Ammonium siloxane emulsions and their use as fiber treatment agents

The present invention relates to a silicone emulsion comprising (I) a water soluble ammonium siloxane composition comprising (A) an aminosiloxane solution comprising a mixture of (i) a triorganosilyl-endblocked aminofunctional siloxane, (ii) an aminofunctional siloxane which it triorganosiloxy-endblocked at one end and hydroxy-endblocked at the other end, and (iii) a hydroxy-endblocked aminofunctional siloxane, (B) a cyclic aminofunctional siloxane, and (C) a polydimethylcyclosiloxane where the aminofunctional group is selected from ##STR1## where R.sup.3 is a divalent hydrocarbon radical, R.sup.4 is a divalent hydrocarbon radical, R.sup.5 is hydrogen, alkyl, aryl, or arylalkyl, R.sup.6 is a --C(O)R.sup.7 group where R.sup.7 is a monovalent hydrocarbon group or aryl, and A.sup.- is a halide anion, carboxylate anion, or inorganic oxoanion, and (II) an organopolysiloxane emulsion. This invention further relates to a method of making the silicone emulsion, and to a method of treating a substrate with the silicone emulsion.

BACKGROUND OF THE INVENTION 
The present invention relates to ammonium siloxane emulsions. More 
particularly, the present invention relates to emulsions containing water 
soluble ammonium siloxanes, a method of making ammonium siloxane 
emulsions, and the use of these emulsions as fiber treatment agents. 
Quaternary ammonium polydiorganosiloxanes which are cationic and water 
soluble have been disclosed. For example, Schaefer et al. in U.S. Pat. No. 
4,891,166 discloses diquaternary polysiloxanes whose quaternary nitrogen 
groups are terminally linked to the polysiloxane molecule, and their use 
in cosmetic preparations, especially in preparations for the care of hair. 
Margida in U.S. Pat. No. 4,895,964 discloses a process for the manufacture 
of quaternary ammonium pendant siloxane copolymers by the reaction of 
epoxy pendant siloxane copolymers with a tertiary amine acid salt using a 
catalytic amount of a free tertiary amine as the catalyst. Snow in U.S. 
Pat. No. 5,041,590 discloses a quaternary ammonium functional siloxane 
compound having the formula (R.sub.3 SiO).sub.2 --SiR--(CH.sub.2).sub.a 
!.sub.b N.sup.+ R'.sub.4-b X-- where R is an alkyl radical having one to 
six carbon atoms, R' is an alkyl or aryl radical having one to eight 
carbon atoms, X is a chloride, bromide, iodide, nitrate, or 
RSO.sub.4.sup.-, a is an integer having a value from 1 to 10, and b is an 
integer having a value of 2 or 3. Snow further discloses that these 
siloxane compounds are useful in reducing the surface tension of an 
aqueous solution. Hill et al. in U.S. Pat. No. 5,235,082 discloses 
diquaternary ammonium functional siloxanes which have a variable amount of 
hydrophobicity at the center of the molecule which makes them useful in 
the field of fabric softening and fabric conditioning. Hill et al. in U.S. 
Pat. No. 5,364,633 discloses a method of entrapping a water-soluble 
substance in vesicles formed from a siloxane surfactant, where suitable 
siloxane surfactants include organosilicon compounds having the formula 
RMe.sub.2 SiO(Me.sub.2 SiO).sub.a (MeRSiO).sub.b SiMe.sub.2 R, Me.sub.3 
SiO(Me.sub.2 SiO).sub.a (MeRSiO).sub.b SiMe.sub.3, or Me.sub.3 
SiO(MeRSiO)SiMe.sub.3 where R can be a --(CH.sub.2).sub.x N.sup.+ R.sub.3 
"A.sup.-, R" is an alkyl radical having from 1 to 6 carbon atoms, a benzyl 
radical, a phenyl radical, or the radical --CH.sub.2 CH.sub.2 OH, A.sup.- 
is chloride, bromide, iodide, cyanide, a methyl sulfate radical, a 
salicylate radical, or a dodecylsulfate radical, a has a value of 0 to 
200, and b has a value of 0 to 50 with the proviso that both a and b 
cannot both be zero. O'Lenick Jr. in U.S. Pat. No. 5,098,979 discloses 
silicone polymers which contain a quaternary nitrogen pendant group, where 
in one embodiment the quaternary nitrogen group has an alkylamido 
functionality and in a second embodiment it contains an imidazoline 
derived functionality. O'Lenick Jr. further discloses that these polymers 
are useful in softening hair, textile fibers, and conditioning skin. 
In addition, other low molecular weight aminofunctional siloxanes are known 
to be water-soluble. For example, Snow in U.S. Pat. Nos. 5,087,715 and 
5,104,576 discloses alkanolaminofunctional siloxanes which are useful in 
altering the surface activity of water, the siloxanes having the formula 
R.sup.1.sub.3 SiO(R.sup.1 MSiO).sub.y SiR.sup.1.sub.3 or R.sup.1.sub.3 
SiO(R.sup.1.sub.2 SiO).sub.x (R.sup.1 MSiO).sub.y SiR.sup.1.sub.3 where x 
is an integer from 1 to 100, y is an integer from 1 to 10, R.sup.1 is a 
lower alkyl group, and M is an alkanolamino group having the formula 
--(CH.sub.2).sub.a N(R.sup.2)--(CH.sub.2).sub.b OR.sup.3 or 
--(CH.sub.2).sub.a N+(R.sup.2)(R.sup.4)--(CH.sub.2).sub.b OR.sup.3 Z.sup.- 
where a is an integer from 1 to 10, b is an integer from 1 to 10, R.sup.2 
is hydrogen, a C.sub.1 to C.sub.18 alkyl group, a C.sub.6 to C.sub.18 aryl 
group, --CH.sub.2 --C.sub.6 H.sub.5, or a C.sub.5 to C.sub.18 cycloalkyl 
group, R.sup.3 is hydrogen, a C.sub.1 to C.sub.18 alkyl group, a C.sub.6 
to C.sub.18 aryl group, a C.sub.5 to C.sub.18 cycloalkyl group, 
--C(O)R.sup.5, --C(O)NHR.sup.6, --SO.sub.3.sup.-, --Si(CH.sub.3).sub.3, or 
--P(O)(OCH.sub.3).sub.2, R.sup.4 is hydrogen, a C.sub.1 to C.sub.18 alkyl 
group, a C.sub.6 to C.sub.18 aryl group, --CH.sub.2 --C.sub.6 H.sub.5, or 
a C.sub.5 to C.sub.18 cycloalkyl group, R.sup.5 and R.sup.6 are a C.sub.1 
to C.sub.18 alkyl group, a C.sub.6 to C.sub.18 aryl group, or a C.sub.5 to 
C.sub.18 cycloalkyl group, and Z is Cl, Br, I, NO.sub.3, a C.sub.1 to 
C.sub.8 alkylsulfate group, --CH.sub.3 COO.sup.-, BF.sub.4.sup.- or 
PF.sub.6.sup.-. Snow et al. in U.S. Pat. No. 5,026,489 discloses a fabric 
softening composition which includes an alkanolamino functional silicone 
compound having the formula (R.sub.3 SiO).sub.2 SiR--(CHR').sub.a N.sup.+ 
R'.sub.b R".sub.3-b X-- where R is an alkyl radical having one to six 
carbon atoms, R' is hydrogen, alkyl and aryl radicals having one to 
eighteen carbon atoms, R" is (CHR')OH, X is a chloride, bromide, iodide, 
nitrate, or RSO.sub.4.sup.-, a is an integer having a value from 1 to 10, 
and b is an integer having a value of 1 or 2. 
Polymeric ammonium functional siloxanes have also been taught. For example, 
Ziemelis et al. in U.S. Pat. Nos. 4,472,566 and 4,597,964 discloses 
cationic polydiorganosiloxanes having the general formula QMe.sub.2 
SiO(Me.sub.2 SiO).sub.x (MeRSiO).sub.y SiMe.sub.2 Q where Me denotes 
methyl, and R is a radical having the formula --C.sub.m H.sub.2m NHC.sub.n 
H.sub.2n N.sup.+ H.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl.sup.- or --C.sub.m 
H.sub.2m N.sup.+ (CH.sub.2 C.sub.6 H.sub.5 Cl.sup.-)HC.sub.n H.sub.2n 
N.sup.+ H.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl.sup.- where m has a value of 
2 to 5 inclusive, and n has a value of 1 to 5 inclusive, Q is R, methyl, 
or OH, x has a value of 5 to 200, and y has a value of 1 to 30. Ziemelis 
et al. further discloses that these siloxanes are useful for treating 
human hair, human skin, and animal fur. 
Reactive ammonium-functional siloxanes have also been disclosed in the art. 
For example, Brown in U.S. Pat. No. 3,355,424 discloses a process for the 
preparation of polyaminoalkyl-substituted organosiloxane copolymers and 
salts thereof, and to the reaction products of said processes. Holdstock 
et al. in U.S. Pat. Nos. 3,544,498 and 3,576,779 discloses an 
organopolysiloxane copolymer which is prepared by the partial hydrolysis 
and condensation of a silanol-chainstopped polydimethylsiloxane having 5 
siloxy units, an aminoalkyltrialkoxysilane, and an 
aminoalkoxyalkyltrialkoxysilane. Holdstock et al. further teaches that a 
second organopolysiloxane copolymer can be prepared by the partial 
hydrolysis and condensation of a silanol-chainstopped polydimethylsiloxane 
having 800 dimethylsiloxy units with an aminoalkoxyalkenyltrialkoxysilane. 
Holdstock et al. further teaches that the first organopolysiloxane polymer 
can be converted to a partial amine salt by reaction with an aliphatic 
carboxylic acid, then mixed with the second organopolysiloxane. Martin in 
U.S. Pat. No. 3,890,269 discloses a process for preparing aminofunctional 
organopolysiloxanes which comprises equilibrating a mixture containing an 
organopolysiloxane and an aminofunctional silane or siloxane in the 
presence of a catalyst. Martin further discloses that the aminofunctional 
groups present in the organopolysiloxanes which are prepared can be 
reacted with organic or inorganic acids to form the corresponding ammonium 
salts. Cifuentes et al. in U.S. Pat. No. 5,110,891 teaches a polish 
formulation which contains a reactive amine functional silicone polymer 
Furthermore, other water-insoluble ammonium siloxanes which result from the 
reaction of amino-siloxanes and organic carboxylic acids have been taught. 
For example, Imperante et al. in U.S. Pat. No. 5,115,049 discloses fatty 
carboxylic acid salts of organofunctional silicone amines where the amino 
pendant functionality is present within the polymer. 
Unreactive linear amino-siloxanes have also been described. For example, 
Bailey in U.S. Pat. No. 2,947,771 discloses the production of endblocked 
organopolysiloxanes containing among other siloxane units, 
aminoalkylalkylsiloxane or aminoalkylarylsiloxane units in which the amino 
group is linked to the silicon atoms through a polymethylene chain of at 
least three carbon atoms. 
Organopolysiloxane emulsions have also been described in the art. For 
example, Hyde et al. in U.S. Pat. No. 2,891,920 teaches an 
organopolysiloxane emulsion formed by an emulsion polymerization where the 
polysiloxane, emulsifying agent such as a cationic, anionic, or nonionic 
surfactant, catalyst such as a strong mineral acid or strong alkali, and 
water are blended together in various orders of addition to form an 
emulsion and then allowed to react at room temperature or greater. 
Findley et al. in U.S. Pat. No. 3,294,725 discloses an organopolysiloxane 
emulsion formed by polymerizing and copolymerizing an organosiloxane or a 
silcarbane in an aqueous medium while in a dispersed state, in the 
presence of a surface active sulfonic acid catalyst. 
Cekada et al. in U.S. Pat. No. 3,433,780 teaches colloidal suspensions of 
silesquioxanes having an average particle size in the range of 10 to 1000 
A and having the unit formula RSiO.sub.3/2, wherein R is a hydrocarbon or 
a substituted hydrocarbon radical having 1 to 7 carbon atoms, in a 
water-surfactant mixture. It is further disclosed that these suspensions 
are prepared by adding the appropriate silane to a water-surfactant 
mixture with agitation. 
Polyorganosiloxane microemulsions have also been disclosed. For example, 
Gee, in U.S. Pat. No. 4,620,878 discloses a method of preparing fine 
polyorganosiloxane emulsions having an average particle size of less than 
0.3 micron and polyorganosiloxane microemulsions with an average particle 
size of less than 0.14 micron by preparing a translucent oil concentrate 
by mixing a polyorganosiloxane having polar groups such as an amino group, 
a surfactant which is insoluble in the polyorganosiloxane, and sufficient 
water to obtain the translucent mixture, the translucent concentrate is 
then rapidly dispersed in water to form the emulsion or microemulsion. 
Gravier et al. in U.S. Pat. No. 4,999,398 discloses a clear, stable, 
aqueous microemulsion of polydiorganosiloxane produced by sequentially 
adding a precursor emulsion comprised of cyclopolydiorganosiloxane, 
surfactant, and water to a polymerization medium comprising water and an 
effective amount of a polymerization catalyst while mixing wherein the 
rate of addition of the precursor emulsion is effective to form a clear, 
stable microemulsion which has polydiorganosiloxane droplets of less than 
0.15 micron average particle size, and which contains a surfactant to 
polydiorganosiloxane weight ratio of 0.15 to 5. 
SUMMARY OF THE INVENTION 
The present invention relates to ammonium siloxane emulsions, a method of 
making ammonium siloxane emulsions, and the use of these emulsions as 
fiber treatment agents. 
It is an object of the present invention to produce emulsions which contain 
linear silicone-unreactive water-soluble ammonium functional siloxanes. 
It is a further object of this invention to produce ammonium functional 
siloxane emulsions which are useful as fiber treatment agents. 
It is another object of this invention to prepare ammonium functional 
siloxane emulsions which, when applied to fibers such as paper pulp or 
tissue, render the fibers soft and smooth to the touch. 
It is another object of this invention to produce silicone emulsions in 
which the water-soluble ammonium functional siloxane compositions 
contained therein have at least 10 mole percent ammonium-methylsiloxane 
functionality. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates, in a first embodiment, to a silicone 
emulsion comprising (I) an ammonium siloxane composition comprising (A) 
0.01 to 90 weight percent of an aminosiloxane blend comprising a mixture 
of (i) an aminofunctional siloxane having its formula selected from the 
group consisting of (a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 
SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.3 and (b) R.sub.3 SiO(Me.sub.2 
SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3, and (ii) an aminofunctional 
siloxane having its formula selected from the group consisting of (a) 
R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z 
SiR.sub.2 OH and (b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y 
SiR.sub.2 OH, and (iii) an aminofunctional siloxane having its formula 
selected from the group consisting of (a) HOR.sub.2 SiO(Me.sub.2 
SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and (b) 
HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH, (B) 
0.1 to 90 weight percent of a cyclic aminofunctional siloxane having the 
formula 
##STR2## 
and (C) 0.1 to 10 weight percent of a compound having the formula: 
##STR3## 
wherein Me denotes methyl, R is independently a monovalent hydrocarbon 
radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a 
group having its formula selected from the group consisting of 
##STR4## 
and wherein R.sup.3 is a divalent hydrocarbon radical having at least 3 
carbon atoms, R.sup.4 is a divalent hydrocarbon radical having at least 2 
carbon atoms, R.sup.5 is selected from the group consisting of hydrogen, 
an alkyl radical having from 1 to 6 carbon atoms, an aryl radical, and an 
arylalkyl radical, R.sup.6 is a --C(O)R.sup.7 group where R.sup.7 is 
selected from the group consisting of a monovalent hydrocarbon group 
having from 1 to 20 carbon atoms and an aryl radical, and A.sup.- is an 
anion selected from the group consisting of halide anions, carboxylate 
anions, and inorganic oxoanions, R.sup.2 is independently selected from 
the group consisting of a monovalent hydrocarbon radical having from 2 to 
6 carbon atoms and an aryl radical, x has a value of 10 to 10,000, y has a 
value of 1 to 8,000, z has a value of 1 to 250, x' has an average value of 
1 to 8 and y' has an average value of 1 to 8 with the proviso that the 
value of x'+y' is from 4 to 9, n has an average value of 4 to 9, and with 
the proviso that the value of y/x+y+z+2 is at least 0.1; and (II) an 
organopolysiloxane emulsion. 
The monovalent hydrocarbon radicals of R in component (I) are exemplified 
by alkyl radicals such as methyl, ethyl, propyl, pentyl, or hexyl, and the 
aryl radicals are exemplified by phenyl, tolyl, or xylyl. In the 
compositions of this invention R is preferably methyl or phenyl. The 
monovalent hydrocarbon radicals of R.sup.2 are exemplified by ethyl, 
propyl, butyl, pentyl, or hexyl and the aryl radicals are as defined above 
for R. Preferably R.sup.2 is independently selected from the group 
consisting of ethyl, propyl, butyl, hexyl, phenyl, tolyl, and xylyl. 
In component (I), the divalent hydrocarbon radicals of R.sup.3 are 
exemplified by groups such as alkylene groups including propylene, 
butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, 
hexamethylene, 3-ethyl-hexamethylene, octamethylene, --CH.sub.2 
(CH.sub.3)CH--, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --, --(CH.sub.2).sub.18 
--, and cycloalkylene radicals such as cyclohexylene, arylene radicals 
such as phenylene, combinations of divalent hydrocarbon radicals such as 
benzylene (--C.sub.6 H.sub.4 CH.sub.2 --), and oxygen containing groups 
such as --CH.sub.2 OCH.sub.2 --, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 --, 
--CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, --COOCH.sub.2 CH.sub.2 OOC--, 
--CH.sub.2 CH.sub.2 OCH(CH.sub.3)CH.sub.2 --, and --CH.sub.2 OCH.sub.2 
CH.sub.2 OCH.sub.2 CH.sub.2 --. Preferably R.sup.3 is selected from the 
group consisting of propylene, butylene, pentylene, trimethylene, 
2-methyltrimethylene, pentamethylene, hexamethylene, 
3-ethyl-hexamethylene, and octamethylene. 
In component (I), the divalent hydrocarbon radicals of R.sup.4 are 
exemplified by ethylene or any of the divalent hydrocarbon radicals 
delineated for R.sup.3 hereinabove. Preferably R.sup.4 is selected from 
the group consisting of ethylene, propylene, butylene, pentylene, 
trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 
3-ethyl-hexamethylene, and octamethylene. 
In component (I), the alkyl radicals and aryl radicals of R.sup.5 are as 
delineated for R hereinabove. The arylalkyl radicals of R.sup.5 are 
exemplified by benzyl and 2-phenylethyl. It is preferred that R.sup.5 is 
selected from the group consisting of hydrogen, methyl, phenyl, and 
benzyl. 
The group R.sup.6 is a 
##STR5## 
group where R.sup.7 is a monovalent hydrocarbon group having from 1 to 20 
carbon atoms or an aryl radical. The monovalent hydrocarbon groups of 
R.sup.7 are exemplified by methyl, ethyl, propyl, --C.sub.6 H.sub.5, and a 
group having the formula --(CH.sub.2).sub.n CH.sub.3 where n has a value 
of 4 to 18. 
In component (I), the halide anions of A.sup.- are exemplified by 
Cl.sup.-, Br.sup.-, I.sup.-, and F.sup.-, the carboxylate anions of 
A.sup.- are exemplified by CH.sub.3 COO.sup.-, HOCH.sub.2 COO.sup.-, 
C.sub.6 H.sub.5 COO.sup.-, HOC.sub.6 H.sub.4 COO.sup.-, CH.sub.3 CH.sub.2 
COO.sup.-, CH.sub.3 CH.sub.2 CH.sub.2 COO.sup.-, CH.sub.3 CH(OH)CH.sub.2 
COO.sup.-, CH.sub.3 (CH.sub.2).sub.4 COO.sup.-, CH.sub.3 (CH.sub.2).sub.3 
CH(OH)COO.sup.-, CH.sub.3 (CH.sub.2).sub.6 COO.sup.-, CH.sub.3 
(CH.sub.2).sub.8 COO.sup.-, HO(CH.sub.2).sub.9 COO.sup.-, CH.sub.3 
(CH.sub.2).sub.10 COO.sup.-, HO(CH.sub.2).sub.11 COO.sup.-, CH.sub.3 
(CH.sub.2).sub.14 COO.sup.-, HO(CH.sub.2).sub.15 COO.sup.-, CH.sub.3 
(CH.sub.2).sub.16 COO.sup.-, CH.sub.3 (CH.sub.2).sub.5 
CH(OH)(CH.sub.2).sub.10 COO.sup.-, and ClC.sub.6 H.sub.4 COO.sup.-, and 
the inorganic oxoanions are exemplified by ClO.sup.-, ClO.sub.3.sup.-, 
ClO.sub.2.sup.-, ClO.sub.4.sup.-, SO.sub.4.sup..dbd., PO.sub.4.sup..tbd., 
HCO.sub.2.sup.-, NO.sub.3.sup.-, CO.sub.3.sup..dbd., and HCO.sub.3.sup.-. 
Preferably, (A)(i) is an aminofunctional siloxane having the formula 
Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.3, (A)(ii) 
is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 
SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, (A)(iii) is an 
aminofunctional siloxane having the formula HOMe.sub.2 SiO(Me.sub.2 
SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, and (B) is a cyclic 
aminofunctional siloxane having the average formula: 
##STR6## 
wherein R.sup.1 is a group having its formula selected from the group 
consisting of: 
EQU --CH.sub.2 CH.sub.2 CH.sub.2 --.sup.+ NH.sub.2 --CH.sub.2 CH.sub.2 --.sup.+ 
NH.sub.3 .multidot.2A.sup.-, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --.sup.+ 
NH.sub.2 --CH.sub.2 CH.sub.2 --.sup.+ NH.sub.3 .multidot.2A.sup.-, 
##STR7## 
wherein A.sup.- is selected from the group consisting of CH.sub.3 
COO.sup.-, Cl.sup.-, HOCH.sub.2 COO.sup.-, C.sub.6 H.sub.5 COO.sup.- and 
HOC.sub.6 H.sub.4 COO.sup.- wherein x, y, x', and y' are as defined 
above. 
It is also preferred that component (I), x has a value of 10 to 100, y has 
a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 
to 2 with the proviso that the value of x'+y' is 4. 
In component (I) there is present 0.01 to 90 weight percent of component 
(A), 0.1 to 90 weight percent of component (B), and 0.1 to 10 weight 
percent of component (C) such that the combined weight percent of 
components (A)+(B)+(C) is 100 weight percent. 
Component (I), the ammonium siloxane composition, should be present in the 
silicone emulsion compositions of this invention in an amount ranging from 
0.1 to 50 weight percent, and preferably 0.1 to 10 weight percent. 
The organopolysiloxane emulsion of component (II) preferably comprises (A) 
an organopolysiloxane polymer, (B) at least one surfactant, and (C) water. 
The organopolysiloxane polymer (A) of component (II) is preferably a 
compound having the formula R.sup.8.sub.3 SiO(R.sup.8.sub.2 SiO).sub.a 
SiR.sup.8 .sub.3, wherein R.sup.8 is independently a monovalent 
hydrocarbon radical having from 1 to 20 carbon atoms or an aryl radical, 
and a has a value of greater than zero to 1000. 
The monovalent hydrocarbon radicals of R.sup.8 are exemplified by alkyl 
radicals such as methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl, 
cycloaliphatic radicals, such as cyclohexyl, aryl radicals such as phenyl, 
tolyl, and xylyl, aralkyl radicals such as benzyl and phenylethyl. It is 
preferred that R.sup.8 is methyl or phenyl. Preferably a has a value of 10 
to 200. It is especially preferred that the organopolysiloxane polymer is 
a compound having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.a SiMe.sub.3 
wherein a has a value such that the viscosity of the organopolysiloxane 
polymer ranges from about 100 to about 1000 mm.sup.2 /s (1 mm.sup.2 /s=1 
centistoke (cS)). 
The organopolysiloxane also comprises (B) at least one surfactant. The 
surfactant may be an anionic, cationic, nonionic, or amphoteric 
surfactant. The (emulsifying agents) surfactants may be employed 
separately or in combinations of two or more. Suitable emulsifying agents 
for the preparation of a stable aqueous emulsion are known in the art. 
Examples of suitable anionic surfactants include alkali metal 
sulforicinates, sulfonated glyceryl esters of fatty acids such as 
sulfonated monoglycerides of coconut oil acids, salts of sulfonated 
monovalent alcohol esters such as sodium oleylisethianate, amides of amino 
sulfonic acids such as the sodium salt of oleyl methyl tauride, sulfonated 
products of fatty acids nitriles such as palmitonitrile sulfonate, 
sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene 
monosulfonate, condensation products of naphthalene sulfonic acids with 
formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl 
sulfates such as ammonium lauryl sulfate or triethanol amine lauryl 
sulfate, ether sulfates having alkyl groups of 8 or more carbon atoms such 
as sodium lauryl ether sulfate or sodium alkyl aryl ether sulfates, 
alkylarylsulfonates having 1 or more alkyl groups of 8 or more carbon 
atoms, alkylbenzenesulfonic acids which are exemplified by 
hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic 
acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, and 
myristylbenzenesulfonic acid, salts of alkylbenzenesulfonic acids, 
sulfuric esters of polyoxyethylene alkyl ether including CH.sub.3 
(CH.sub.2).sub.6 CH.sub.2 O(C.sub.2 H.sub.4 O).sub.2 SO.sub.3 H, CH.sub.3 
(CH.sub.2).sub.7 CH.sub.2 O(C.sub.2 H.sub.4 O).sub.3.5 SO.sub.3 H, 
CH.sub.3 (CH.sub.2).sub.8 CH.sub.2 O(C.sub.2 H.sub.4 O).sub.8 SO.sub.3 H, 
CH.sub.3 (CH.sub.2).sub.19 CH.sub.2 O(C.sub.2 H.sub.4 O).sub.4 SO.sub.3 H, 
and CH.sub.3 (CH.sub.2).sub.10 CH.sub.2 O(C.sub.2 H.sub.4 O).sub.6 
SO.sub.3 H, sodium salts, potassium salts, and amine salts of 
alkylnaphthylsulfonic acid. 
Examples of cationic surfactants include various fatty acid amines and 
amides and their derivatives, and the salts of the fatty acid amines and 
amides. Examples of aliphatic fatty acid amines include dodecylamine 
acetate, octadecylamine acetate, and acetates of the amines of tallow 
fatty acids, homologues of aromatic amines having fatty acids such as 
dodecylanalin, fatty amides derived from aliphatic diamines such as 
undecylimidazoline, fatty amides derived from aliphatic diamines such as 
undecylimidazoline, fatty amides derived from disubstituted amines such as 
oleylaminodiethylamine, derivatives of ethylene diamine, quaternary 
ammonium compounds and their salts which are exemplified by tallow 
trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, 
didodecyldimethyl ammonium chloride, dihexadecyl ammonium chloride, 
alkyltrimethylammonium hydroxides such as octyltrimethylammonium 
hydroxide, dodecyltrimethylammonium hydroxide, or 
hexadecyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxides 
such as octyldimethylammonium hydroxide, decyldimethylammonium hydroxide, 
didodecyldimethylammonium hydroxide, dioctadecyldimethylammonium 
hydroxide, tallow trimethylammonium hydroxide, coconut oil, 
trimethylammonium hydroxide, methylpolyoxyethylene cocoammonium chloride, 
and dipalmityl hydroxyethylammonium methosulfate, amide derivatives of 
amino alcohols such as beta-hydroxylethylstearylamide, and amine salts of 
long chain fatty acids. 
Examples of nonionic surfactants include polyoxyethylene alkyl ethers, 
polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, 
polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, 
polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene 
glycol, diethylene glycol, ethoxylated trimethylnonanols, and 
polyoxyalkylene glycol modified polysiloxane surfactants. 
Examples of the amphoteric surfactants that can be used include amino acid 
surfactants and betaine acid surfactants. Combinations of 2 or 3 types of 
nonionic surfactants, combinations of nonionic surfactants and anionic 
surfactants, and combinations of nonionic surfactants and cationic 
surfactants can also be employed as component (B). 
Preferred surfactants as component (B) include trimethylnonyl polyethylene 
glycol ethers and polyethylene glycol ether alcohols containing linear 
alkyl groups having from 11 to 15 such as 
2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) (sold as 
Tergitol.RTM.TMN-6 by OSi Specialties, A Witco Company, Endicott, N.Y.), 
2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (10 EO) (sold as 
Tergitol.RTM.TMN-10 by OSi Specialties, A Witco Company, Endicott, N.Y.), 
alkylene-oxypolyethylene oxyethanol (C.sub.11-15 secondary alkyl, 9 EO) 
(sold as Tergitol.RTM.15-S-9 by OSi Specialties, A Witco Company, 
Endicott, N.Y.), alkylene-oxypolyethylene oxyethanol (C.sub.11-15 
secondary alkyl, 15 EO) (sold as Tergitol.RTM.15-S-15 by OSi Specialties, 
A Witco Company, Endicott, N.Y.), octylphenoxy polyethoxy ethanols having 
varying amounts of ethylene oxide units such as octylphenoxy polyethoxy 
ethanol (40 EO) (sold as Triton.RTM. X405 by Rohm and Haas Company, 
Philadelphia, Pa.), nonionic ethoxylated tridecyl ethers available from 
Emery Industries, Mauldin, S.C. under the general tradename Trycol, alkali 
metal salts of dialkyl sulfosuccinates available from American Cyanamid 
Company, Wayne, N.J. under the general tradename Aerosol, polyethoxylated 
quaternary ammonium salts and ethylene oxide condensation products of the 
primary fatty amines, available from Armak Company, Chicago, Ill. under 
the tradenames Ethoquad, Ethomeen, or Arquad, and polyoxyalkylene glycol 
modified polysiloxanes. These preferred surfactants may also be obtained 
from other suppliers under different tradenames. 
Surfactant (B) should be present in the organopolysiloxane emulsion 
compositions in an amount ranging from 1 to 20 parts by weight, and 
preferably 1 to 10 parts by weight per 100 parts by weight of 
organopolysiloxane polymer (A) of component (II). 
Water (C) forms the remainder of component (II) in the compositions of this 
invention and is generally present at a level of from about 50 to 95 parts 
by weight, preferably from about 60 to about 90 parts by weight per 100 
parts by weight of organopolysiloxane polymer (A) of component (II). 
Preparation of the organopolysiloxane emulsions of component (II) can be 
carried out by any conventional technique and are generally separated into 
two types, mechanical means and emulsion polymerization means. Mechanical 
means typically involve homogenizing a mixture of a polydiorganosiloxane, 
one or more surfactants, and water using milling machinery such as a 
colloid mill or a sonolator to obtain the desired droplet sizes. Emulsion 
polymerization methods for making emulsions involve starting with low 
viscosity polymer precursors such as monomers or reactive oligomers, which 
are immiscible in water, a surfactant to stabilize the polymer precursor 
droplet in water, and a water soluble polymerization catalyst which will 
polymerize cyclopolysiloxanes in the presence of water such as quaternary 
ammonium hydroxides, for example tallow trimethylammonium hydroxide, 
quaternary ammonium chlorides such as tallow trimethylammonium chloride, 
metal hydroxides such as sodium hydroxide, strong mineral acids, 
aliphatically substituted benzenesulfonic acids, and aliphatic sulfonic 
acids. These components are added to water, the mixture is stirred and 
polymerization is allowed to advance until the reaction is complete or the 
desired degree of polymerization is reached and a standard emulsion of the 
polymer is formed. 
Component (II), the organopolysiloxane emulsion, should be present in the 
silicone emulsion compositions of this invention in an amount ranging from 
50 to 99.9 weight percent, and preferably 90 to 99.9 weight percent. In 
the silicone emulsions of the present invention Components (I) and (II) 
are present in the amounts described above such that the combined weight 
percent of components (I)+(II) is 100 weight percent. 
The silicone emulsions of this invention can be prepared by homogeneously 
mixing Components (I) and (II) and any optional components in any order. 
Thus it is possible to mix all components in one mixing step immediately 
prior to using the emulsion compositions of the present invention. The 
silicone emulsions of the present invention may also be in the form of 
silicone macroemulsions or silicone microemulsions and may also contain 
optional ingredients, for example antifreeze additives, biocides, organic 
softeners, antistatic agents, preservatives, dyes and flame retardants. 
Preferred preservatives include Kathon.RTM. LX 
(5-chloro-2-methyl-4-isothiazolin-3-one from Rohm and Haas, Philadelphia, 
Pa. 19106), Giv-gard.RTM. DXN (6-acetoxy-2,4-dimethyl-m-dioxane from 
Givaudan Corp., Clifton N.J. 07014), Tektamer.RTM. A.D. (from Calgon 
Corp., Pittsburgh, Pa. 152300), Nuosept.RTM. 91,95 (from Huls America, 
Inc., Piscataway, N.J. 08854), Germaben.RTM. (diazolidinyl urea and 
parabens from Sutton Laboratories, Chatham, N.J. 07928), Proxel.RTM. (from 
ICI Americas Inc., Wilmington, Del. 19897), methyl paraben, propyl 
paraben, sorbic acid, benzoic acid, and lauricidin. The above optional 
components can be present in the silicone emulsions up to about 20 weight 
percent of the total composition, however it is preferred that the 
optional components comprise up to 5 weight percent of the total 
composition. 
In a second embodiment, the present invention relates to a method of making 
a silicone emulsion comprising the steps of (I) mixing (i) a blend 
comprising (A) 0.01 to 90 weight percent of an aminosiloxane solution 
comprising a mixture of (i) an aminofunctional siloxane having its formula 
selected from the group consisting of (a) R.sub.3 SiO(Me.sub.2 SiO).sub.x 
(RR.sup.1 SiO).sub.y (RR.sub.2 SiO).sub.z SiR.sub.3 and (b) R.sub.3 
SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3, and (ii) an 
aminofunctional siloxane having its formula selected from the group 
consisting of (a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y 
(RR.sub.2 SiO).sub.z SiR.sub.2 OH and (b) R.sub.3 SiO(Me.sub.2 SiO).sub.x 
(RR.sup.1 SiO).sub.y SiR.sub.2 OH, and (iii) an aminofunctional siloxane 
having its formula selected from the group consisting of (a) HOR.sub.2 
SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z 
SiR.sub.2 OH and (b) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 
SiO).sub.y SiR.sub.2 OH, (B) 0.1 to 90 weight percent of a cyclic 
aminofunctional siloxane having the average formula 
##STR8## 
(C) 0.1 to 10 weight percent of a compound having the average formula: 
##STR9## 
wherein Me denotes methyl, R is independently a monovalent hydrocarbon 
radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a 
group having its formula selected from the group consisting of --R.sup.3 
NH--R.sup.4 --NH.sub.2 and --R.sup.3 --NH.sub.2 wherein R.sup.3 is a 
divalent hydrocarbon radical having at least 3 carbon atoms, R.sup.4 is a 
divalent hydrocarbon radical having at least 2 carbon atoms, R.sup.2 is 
independently selected from the group consisting of a monovalent 
hydrocarbon radical having from 2 to 6 carbon atoms and an aryl radical, x 
has a value of 10 to 10,000, y has a value of 1 to 8,000, z has a value of 
1 to 250, x' has an average value of 1 to 8 and y' has an average value of 
1 to 8 with the proviso that the value of x'+y' is from 4 to 9, n has an 
average value of 4 to 9, and with the proviso that the value of y/x+y+z+2 
is at least 0.1; (ii) an acid compound; and (iii) water to form a water 
soluble ammonium siloxane composition; and (II) adding the water soluble 
ammonium siloxane composition of step (I) to an organopolysiloxane 
emulsion. 
In the above method, the monovalent hydrocarbon radicals and aryl radicals 
of R are as described hereinabove. Preferably R is methyl or phenyl. The 
monovalent hydrocarbon radicals and aryl radicals of R.sup.2 are as 
described hereinabove. Preferably R.sup.2 is independently selected from 
the group consisting of ethyl, propyl, butyl hexyl, phenyl, tolyl, and 
xylyl. 
The divalent hydrocarbon radicals of R.sup.3 are as described hereinabove. 
Preferably R.sup.3 is selected from the group consisting of propylene, 
butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, 
hexamethylene, 3-ethyl-hexamethylene, and octamethylene. 
The divalent hydrocarbon radicals of R.sup.4 are as described hereinabove. 
Preferably R.sup.4 is selected from the group consisting of ethylene, 
propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, 
pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene. 
In this method of the invention it is preferred that (A)(i) is an 
aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 
SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.3, (A)(ii) is an aminofunctional 
siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 
SiO).sub.y SiMe.sub.2 OH, (A)(iii) is an aminofunctional siloxane having 
the formula HOMe.sub.2 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y 
SiMe.sub.2 OH, and (B) is a cyclic aminofunctional siloxane having the 
formula: 
##STR10## 
wherein R.sup.1 is a group having its formula selected from the group 
consisting of --CH.sub.2 CH.sub.2 CH.sub.2 --NH--CH.sub.2 CH.sub.2 
--NH.sub.2, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --NH--CH.sub.2 CH.sub.2 
--NH.sub.2, and --CH.sub.2 CH.sub.2 CH.sub.2 --NH.sub.2 wherein x, y, x', 
and y' are as defined above. 
It is preferred in this method of the invention that x has a value of 10 to 
100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a 
value of 0.5 to 2 with the proviso that the value of x'+y' is 4. 
In the method of the present invention there is present in component (i), 
0.01 to 90 weight percent of component (A), 0.1 to 90 weight percent of 
component (B), and 0.1 to 10 weight percent of component (C) such that the 
combined weight percent of components (A)+(B)+(C) is 100 weight percent. 
It is preferred for purposes of this invention that from 0.01 to 90 weight 
percent of Component (i) is used, and it is highly preferred that from 0.1 
to 90 weight percent of Component (i) be employed. 
The acid compound of component (ii) in this method of the invention can be 
an inorganic acid or an organic acid and can be a strong acid or a weak 
acid. Preferably the acid is a mineral acid or a carboxylic acid. The 
carboxylic acid can be for example, an aliphatic carboxylic acid 
exemplified by acetic acid ann formic acid, or an aromatic carboxylic acid 
exemplified by benzoic acid or salicylic acid. Acids suitable as component 
(ii) include CH.sub.3 COOH (acetic acid), HCOOH (formic acid), HOCH.sub.2 
COOH (glycolic acid), C.sub.6 H.sub.5 COOH (benzoic acid), HOC.sub.6 
H.sub.4 COOH (2-, 3-, or 4-hydroxybenzoic acid), CH.sub.3 CH.sub.2 COOH 
(propionic acid), CH.sub.3 CH.sub.2 CH.sub.2 COOH (butyric acid), CH.sub.3 
CH(OH)CH.sub.2 COOH (3-hydroxybutyric acid), CH.sub.3 (CH.sub.2).sub.4 
COOH (hexanoic acid), CH.sub.3 (CH.sub.2).sub.3 CH(OH)COOH 
(2-hydroxyhexanoic acid), CH.sub.3 (CH.sub.2).sub.6 COOH (octanoic acid), 
CH.sub.3 (CH.sub.2).sub.8 COOH (decanoic acid), HO(CH.sub.2).sub.9 COOH 
(10-hydroxydecanoic acid), CH.sub.3 (CH.sub.2).sub.10 COOH (lauric acid), 
HO(CH.sub.2).sub.11 COOH (12-hydroxydodecanoic acid), CH.sub.3 
(CH.sub.2).sub.14 COOH (palmitic acid), HO(CH.sub.2).sub.15 COOH 
(16-hydroxyhexadecanoic acid), CH.sub.3 (CH.sub.2).sub.16 COOH (stearic 
acid), CH.sub.3 (CH.sub.2).sub.5 CH(OH)(CH.sub.2).sub.10 COOH 
(12-hydroxystearic acid), CH.sub.3 (CH.sub.2).sub.7 
CH.dbd.CH(CH.sub.2).sub.7 COOH (oleic acid), ClC.sub.6 H.sub.4 COOH (2-, 
3-, or 4-chlorobenzoic acid), HCl (hydrochloric acid), HBr (hydrobromic 
acid), HI (hydrogen iodide), HF (hydrogen fluoride), H.sub.2 CO.sub.2 
(formic acid), HNO.sub.3 (nitric acid), H.sub.3 PO.sub.4 (phosphoric 
acid), H.sub.2 CO.sub.3 (carbonic acid), H.sub.2 SO.sub.4 (sulfuric acid), 
HClO.sub.4 (perchloric acid), HClO.sub.3 (chloric acid), HClO.sub.2 
(chlorous acid), and HClO (hyprochloric acid). 
It is preferred for purposes of this invention that from 0.01 to 50 weight 
percent of Component (ii) is used, and it is highly preferred that from 
0.1 to 10 weight percent of Component (ii) be employed. 
Component (iii) in this method of the invention is water. It is preferred 
for purposes of this invention that from 1 to 99.9 weight percent of 
Component (iii) is used, and it is highly preferred that from 10 to 99.9 
weight percent of Component (iii) be employed. 
In the method of this invention, Component (i) is present at 0.01 to 90 
weight percent, Component (ii) is present at 0.01 to 50 weight percent, 
and Component (iii) is present at 1 to 99.9 weight percent such that the 
combined weight percent of components (i)+(ii)+(iii) is 100 weight 
percent. In Step (I), components (i), (ii), and (iii) are mixed and/or 
agitated preferably until a homogeneous mixture is formed. 
The organopolysiloxane emulsion of step (II) in this method of the 
invention is as described hereinabove including preferred embodiments and 
amounts thereof. The water soluble ammonium siloxane composition of Step 
(I) is then added to the organopolysiloxane emulsion in step (II). About 
0.1 to 50 weight percent of water soluble ammonium siloxane composition 
can be added to the organopolysiloxane emulsion, however, it is preferred 
that about 0.1 to 10 weight percent of the ammonium siloxane composition 
formed in step (I) is added to the organopolysiloxane emulsion, the 
organopolysiloxane emulsion making up the remainder of the silicone 
emulsion (i.e. the water soluble ammonium siloxane 
composition+organopolysiloxane emulsion is equal to 100 weight percent). 
The method of this invention can further comprise adding an acid anhydride 
during step (I). The acid anhydride is exemplified by (CH.sub.3 CO).sub.2 
O (acetic anhydride), (C.sub.6 H.sub.5 CO).sub.2 O (benzoic anhydride), 
CH.sub.3 CH.sub.2 COOCOCH.sub.2 CH.sub.3 (proprionic anhydride), (CH.sub.3 
CH.sub.2 CH.sub.2 CO).sub.2 O (butyric anhydride), (CH.sub.3 
(CH.sub.2).sub.4 CO).sub.2 O (hexanoic anhydride), (CH.sub.3 
(CH.sub.2).sub.8 CO).sub.2 O (decanoic anhydride), (CH.sub.3 
(CH.sub.2).sub.10 CO).sub.2 O (lauric anhydride), (CH.sub.3 
(CH.sub.2).sub.14 CO).sub.2 O (palmitic anhydride), (CH.sub.3 
(CH.sub.2).sub.16 CO).sub.2 O (stearic anhydride). 
It is preferred that if an acid anhydride is employed, that from 0.01 to 20 
weight parts of acid anhydride is used, and it is highly preferred that 
from 0.01 to 10 weight parts of acid anhydride be employed per 100 weight 
parts of components (i)+(ii)+(iii). 
The method of this invention can further comprise adding an aryl halide 
during step (I). The aryl halide is exemplified by benzyl chloride, benzyl 
bromide, benzyl iodide, benzyl fluoride, phenyl chloride, phenyl bromide, 
or phenyl fluoride. 
It is preferred that if an aryl halide is employed, that from 0.01 to 10 
weight parts of aryl halide is used, and it is highly preferred that from 
0.01 to 5 weight parts of aryl halide be employed per 100 weight parts of 
components (i)+(ii)+(iii). 
In a third embodiment, the present invention relates to a method of 
treating a substrate, the method comprising the step of (I) applying to a 
substrate a silicone emulsion wherein the silicone emulsion comprises the 
silicone emulsion described in the first embodiment of this invention 
hereinabove including preferred embodiments and amounts thereof. 
The silicone emulsions of this invention may be applied to the substrate by 
employing any suitable application technique, for example by padding or 
spraying, or from a bath. The concentration of the treating solution will 
depend on the desired level of application of siloxane to the substrate, 
and on the method of application employed, but it is believed by the 
inventors herein that the most effective amount of the silicone emulsion 
should be in the range such that the substrate picks up the silicone 
composition at about 0.05% to 10% based on the weight of the substrate. 
In this method of the invention the substrate is preferably a fiber or 
fabric. The fibers usually in the form of tow, or knitted or woven 
fabrics, are immersed in the silicone emulsion whereby the emulsion 
becomes selectively deposited on the fibers. The deposition of the 
silicone emulsion on the fibers may also be expedited by increasing the 
temperatures of the bath with temperatures in the range of from 20.degree. 
to 60.degree. C. being generally preferred. 
The silicone emulsions of this invention can be employed for the treatment 
of substrates such as animal fibers such as wool, cellulosic fibers such 
as cotton, and synthetic fibers such as nylon, polyester and acrylic 
fibers, or blends of these materials, for example, polyester/cotton 
blends, and may also be used in the treatment of leather, paper, paper 
pulp, tissues such as bath tissue or facial tissue, and gypsum board. The 
fibers may be treated in any form, for example as knitted and woven 
fabrics and as piece goods. They may also be treated as agglomerations of 
random fibers as in filling materials for pillows and the like such as 
fiberfil. The compositions of the invention are especially useful for 
treating paper pulp and bath or facial tissue. 
In this embodiment of the invention the method can further comprise heating 
the substrate after step (I). Thus following the application of the 
silicone emulsion to the substrate, the siloxane can then be cured. 
Preferably curing is expedited by exposing the treated fibers to elevated 
temperatures, preferably from 50.degree. to 200.degree. C. 
The silicone emulsion of this invention should be used at about 0.05 to 25 
weight percent in the final bath for exhaust method applications, and 
about 5 gm/l to 80 gm/l in a padding method of application, and about 5 
gm/l to 600 gm/l for a spraying application. The fibers or fabrics treated 
with the emulsions of this invention have superior slickness, have no oily 
feeling, and are soft to the touch.

EXAMPLES 1-15 
A water soluble ammonium siloxane composition was prepared by mixing about 
33 weight percent of an aminosiloxane solution and 3.0 weight percent of 
glacial acetic acid in a container under nitrogen. Next, about 64 weight 
percent of water was added to this mixture and the mixture was then 
agitated until it was homogenous. 
The aminosiloxane solution contained about (i) 44 weight percent of a 
mixture of an aminofunctional siloxane having the average formula Me.sub.3 
SiO(Me.sub.2 SiO).sub.23 (MeRSiO).sub.13 SiMe.sub.3, an aminofunctional 
siloxane having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.23 
(MeRSiO).sub.13 SiMe.sub.2 OH, and an aminofunctional siloxane having the 
average formula HOMe.sub.2 SiO(Me.sub.2 SiO).sub.23 (MeRSiO).sub.13 
SiMe.sub.2 OH, (ii) 51 weight percent of an aminofunctional siloxane 
having the average formula 
##STR11## 
(iii) 5 weight percent of a cyclosiloxane having the formula 
##STR12## 
where R is a group having the formula --CH.sub.2 CH(CH.sub.3)CH.sub.2 
--NH--CH.sub.2 CH.sub.2 --NH.sub.2, the value of x'+y' is from 4 to 9, and 
n has an average value of 4 to 9. The resulting solution (example) 
contained components (i), (ii), and (iii) in the amounts delineated above 
however, R was a group having the formula 
##STR13## 
Next, an amount of this ammonium siloxane solution was mixed with three 
different organopolysiloxane emulsions: 
Organopolysiloxane Emulsion A contained about 55 weight percent of an 
organopolysiloxane polymer having the formula Me.sub.3 SiO(Me.sub.2 
SiO).sub.a SiMe.sub.3 and having a viscosity of about 350 mm.sup.2 /s, 
about 3 weight percent of a nonionic surfactant (Tergitole.RTM.TMN-6 
(2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO)) sold by OSi 
Specialties, A Witco Company, Endicott, N.Y.), about 0.2 weight percent of 
a cationic surfactant (tallow trimethyl ammonium chloride) and about 41 
weight percent of water. The emulsion also contained a preservative 
(2-methyl-4-Isothiazolin-3-One). 
Organopolysiloxane Emulsion B contained about 50 weight percent of an 
organopolysiloxane polymer having the formula Me.sub.3 SiO(Me.sub.2 
SiO).sub.a SiMe.sub.3 and having a viscosity of about 350 mm.sup.2 /s, 
about 3.9 weight percent of a nonionic surfactant (a polyoxyethylene 
lauryl ether having (2-3 EO), about 1.5 weight percent of a nonionic 
surfactant (a polyoxyethylene lauryl ether (23 EO)), and 43 weight percent 
water. The emulsion also contained a biocide (glycerine). 
Organopolysiloxane Emulsion C contained about 60 weight percent of an 
organopolysiloxane polymer having the formula Me.sub.3 SiO(Me.sub.2 
SiO).sub.a SiMe.sub.3 and having a viscosity of about 350 mm.sup.2 /s, 
about 3 weight percent of a nonionic surfactant (Tergitole.RTM.TMN-6 
(2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO)) sold by OSi 
Specialties, A Witco Company, Endicott, N.Y.), about 0.2 weight percent of 
an anionic surfactant (sodium alkyl aryl ether sulfate), and about 36 
weight percent of water. The emulsion also contained a preservative 
(Giv-gard.RTM. DXN Bactericide (6-acetoxy-2,4-dimethyl-m-dioxane) from 
Givaudan Corp., Clifton N.J. 07014). The amount of solution and the amount 
and type of organopolysiloxane emulsion for each example is shown in Table 
1 hereinbelow. 
TABLE 1 
______________________________________ 
Wt % Wt % Organopolysiloxane 
Example Solution Emulsion Emulsion 
______________________________________ 
1 0.1 99.9 A 
2 0.5 99.5 A 
3 1.0 99.0 A 
4 5.0 95.0 A 
5 10.0 90.0 A 
Control 0.0 100.0 A 
6 0.1 99.9 B 
7 0.5 99.5 B 
8 1.0 99.0 B 
9 5.0 95.0 B 
10 10.0 90.0 B 
Control 0.0 100.0 B 
11 0.1 99.9 C 
12 0.5 99.5 C 
13 1.0 99.0 C 
14 5.0 95.0 C 
15 10.0 90.0 C 
Control 0.0 100.0 C 
______________________________________ 
Each silicone emulsion prepared above was then placed on the fabric by 
soaking a 12.5 inch by 10 inch 100% cotton sheet in the solution in a 400 
g bath. The sheet was removed, run through a padder to dry and placed in a 
150.degree. C. oven for 3.5 minutes to dry. 
These sheets were then tested for relative hand value. The relative hand 
value was determined by a survey of panelists. The panelists first rank 
treated samples in order of increasing softness. This ranking is then 
repeated a number of times to insure reproducibility. Samples are then 
given ratings based on comparisons to the controls and each other. The 
rating scale is between 0 and 5 in increments of 0.25, with the higher 
ratings indicating increased softness. A rating difference of 0.25 between 
samples indicates that the panelists could consistently detect a 
difference in the softness after handling the samples for a period of 
about 15 seconds. When two samples were 0.50 points apart, panelists could 
perceive a difference in around 5 seconds, while a difference of 0.75 or 
higher indicated an immediately noticeable distinction. The results of the 
test are reported in Table 2 hereinbelow. 
TABLE 2 
______________________________________ 
Example Relative Hand Value (5 = best) 
______________________________________ 
1 1 
2 2 
3 3 
4 4 
5 5 
Control 0 
6 1 
7 2 
8 3 
9 4 
10 5 
Control 0 
11 1 
12 2 
13 3 
14 4 
15 5 
Control 0 
______________________________________ 
It is apparent from Table 2 that the emulsions of the present invention 
render fibers smooth and soft and are thus useful as fiber treatment 
agents. 
The emulsions prepared above were then tested for percent settling, percent 
creaming and oil. Settling was determined by visual inspection of the 
sample, if a clear liquid separated out from the emulsion near the bottom 
of the sample, then the sample was determined to have some settling. 
Creaming was determined by placing the sample in a centrifuge and running 
it at high speeds for a period of time. After centrifuging the sample, it 
was visually inspected to see if any separation had occurred in the middle 
of the centrifuge tube which would indicate creaming had occurred. There 
was no creaming in Examples 1-15 or in any of the controls. 
The sample was also visually inspected for any loose oil floating on top of 
the centrifuge tube. There was no oil present in Examples 1-15 or in any 
of the controls. The percent settling of each sample is reported in Table 
3 hereinbelow. 
TABLE 3 
______________________________________ 
Example 
Settling (%) 
______________________________________ 
1 0 
2 0 
3 0 
4 Trace 
5 1 
Control 
0 
6 4.5 
7 6.3 
8 6.7 
9 6.6 
10 1.2 
Control 
2 
11 0 
12 0 
13 0 
14 0.6 
15 6.6 
Control 
0 
______________________________________ 
It is apparent from Table 3 that the emulsions of the present invention are 
resistant to settling and creaming and contain no free oil,