# US 5,707,435 A · Ammonium siloxane emulsions and their use as fiber treatment agents

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- Number: US 5,707,435 A
- Document ID: US5707435A
- Status: Granted
- Kind: A
- Application number: 08/730,983
- Filed: 1996-10-16
- Granted: 1998-01-13
- Earliest claimed: 1996-10-16
- Assignees: Dow Corning Corporation
- Inventors: Daniel Joseph Halloran
- Web page: https://patentgrep.com/patent/US5707435A

## CPC

- C04B 41/009: {characterised by the material treated}
- C04B 41/4961: {Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"}
- C04B 41/64: Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
- C08L 83/04: Polysiloxanes
- C08L 83/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- D06M 15/643: containing silicon in the main chain
- D06M 15/6436: {containing amino groups}
- C08G 77/045: {containing less than 25 silicon atoms}
- C08G 77/16: to hydroxy groups
- C08G 77/26: nitrogen-containing groups
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

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.

## Claims

### Claim 1

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 average formula: ##STR14## (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR15## 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 ##STR16## 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.

### Claim 2 (depends on 1)

An emulsion according to claim 1, wherein R is methyl or phenyl.

### Claim 3 (depends on 1)

An emulsion according to claim 1, wherein R.sup.2 is independently selected from the group consisting of ethyl, propyl, butyl, hexyl, phenyl, tolyl, and xylyl.

### Claim 4 (depends on 1)

An emulsion according to claim 1, wherein R.sup.3 is selected from the group consisting of propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 5 (depends on 1)

An emulsion according to claim 1, wherein R.sup.4 is selected from the group consisting of ethylene, propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 6 (depends on 1)

An emulsion according to claim 1, wherein R.sup.5 is selected from the group consisting of hydrogen, methyl, phenyl, --COCH.sub.3, and --CH.sub.2 C.sub.6 H.sub.5.

### Claim 7 (depends on 1)

An emulsion according to claim 1, 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.-.

### Claim 8 (depends on 1)

An emulsion according to claim 1, wherein (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: ##STR17## wherein R.sup.1 is a group having its formula selected from the group consisting of: ##STR18## 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.

### Claim 9 (depends on 8)

An emulsion according to claim 8, wherein 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 from 4 to 9.

### Claim 10 (depends on 1)

An emulsion according to claim 1, wherein 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 from 4 to 9.

### Claim 11 (depends on 1)

An emulsion according to claim 1, wherein the organopolysiloxane emulsion comprises:
(D) an organopolysiloxane polymer;
(E) at least one surfactant; and
(F) water.

### Claim 12 (depends on 11)

An emulsion according to claim 11, wherein (D) 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 is from 100 to 1000 mm.sup.2 /s.

### Claim 13 (depends on 11)

An emulsion according to claim 11, wherein (E) is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, a mixture of nonionic surfactants, a mixture of nonionic surfactants and anionic surfactants, and a mixture of nonionic surfactants and cationic surfactants.

### Claim 14 (depends on 13)

An emulsion according to claim 13, wherein the anionic surfactant is selected from the group consisting of alkali metal sulforicinates, sulfonated glyceryl esters of fatty acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sulfonated products of fatty acids nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulfates, alkyl ether sulfates having at least 8 carbon atoms, alkyl aryl ether sulfates, alkylarylsulfonates having at least 8 carbon atoms, alkylbenzenesulfonic acids, salts of alkylbenzenesulfonic acids, sulfuric esters of polyoxyethylene alkyl ether, and amine salts or sodium salts or potassium salts of alkylnaphthylsulfonic acid.

### Claim 15 (depends on 13)

An emulsion according to claim 13, wherein the cationic surfactant is selected from the group consisting dodecylamine acetate, octadecylamine acetate, acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids, fatty amides derived from aliphatic diamines, fatty amides derived from aliphatic diamines, fatty amides derived from disubstituted amines, derivatives of ethylene diamine, quaternary ammonium compounds, salts of quaternary ammonium compounds, alkyltrimethylammonium hydroxides, dialkyldimethylammonium hydroxides, coconut oil, methylpolyoxyethylene cocoammonium chloride, dipalmityl hydroxyethylammonium methosulfate, amide derivatives of amino alcohols, and amine salts of long chain fatty acids.

### Claim 16 (depends on 13)

An emulsion according to claim 13, wherein the nonionic surfactant is selected from the group consisting of 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 polysiloxanes.

### Claim 17

A method of making a silicone emulsion comprising the steps of:
(1) 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.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 average formula: ##STR19## (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR20## 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
(2) adding the water soluble ammonium siloxane composition of step (1) to an organopolysiloxane emulsion.

### Claim 18 (depends on 17)

A method according to claim 17, wherein (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: ##STR21## 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.

### Claim 19 (depends on 17)

A method according to claim 17, wherein (II) is selected from the group consisting of CH.sub.3 COOH, HOCH.sub.2 COOH, C.sub.6 H.sub.5 COOH, HOC.sub.6 H.sub.4 COOH, and (CH.sub.3 CO).sub.2 O.

### Claim 20 (depends on 17)

A method according to claim 17, wherein the method further comprises adding an acid anhydride during step (1).

### Claim 21 (depends on 20)

A method according to claim 20, wherein the acid anhydride is selected from the group consisting of acetic anhydride, benzoic anhydride, proprionic anhydride, butyric anhydride, hexanoic anhydride, decanoic anhydride, lauric anhydride, palmitic anhydride, and stearic anhydride.

### Claim 22 (depends on 17)

A method according to claim 17, wherein the method further comprises adding an aryl halide during step (1).

### Claim 23 (depends on 22)

A method according to claim 22, wherein the aryl halide is selected from the group consisting of benzyl chloride, benzyl bromide, benzyl iodide, benzyl fluoride, phenyl chloride, phenyl bromide, and phenyl fluoride.

### Claim 24

A method of treating a substrate, the method comprising the step of:
(1) applying to a substrate a silicone emulsion wherein the silicone emulsion comprises:
(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 average formula: ##STR22## (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR23## 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 ##STR24## 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.

### Claim 25 (depends on 24)

A method according to claim 24, wherein the method further comprises heating the substrate after step (1).

### Claim 26 (depends on 24)

A method according to claim 24, wherein the substrate is selected from the group consisting of wool, cotton, nylon, polyester, acrylic fibers, polyester-cotton blends, leather, paper, gypsum board, and fiberfil.

### Claim 27

A composition of matter obtained by mixing the incipient ingredients:
(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 average formula: ##STR25## (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR26## 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 ##STR27## 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.