANT COMPOSITIONS
ABSTRACT
One component detergent resistant compositions are made by reacting a hydroxyter-minated polydimethylsiloxane fluid (I) and a aminoalkoxysilane containing four to six alkoxy groups (II) and optionally an organotrialkoxysilane (III).

Description

ONE COMPONENT DETERGENT RESISTANT COMPOSITIONS
TECHNICAL FIELD
This invention relates to the production of one component detergent resistant compounds composed of silicones, aminosilanes, and organotrial~oxy silane6, which may be partially hydrolyzed. This invention also relates to the use of these one component detergent resistant compounds in forming detergent resistant films, finishes or coatings for car poli6hes and vinyl protectants.
BACKGROUND ART
The main function of polishes and vinyl protectants is to protect the materials to which whey are applied. Characteristically, polishes should impart to these materials the properties of gloss (appearance), durability to water and solvent, ease of application, and detergent resistance with little or no build-up with repeated applications. A composition is needed, which when incorporated into a poli6h or vinyl protectant can improve the poli~h's detergent resistant properties without sacrificing the properties of protection and appearance.
U.S. Patent 3,508,933 discloses a wax containing detergent resistant automobile polish which is produced by incorporating therein the reaction product of a hydroxyl end blocked polydimethylsiloxane and a silane. U.S. Patents 3,836,371, and U.S. 3,890,271, disclose compositions consisting of a end blocked polydimethylsiloxane, and aminoal~ylsilane and organosilane. U.S. Patent D-13,874 `~

~2313~9~7 3,876,459 disclo6es a composition con6i6ting of a polydiorganosiloxane and organosilane. All of these composition6, however. contain predominantly aminoalkyl6ilane6 containing three alkoxy group6.
U.S. Patent 4,273,584 di~close6 detergent resistant compositions made by blending a hydroxyterminated polydimethylsiloxane, an amino-poly~ilane and an organotrialkyl6ilane which may be partially hydrolzed. ~ecau6e of the high molecular weights of the reactants of the pre6ent invention, highly cro6slinkable aminoalkylsilanes and partially hydrolyzed ~ilanes are pre6ent. The interactive effect of these highly crosslinkable components can cause agglomeration and separation when a blend of these component6 is incorporated into a polish.
It is an object of the present invention to 2rovide a one component storaCJe stable composition which has detergent resistant properties.
It is an object of the present invention to provide a one component storage stable composition which cure6 upon exposure to ambient conditions or other activating means to a durable detergent resi6tant film, finish or coating.
It is an object of the present invention to provide one component 6torage table compo6itions which can be used as a detergent re6istant additive in polishes and vinyl protectants.
It is an object of the pre6ent invention to provide one component storage stable composition which do not cause agglomeration when added Jo polish formula~ion6 containinq thickener6.

D-13,874 ~23~ 7 _ 3 -Other object and advantage of the pre6ent invention will be apparent from the following description, examples and claims.
SUMMARY OF THE INVENTION
Novsl one component detergent reliant compound 6elec~ed from the group consisting of:
(a) a mixture of a hydroxy-terminated polydimethylsiloxane fluid and an aminoalkoxypoly6ilane containing four to six silicon-bonded alkoxy groups or a hydrolyzate of the polysilane;
(by a mixture of a hydroxy-terminated polydimethylsiloxane fluid, an aminoalkoxypolysilane containing four to six silicon-bonded alkoxy groups or a hydrolyzate of the poly~ilane: and an organotrialkoxysilane or a hydrolyzate of the silane;
a a reaction product of a hydroxy terminated polydimethylsiloxane fluid and an aminoalkoxypolysilane containing four to six silicon-bonded alkoxy groups or a hydrolyzate of the polysilane; and (d) a reaction product of a hydroxy terminated polydimethylsiloxane fluid, and an aminoalkoxypolysilane containing four Jo six silicon-bonded al~oxy groups or a hydrolyzate of the poly6ilane, and an organotrialkoxysilane or a hydrolyzate of the ~ilane, said composition having a molar ratio of ~ilicon-bonded alkoxy groups to hydroxy groups of the fluid of no greater than five.
This invention also relate to the production of a one component detergent resistant composition as described above which comprise:

D-13,874 ~23~7 _ 4 -i) from I% to 99.5~ by weight of a hydroxyterminated polydimethyl6iloxane fluid having the ~or~ula, ~otsi(cH3l2o~yH (I) wherein z it a numerical valt;e which will provide said fluid with a vi~co~ity in the range of no approximately 5 to lO0.000 cl~nti~toke6 at room temperature and, ii) prom 0.1~ to 50~ by weight of an aminoalkoxysil~ne having the formula, (R~)3 aRa~iR"NH~R"NH~nR"SiRb~oR~3 h (II) wheEein R and R' are alkyl ~roup6 from one to eight carbons, R" an alkylene group of rom two to eight carbon atoms, "a" and "b" are integer from 0 to l, and n it an integer from 0 to lO.
Thi6 invention al60 relate6 to the production o$ a one component detergent resistant cosnpo~ition as described above which compri~e6:
(it from 50~ to 99.5% by weight of a hydroxyterminated polydimethylsiloxane fluid having the formula, Hotsi(cH3)2o]zH (I) wherein z i6 a numerical value which will provide 6aid fluid with a vi6c06ity in toe range of from approximately 5 to lO0,000 centi~toke6 at room temperature, it from 0.1~ to 50~ by weight of an aminsalkoxy~ilane having the formula, ~R0)3 aR'aSiR"NH[R"NH] R"SilR'plOX~3 b (II) wherein R, and R' are alkyl group from one to eight ~arbon~, R" i6 an alkylene group of from two to eight carbon ~om6, "a" and "b" are integer6 from 0 to l, and n an ~nseger from 0 to lO, ~-13,~7~

(ii) and from 0.1% to 50% by weight of an organo~rialkyoxsilane having the formula, X3SiY (III) wherein X is an alkoxy group containing one to four carbon, and Y is a nonhydrolyzable hydrocarbon:
halo~arbon radical: a nonhydrolyzable radical of carbon, hydrogen an oxygen atoms where the oxygen atoms are present in hydroxyl groups, ester groups, or ether linkages, having one to Zen carbon atoms:
or a nonhydrolyzable radical composition of carbon, hydrogen and sulfur.
DETAILED DESCRIPTION OF THE INVENTION
This invention relate to the production of novel one component detergent resistant compositions which are formed by reacting a hydroxyterminated eolydimethylsiloxane fluid, an aminoalkoxysilane containing four to six alkoxy groups, and optionally an organotrialkoxysilane as described above.
Formula (I) is a hydLoxyterminated polydimethylsiloxane fluid in an amount from 50% to 99.5~ by weight of the composition of the form HO[Si(CH3)20JzH where z ha values from approximately 5 to 1000 to give viscositie6 from about 5 to 100,000 centistokes at room temperature.
Small amounts of various groups, preferably less than two mole percent, can be substituted for methyl in the fluid. The6e groups include ethyl, propyl, p~enyl, vinyl, 3.3,3 trifluoropropyl, and cyanoethyl. lends of these ~ilanol fluids can a1EO
be used.
Formula (II) is an aminoalkoxysilane D-13,874 ~23~ 7 usually in an amount from 0.1~ to 50~ by weight which is of the form:
(R0~3-aR~asiR"NH[R"NH]nR"siR~b~oR~3 b where R, R' are alkyl groups from one to eight carbons, e.g., methyl, octyl; R" is an alkylene group of from two to eight carbon atoms; "a" and "b"
have values of zero and one and n has a value from zero to ten. Included as part of Formula (II) are aminoalkoxysilanes in cyclic adduct form as described infra. Because of the manner in which Formula (II) is made, lower and higher alkoxy functional aminoalkoxysilane impurities such a 1.

2, 3 (illustrated below) are found in Formula (II).

[CH30)~SiC3H6]3N (1) [C~30)3Sic3H6NcH2~2 (2) C3H6Si(ocH3)3 (CH30)3SiC3H6NH2 No individual impurity, howeve!r, comprises more than five percent by weight and the total impurity level 2~ is never more than fift2en percent by weight. Mora simply, a~inoalkoxysilane~ of this invention and their cyclic adduct comprise at least eighty-five percent of Formula (II) and typically comprise ninety-percent of more of Formula (II).
Illustrative of the compound represented by Formula (II) are the following:

D-13,374 [ (CH30)3SiC3H632NH

~(c2H5o)3sic3H6]zNH

[ (CH30)3SiC3H6NHCHZ]2 [(CH30)3Si~3H6NHc2H4NHc2H4]2 ~(C2H50)3Sic3H6NHc2H4NHc2~4]2 (CH30)~Si~ - rC3~6Si(oCH3)3 (CH30)2Si\ - / C2H4NC3H6Si(oZH3)3 : 10 3 )2S\ -/~Nc2H4~ - S~i(OCH3)2 Formula (III) i6 an organotrialkoxysilane in an amount from 0.1% to 50% by weight wherein X is an alkoxy group containing one to four carbons and Y
is a nonhydrolyzable hydrocarbon; a halocarbon radical: a nonhydrolyzable radical of carbon, hydrogen, and oxygen atoms where the oxygen atoms are present in hydroxyl groups, ester groups, or ether linkage, there being from one to ten carbon atoms in Y: or a nonhydrolyzable radical composition of carbon, hydrogen, and sulfur.
Illustrative of the compound6 represented by Y in Formula (III) are as Eollows: methyl, D-13,874

3~Z;~ 7 ethyl, propyl, isopropyl, butyl, amyl, hexyl, vinyl alkyl, phenyl, and benzyl radicals; halogenated radicals such as chlorophenyl, and hydroxy butyl, hydroxyphenyl, msrcapto propyl and ester (4) and ether (5, 6) radicals as illustrated below:.

2 ,,( 3) 2 ~4) o 2 Z \O/ 2 -CH2OCH3 (6) Typical of the compounds represented by Formula (III) are as follows:

CH3Si(oCH3)3 CH3Si(oc2H5)3 C2H5Si(oc2H5)3 C2H5Si(oc2H5)3 C4H9Si(oc2H5)3 CH2=CHSi(oCH3)3 ClC3H65i(OC~3)3 CH2=C(CH3)Co(CH2)3Si(oCH~)~

D-13,874 f H2~-lcH2o~cH2)3si(OcH3)3 Hsc3H6si(ocH3)~
The one component detergent resistant compositions of this invention can be produced by reacting two components: a hydroxyterminated polydime~hylsiloxane fluid (I) and aminoalkoxysilane containing four to six alknxy groups (II) or by reacting three components (I), (II), and an organotrialkoxy~ilane (III) in any order at room or elevated temperatures up to the boiling point of the lowest boiling component in dry environment (moisture free). The compositions of this invention have an average molar ratio of silicon-bonded alkoxy groups to the hydroxy groups of the fluid of no greater than five. This preferred average molar ratio for the combination of (I) and (II) is five and the ratio for the combination of (It, (II) and (III) is approximately four. The reaction can be carried out utilizing 100% solids in organic ~olvent6 (e.g., mineral spirits, ~oluene, hexane) or utilizing solvent blends (e.g., mineral 6pirit~alcohols).
Preferably, a,dded to ~II) or to a blend of (II) and (III) at a moderate rate at room temperature and in a dry environment. The reacted compo6ition6 can be applied in 100% solids~from an organic solvent solution or dispersion, or in a water based emulsion to various surfaces (e.g., vinyl, painted metal, wood, leather, plastic, rubber). Alternatively, the reacted composition can alto ye added to various product6 {e.g., car polishes, vinyl protectan~) and the formulated products can then applied to the above surfaces.
D-13,874 ~3~ 7 It is preferred what the reacted composition6 are stirred or 6haken at room temperature for at least one hour and allowed to stand for a total of 24 hour in a dry environment (moisture free) to injure complete reaction among the components. The composition6 can then be applied either in 100% solids from organic solvent6 or water based products such as car polishes and vinyl protectants Jo a var;ety of surface6. When components (I, II, III) are reacted in organic solvents such as mineral spirits, elevated temperatures and concentrations of 10% by weight or more of the composition i6 preferred to insure a fast buildup of detergent resistance.
The composition6 of this invention either in 100% solids or diluted with dry organic 601vents, must be stored in the absence of moisture otherwise viscosity buildup or rapid gellation can occur.
Composition6 of this invention have excellent 6torage stability (usually greater than six months) when stored in the absence of moisture.
The weight ratio of the hydroxyterminated polydimethyl6iloxane fluid (I) to aminoalkoxysilane or silane blend is deteImined by the viscosity of (I). when Formula I) has a vi6c06ity of approximately lO0 centistokes at room temperature, a useful weight ratio of Formula (I) to Formula (II) or Formula (I) Jo a blend of Formulas (II) and (III) i6 five to one. When Formula (I) has a viscosity of lO00 centistokes at room temperature, a useful weight ratio of Formula (I) to Formula (II) or to a blend of Formulas (II) and ~III) is fifteen to one.

D-13,874 ~23~ 97 The weight ratio of (II) $o (III) can vary over a wide range but is typically near a weight ratio of one to one.
The reactants of the present invention, (I), (II), and (III) are highly ver6atile materials because they have propertie6 associated with dimethyl silicones, organic amines, and alkoxy containing compound6. A broad fipectrum of properties and applications are possible, simply by varying the viscosity of the hydroxysilicone fluid (I) and varying the weight ratio of components I, II, III). The alkoxy groups allow for crosslinking reactions. The amino and other polar organic groups can provide both crosslinking and polar adhesion to various surfaces. Furthermore, the dimethylsilicone backbone can provide good application and rubout onto various surfaces, high shine and depth of gloss, and water repellency. The alkoxy, amino, and other polar groups in combination make the compositions of this invention highly durable and detergent resistant when rubbed out or coated onto various 6urfaces such as painted metal, vinyl, plastic, rubber, leather, and wood surfaces.
The resulting compositions made by reacting ~5 (I) with tII) or alternatively, (I) with (II) and (IlI) can be used as detergent resistant Eini6hes, films, or coatings, detergent resistant additives in polishes and vinyl protectants; components of release coatings: components of latex and solvent ; 30 based organic resin polymer coating and printing ink systems; components of silicone room temperature vulcanizates; fabric treating agents: dye receptors:

D-13,874 ~L2.~ 37 antistat and flow control additives in plastics; and others.
The compositions of this invention also include the hydrolyzed versions of (I) reacted with (II) or alternatively, (I) reacted with (II) and (III), since when compositions of these inventions are added to water based polishes or other water based products they are partially or completely hydrolyzed. These hydrolyzed versions are encompassed by compo6itions of this invention.
The prevent invention al o encompasses the "in-situ" formation of composition of this invention in 601vent or water based polishes and other silicone products. In "in-situ" formation, each component (I, II, III) is added to the solvent and water based polishes and similar products, and the components react in the polish to make compositions of this invention. No preblends of (1) and (II) or alternatively, (I), (II) and (III) are made before addition Jo polish or other similar products.

D-13,874 ExPer imenta 1 The following experimental description illustrate6 the present invention. with respect to the Test Method6 and Procedures outlined in Procedures A-C, it should be noted that testing is done on a text panel finished with black automotive paint, measuring twelve inche6 by twelve inches (12"
x 12"). The panel 6hould be used or "pre-conditioned": not new or "virgin".
Procedure A - Pre~ar~ation of the Test Panel I. Cleaning of_the Panel Fir6t, tbe panel is pre-cleaned with a rubbing compound. Any abrasive containing material which takes off oxidized layer of paint film can be used. Then it is wa6hed with the detergent solution (pre-wash step), until water fully wets the panel and doe not bead-up on the surface. A
detailed description~of the washing procedure can be found in Procedure B.
II. Application of the Polishes The panel is divided into two equal parts with strip6 of one-inch masking tape. Using a Gardner glos6 meter (60), that has been standardi2ed, base point gloss measurements (See Procedure C-Part r II) are taken of each section of the unpolished panel that is subsequently used for A evaluation of the various polishes to be tested.
Ths polishes to be compared are applied in about the same amount, approximately 15 gms (providing they have the same concentration) with a two-inch by D-13,874 two-inch (2" x 2") four layered swatch of cheesecloth. After the films were dried they are polished with a new two-inch by two-inch (2" x 2") cheesecloth swatch. Application ease of poli6h and ease of rubou~ of dried polishes are judged subjectively.
III. Aqinq The panel is then aged for at least t~enty-four hours at room temperature.
IV. Test_for Deterrent Resistance A gloss measurement (See Procedure C - Part III) of each poli6hed section of the panel is again taken. The detergent resistance properties are then measured as per Procedure C.

* The detergent solution consist6 of 1% o 10 mole %
ethoxylate of octophenol (commercially known as l'Triton X-100"), 4% of pota66ium tripolypho~phate and 95% water (preferably deionized 100%).

~-13,~74 ~3~7 Procedure B - asking Procedure I. Washinq Procedure The poli6hed panels are placed into a support stand over a sink. The Panels are wet down with a cold water rin6e. Any marring of the panels by water it noted. A clean towel is dipped into the detergent solution and drained except in the prewash step). The whole panel is washed back and forth, up and down, and back and forth. The panel 10 i8 then rin&ed with told water until no detergent film remains. Cold water is poured through funnels onto the panels. The water run-off properties are observed. This i8 done three times. The panel is then dried and a gloss measurement is done or, the next washing is done.

D-13,874 - ~6 -Procedure C - Measurement of the Deteraent Resistance Properties I. Water Runoff Water runoff was measured after each washing in seconds. The time period measurea (runoff time) began when the water stream from the funnel hit the panel and ended when the water stream on the panel began to totally bead up. Runoff times of 1-2 seconds were excellent: 3-4 seconds good: 5-6 fair; greater than 6 poor.
II. ~a~er Beadinq Water beading was obfierved after each washing. The data way recorded as yes (occurring or no (no longer occurring). Observation of the contact ankle can indicate when detergent resistance of a polish is starting to fail since the smaller the angle the nearer to polish failure). The polish is considered to have failed when beading no longer occurs. Beading failure after 15 or more detergent washing6 was judged excellent; between 10-14, good:
5-9, fair: 0-4, poor.
III. Gloss Measurement Five gloss measurements are made per panel. One i6 made near each corner of the panel and one in the center of the panel. The average measurement is considered the gloss of the panel.
Measurements are made for an unpolished panel by measuring the gloss of these dried panels after abrasive cleaning. Measurements are made for a ~-13,874 ~2.~ 7 polished panel by measuring the gloss of the panel after polish application and buffing.
Prewash-panels are rinsed in cold water.
7S0 mls. of cold water i8 then poured through the funnels onto the top-center of each panel. Gloss measurements for these prewashed panels are first taken from the center of the runoff area three times) and then from the outside area (three times), after wa6h 1, 5, 10, and 15. Gloss retention of 90+% was excellent: 70-90~, good: 50-70%, fair: 50%, poor.

D-13,874 ~;~3~

EXAMPLES
Examples 1-5 Compositions 1-5 of this invention were prepared by reacting at room temperature for 24 hours and under a dry nitrogen atmosphere the following constituents:
a. A hydroxyterminated polydimethylsilicone fluid (I) of the formula Ho[si(cH)2o]z H and a viscosity at room ~elmperature of 60 centi~tokes.
b. A aminoalkoxysilane (II) containing the following constituents and percent by weight;
II-l t(CH30)3SiC3H6]2NH 89%

II-2 3 3 3 6 \C H/ 3 2 6%
; 3 6 II-3 (CH30)3SiC3H6NH2 II-4 [~CH30)3SiC3H6]3N
Five compositions (1-5) were prepared using different weight ratios of (I) to (II). Table I
shows these compositions and blend ratio.

EXAMPLES lPAR~S_BY EIGHT
on~tituent 1 2 3 4 5 - I 2.3 3.0 3.6 4.0 4.7 II 1.0 1.0 1.0 1.0 1.0 .
D-1~,874 , 31 23~7 examples 5-10 The xtorage stability of compositions in Example6 1-5 were monitored. Acceptable storage st,ability i8 defined as the inability of compositions to form a gel ta solid, cured mass of polymer) or not to incur a very large visc06ity increase (of 500% or more) when such compositions are stored in tightly capped containers (glass, plastic, etc.) for at least three months preferably six months or more at room or slightly elevated temperatures (90F).
Compositions 1-5 were tested for storage stability and results ace shown in Table 2.
We note in Table 2 that for compositions 1-5 of this invention, six month storage stability is acceptable, that is no gellation or lacge viscosity increase was indicated.

D-13,874 3 Z3~7 TABLE ?
Initial Six Month Storage Example Composition Viscosity Viscosity Stability __ _(RT) (RT) 6 1 90 90 Acceptable 7 2 122 183 Acceptable 8 3 175 214 Acceptable 9 4 210 274 Acceptable 368 577 Acceptable 1. RT = Room Temperature Viscosity in Centistokes -D-13,874 , :, Examples 11-16 The following examples show a comparison in storage stability of compositions of this invention and compositions of prior art, U.S.P. 4,273,5a4.
The compositionj of this invention are compositions 1-5 in Examples 1-5.
Prior art compositions 11-16 U.S.P.

4,273,5B4 contain the following constituent&:
a. A hydroxy-terminated polydime~hyl silicone fluid (I) of the formula HO[Si(CH3)20]zH and a vi6cosity at room temperature of 60 centi6toke~.
. A complex mixture of aminoalkoxy~ilanes (A with the following constituents and percent by weight:
A-l [(CH30)3SiC3H6~2NH 70%

A-2 (CH30)3SiC3H6~ /i(C~3)2 C3H~

A-3 (C~30)3SiC3H6NH2 A-4 [(CH30)35iC3H6]3N 21%
and c. An approximately 53% hydrolyzed methylt~iethoxy~ilane (B) of the formula (C2H50)2si(CH3)0tSi(0C2H5)(CH3)0~8si(CH3)(0C2H5)2..
The weight ratios for compositions of the present invention are shown in Table 1, Examples 1-5. The weight ratio for prior art compositions are shown below in Table 3.

D-13, e7~

PR IOR ART BLEND EXAMPLE COMPOSITIONS
(PARTS BY WEIGHTl Constituent 11 12 1314 15 16 I 3.2 3.2 6.4 6.4 5.810.4 A 1.0 1.0 1.0 1.0 1.01.0 B 0.3 1.1 0.3 1.1 0.11.1 Storage stability test data for prior art compositions 11-16 are shown below in Table 4.

D~13,874 12;3~97 *
~3 X
o Ul I_ I_ Ul tD
,~-0 æ
O
3 .
I- ,-3 a to I.. O

. g N l ' ^ 0 1 co o on co l n I- r to CO N O W
-em I-~-~ 1~0 I- N
m :~ n ~30 Us o .
COO CC
Us n n n Q
or n D I-CJ O
I- n U
IJ

~2;3~7 The prior art compositions had very poor storage stability. They all formed gels (solid masse6 of cured polymer) within 24 hours after an initial one hour mix was completed under a dry nitrogen environment storage in tightly closed glass containers with a dry nitrogen headspace in said containers.
Furthermore, the prior art compositions had an average molar ratio of nine silicon-bonded alkoxy sroup6 per mole of hydroxy of the fluid. These prior art composition6 had a minimum average molar ratio of approximately seven and a maximum average molar ratio of approximately eleven.
In Examples 6-lO, compositions l-5 (illustrative of the invention) have excellent storage stability: no gellation or large viscosity increases were observed. The composition6 of the present invention contrastingly, have an average molar ratio of approximately four silicon-bonded alkoxy groups per mole of hydroxy. The average molar ratio of silicon-bonded alkoxy groups to hydroxy groups of the fluid is no greater than approximately five. The minimum average molar ratio of the compositions of the present invention is approximately three and the maximum is five.

D-13,874 Examples 17-23 Compositions 17-23 of this invention were prepared by reacting at room temperature and under a dry nitrogen atmosphere for one hour the following constituents:
a. A hydroxy-termina~ed polydimethyl silicon fluid I) of the formula Ho[Si(CH3)2o]zH with a Vi~COfiity at room temperature of 60 centi~toke6.
b. A aminoalkoxysilane (II) containing the following components and percent by weight:

II-l [(CH30)3SiC3H6]2NH ~9%

II 2 tC 30)3S 3 6 \ / ( 3)2 6%
: 3 6 II-3 (CH30)3si~3H6NH2 II-4 [(CH30)3SiC3H6]3N 2%
and (III), where (III) is me~hyltrimethoxysilane (III-l), gamma-chloropropyltrimethoxy silane (III-2), vinyltrimethoxy~ilane (III-3), gamma-amethacryloxypropyltrimethoxysilane (III-4), gamma-glycidoxypropyltrimethoxysilane (III-5), gamma-mercaptopropyltrimethoxysilane (III-6), or beta (3,4 epoxycyclohexyl) ethyltrimethoxy~ilane (III-7).
The weight ratios of compositions 17-~3 are shown in Table 5.

D-13,874 BI.END EXAMPLES/COMPOSITIONS 17-2~ (PARTS BY WEIGHT

Constltuent 17 18 19 20 21 22 23 I 5.6 5.6 5.6 5.6 5.6 5.6 5.6 II 1.0 1.0 1.0 1.0 1.0 1.0 1.0 III-l 1.0 III-2 - 1.0 III-3 - - 1.0 - - - -III-4 - - - 1.0 III-5 - _ _ _ 1.0 III-6 - - - - - 1.0 III-7 - - - - - - 1.0 The 6torage stabllity of compositions 17-23 are shown in Table 6 below.

D-13,874 27 ~3lZ;3~
/

W N i-- O Jo l ¦

l N N N l )-- 3 ') N /-- O 0 to O

O

. H ~3 0 Tl y. l O it r D~ Ox _ c tn.
Ox X
O at Us W ` ' o X
_ C :~
Q
O
rt p it (D t ~'~ h er ~~ F or V cr a ,~

Overall, compositions 17-23, illustrative of the present invention have acceptable storage 6tability. The storage stabilities shown are much better than the prior art compositions (Table 4) which gelled within Z4 hour6 after mixing in a dry environment and storage in tightly capped container.

D-13,874 3~7 Examples Z4-26 Blends of this invention were made using Formula (I) having different viscosities and Formula (II). (I) it a hydroxytermina~ed polydimethylsilicone fluid of formula Hotsi(cH3)2o]zH and (II) it an aminoalkoxysilane described in Examples 1-5. The composition were made by mixing at room temperature or 100C, I) and ~II) under a dry nitrogen environment for one hour and then 6toring in tiqhtly sealed containers whose head6pace was purged with dry nitrogen gas.
Table 7 shows the weight ratios of I) to (II). Table 8 6hows the storage 6tability results.

EXAMPLES/COMPOSITION 24-26 (PARTS BY WEIGHT) ComPOnent 24 25 26 I (1000 C6)* 23.0 - -I (B000 c6)* - 64.0 I (50,000 cs)* - - 91.0 II 1.0 1~0 1.0 * Vi6cosity in centistokes (cs) Compositions containing 1000 and 8000 cs fluids (I) were made at room temperature while that containing 50,000 cs fluid (I) was made at 100C.

D-13,874 _30_ 7 I,) N 1 3 (D

rt O
P

Us O I- I. 3~
O O o ,~ td o o n ,r o o o ~3 o ,-D~

O N

.
o 01 CD I- n o on o Q 3 O O O O
_ .

Q to t-t Of n n to DJ .
O
I-Do D' a ,t O

Examples 27-31 Compo6itions of this invention are jade by blending at room temperature, for 24 hours, and under dry nitrogen or dry air atmosphere the S following constituents:
a. A hydroxytermina~ed polydimethylsilicone (I) of the formula Ho[Si(CH)o~zH and a vi~c08ity at room temperature of 60 centistoke~.
b. A aminoalkoxy~ilane (II) containing the following ~on6tituents and percent by weights II-l [(CH30)3Sic3H6NHcH2]2 II-2(CH30)3siC3H6NHC2H4NH - si(ocH3)2 4 II-3[(CH3025 - ~HCH2]2 2%
C3~6 II-4(CH30)3SiC3H6MHc2H4NH2 2%

II-5 (CH30)3sic3H6NHc2H4Nc3H6si(ocH3)3 1%
C3H6Si(ocH3)3 The five compositions, 27-31, of this invention are prepared using different weight ratios of (I) to (II). table 9 how these compositions and weight ratios.
:

D-13,874 ~L2~33~3~7 ~XAMPLES/COMPOSITIONS 27-31 (PARTS BY WEIGHT) Constituent Z7 28 29 30 31 I 2.1 2.7 3.2 3.6 4.2 II 1.0 1.0 1.0 1.0 1.0 The storage stability of composition 27-31 - in tightly ~toppered containers was excellent. None of the compo~ition~ showed visco6ity increases of more than 100% after six month.

D-13,874 `,.:, 3L~3~ 7 ExamDle6 32-36 Emul~i~nfcleaner poli~he~ were prepared by combining 2 part6 each of the compo6ition~ of Example6 1-5, 1 part of a nonionic ~orbitan monoole~te emulsifier, 23.3 parts of "Mineral TM

Sp;rit~ 66 solvent", 10.5 parts of an uncalcined diatomite celite mineral abra6ive, and 63.3 part8 deioniæed water. The mineral spirit and emulsifier were mixed. Each compo6ition. 1-5, wa6 then mixed wîth the emulsifier/mineral pint blend. The abra6ive way then added and mixed. Finally, deionized water way added and mixed. The emulsion/cleaner polishes were 6haken for one hour at high 6peed.
Toe emul6ion~clea~er automotive polishes are listed below in Table 10.

CAR POLISH EXAMPLES PARTS BY WEIGHTl Inaredient 32 33 34 35 36 Composition 1 2.0 Compo6ition 2 - 2.0 Compo6ition 3 - - 2.0 Compositian 4 - - - 2.0 Composition 5 - - - - 2.0 Emulsifier 1.0 1.0 1.0 1.01.0 mineral Tl Spirits 66 23.2 23.2 23.223.2 23.2 Abrasive 10.5 10.5 10.5 10.510.5 Deionized water 63.3 63.3 63.3 63.363.3 For Examples 32-3~ deterrent ~esifitance testing was conducted according Jo the Procedure A
The re6ult6 are shown in Table 11.

D-13~874 , . , ' Ye X
s,a~
n lo > to lo to g 3 , t it P , O
:~
r 9, y.
OOOOO D
3 l D) o O O O O us Ill I-- ~3 a .
$ $ g Go 00000 O ~3 .. .
O
o o o o o o I~}J ~3 3n l ~3 _ ~~ O O l tq l o N O
(D P g X O X X us l 1' 0 O o _, cry v ~0 .. o o Us K
3 (D Q us U it :~
X X X O .
oh 4 N

O X X O O
..... rt~

N
_~

Example6 37-43 Seven emul~ion/cleaner polishes were prepared as described in Examples 32-36 except compo~ition6 17-23 prom Example 17-23 were used.
Deterger,t reliance testing was conducted a outlined in Examples 33-36 and Procedure A. Table 12 shows tAe car polish compositions and detergent resistance testing results are shown in Table 13.

D-13,87~

~Z;~ 7 3 0 0 0 o O o o - 11 C 3 3 3 3 3 3 ~3 o ~ra~
~~ a) o o o o o o o n y. l ~J. y. I. IJ. IJ. IJ.
O O O Q O O ID
P :~
1' Lo O J O
r Us O
o w l 1 1 1 1 1 I f X
WUl N O
N r o w I I I cn ~3 We o o r 1-- N I W l ~IJ
,, 1-- 1 I II N I 1 1~ w i--l Ul O O l I) N P V

) O C) Us a o w l l l l l l lJ I:
W 1~1 N O O l O
o~1' :r WO W 1-- I N I I I I I ~3 Y
W IJI N O O

W O W I-- N I I I I I I W
We O

-37- ~L;23~7 *of * W W IW
X * w O CO l X
* .
, a C1 k O D r O
tD
~~ o ~-~
Il (D tn ~:2 11~ N N N N l O
1--U3 ,a IT w N t-' O ED W ~'J Us t:l Us It r- p I-ye I- mu ,~
1'- 0 P
g n o I--rr D) ID

o oooo Do p Us o o a o o a us to 1-- Of Ox W
.~3 Do W
I' O 1- Q O 0 I: IY
~c1 a oo oooo 1:1'~ w IJ- rl l O 0 0 0 0 0 O ~~
-'I Dl O O ( L Cl ~3 ~4 0 3- ED O t~J
ED 3~tt~
O I Z D) :E W
DUO OO OOOO ~D~ U) oh p p ~~ ~3 ~3 o D Ye ED :~
O l ED pa 4r r us ED W
P Us ,, Q~ OW O W
Jo Pi o O O I W O O o l o o X o o o o o o :s ~7 - o CL . ,t * W
Ox oh I. o #
WED ~4 ~0 ODD. O
. o r W :~5 Us mw 1-~D P O O ?e O O ED Us O O O O ~J n :1 : O 4 #
Us W 50 I:
o v x o o x ,t o o n o o n o CL CL I. .
#

:~L2;~ 7 ExamDles 44-45 Two emulsion/cleaner polishe6 44 and 45 were prepared which containing composition 1 from Example 1) of this invention and prior art composition 11 (from example 11) respectively. To each polish a thickener was added. After sitting for 24 hours, polish 44 way found to retained its liquid form and was easily pourable from a container. Polish 45 after witting Z4 hours was found to have agglomerated into a solid mass, which had no liquid characteristic and was not pourable from a container. Polish 44 retained its liquid character or over six months.
The two polishes were made as follows: a) the oleic acid, dimethylsilicon oil, organic wax, one~half mineral spirits and kerosene were combined and heated to 90C to melt the wax and to obtain a clear solution, The morpholine was then added with vigorous agitation. Composition 1 or prior art composition 11 was each added to one of the formulations consisting of the remainder of mineral 6pi~its and kerosene and then combined respectively with the two batches of the above ingredients. The abrasive was slurried into the water and the slurry was then added to a hot solvent solution. Agitation it contained until a uniform blend is obtained. The thickener solution is then added with good agitation until a uniform mixture it obtained. The liquid polish is cooled and poured into containers.
Table l shows the compositions of car polish 44 and 45.

D-13,874 CAR POLISH EXAMPLES 44 and 45 Inqredient 44 45 Composition* 2.0 Prior Art Composition 11 - 2.0 Dimethyl~ilicon Fluid, 1000 cs 4.0 4.0 Organic ~ax(l~ 2.0 2.0 Mineral Spirits 15.0 15.0 Kerosene 15.0 15.0 Oleic Acid 2.0 2.0 water (distilled equivalent) 45.9 45.9 Morpholine 1.1 1.1 Abrasive** 10.0 10.0 Thickener (2% in water)*** 3.0 3.0 * Commercially known a "Wax S"
** Commercially known a " Kaopolite 115Z~
I** Commercially known as " Carbopol 934"

D-13,874 Example 46-52 Hhen compositions of 17-20, 22, 23 of this invention were 6ubsti~uted for composition 1 in Example 44, the formulated liquid cleaner/emul6ion poli6he6 retained their ea6ily pourable characteri6~ics for over 6ix month.

D-13,874

Claims (7)

CLAIMS:

1. A one component detergent resistant composition selected from the group consisting of:
(a) a mixture of a hydroxy-terminated polydimethylsiloxane fluid and an aminoalkoxypolysilane containing four to six silicon-bonded alkoxy groups or a hydrolyzate of the polysilane;
(b) a mixture of a hydroxy-terminated polydimethylsiloxane fluid, an aminoalkoxypolysilane containing four to six silicon-bonded alkoxy groups or a hydrolyzate of the polysilane: and an organotrialkoxysilane or a hydrolyzate of the silane;
(c) a reaction product of a hydroxy terminated polydimethylsiloxane fluid and an aminoalkoxypolysilane containing four to six siliscon-bonded alkoxy groups or a hydrolyzate of the polysilane; and (d) a reaction product of a hydroxy terminated polydimethylsiloxane fluid, and an aminoalkoxypolysilane containing four to six silicon-bonded alkoxygroups or a hydrolyzate of the polysilane, and an organotrialkoxysilane or a hydrolyzate of the silane, said composition having an average molar ratio of silicon-bonded alkoxy groups to hydroxy groups of the fluid of no greater than five.

2. A one component detergent resistant composition as in claim 1 which comprises:
i) from 50% to 99.5% by weight of a hydroxyterminated polydimethylsiloxane fluid having the formula, HO[Si(CH3)2O]zH (I) wherein z is a numerical value which will provide said fluid with a viscosity in the range of from approximately 5 to 100,000 centistokes at room temperature and, ii) from 0.1% to 50% by weight of an aminoalkoxysilane having the formula, (RO)3-aR'aSiR"NH[R"NH]nR"SiR'b[OR]3-b (II) wherein R and R' are alkyl groups from one to eight carbons, R" is an alkylene group of from two to eight carbon atoms. "a" and "b" are integers from 0 to 1, and n is an integer from 0 to 10.

3. A one component detergent resistant composition as in claim 1 which comprises:
(i) from 50% to 99.5% by weight of a hydroxyterminated polydimethylsiloxane fluid having the formula, HO[Si(CH3)2O)]zH (I) wherein z is a numerical value which will provide said fluid with a viscosity in the range of from approximately 5 to 100,000 centistokes at room temperature, (ii) from 0.1% to 50% by weight of an aminoalkoxysilane having the formula, (R0)3-aR'aSiR"NH[R"NH]nR"SiR'n[OR]3-b (II) wherein R, and R' are alkyl groups from one to eight carbons, R" is an alkylene group of from two to eight carbon atoms, "a" and "b" are integers from 0 to 1, and n is an integer from 0 to 10, (ii) and from 0.1% to 50% by weight of an organotrialkoxysilane having the formula, X3SiY (III) wherein X is an alkoxy group containing one to four carbons, and Y is a nonhydrolyzable hydrocarbon;
halocarbon radical: a nonhydrolyzable radical of carbon, hydrogen an oxygen atoms where the oxygen atoms are present in hydroxyl groups, ester groups, or ether linkages, having one to ten carbon atoms:
or a nonhydrolyzable radical composition of carbon, hydrogen and sulfur.

4. A solution comprising:
(a) a minor amount of a composition as claimed in claim 1 and (b) a major amount of an organic solvent for said composition as claimed in claim 1.

5. An emulsion comprising:
(a) a major amount of water: and (b) a minor amount of a composition as claimed in claim 1 dispersed in the water.

6. A polish or vinyl protectant containing a minor amount of a composition according to claim 1 or 2 or 3.

7. A solid substrate having on the surface thereof a detergent-resistant film of a composition as claimed in claim 1.