USE OF LOW-CYCLEN DERIVATIZED AMINO-FUNCTIONAL SILICONE POLYMERS FOR TREATING FIBROUS SUBSTRATES
20230287624 · 2023-09-14
Assignee
Inventors
Cpc classification
D06M2200/50
TEXTILES; PAPER
International classification
Abstract
A composition for hydrophilic treatment of fibrous substrates that is washfast in terms of softness contains derivatives of amino-functional organopolysiloxanes containing siloxane units of a general formula (I), optionally siloxane units of a general formula (II), siloxane units of general formula (III), and siloxane units of a general formula (IV). Impurities of octamethylcyclotetrasiloxane (D4 cyclics), decamethylcyclopentasiloxane (D5 cyclics) and dodecamethylcyclohexasiloxane (D6 cyclics) are present in proportions of less than 0.1% by weight in each case and after a storage time of 20 days at a temperature of 50° C. the proportions of D4 cyclics, representative of D4, D5 and D6, remain below 0.1% by weight in each case, based in each case on the total weight of the derivatives of amino-functional organopolysiloxanes.
Claims
1-15 (canceled)
16. The use of compositions for hydrophilic treatment of fibrous substrates that is washfast in terms of softness containing derivatives of amino-functional organopolysiloxanes containing siloxane units of general formula (I)
—R.sup.2—[NR.sup.3(CH.sub.2).sub.n].sub.iNR.sup.4R.sup.5 (V), wherein i is 0, 1, 2, 3 or 4, n is 2, 3, 4, 5 or 6, R.sup.2 represents a divalent, linear or branched C.sub.1- to C.sub.18-hydrocarbon radical, R.sup.3 represents a hydrogen atom, an optionally fluorine-, chlorine-, bromine-, hydroxy- or C.sub.1- to C.sub.5-alkoxy-substituted C.sub.1- to C.sub.18-hydrocarbon radical, or an acyl radical or a radical of general formula (VI), R.sup.4 represents a radical of general formula (VI),
—(C═O)—R.sup.6—OH (VI), R.sup.5 represents a hydrogen atom or an optionally fluorine-, chlorine-, bromine-, hydroxy- or C.sub.1- to C.sub.5-alkoxy-substituted C.sub.1- to C.sub.18-hydrocarbon radical or an acyl radical, R.sub.6 represents a divalent, linear or branched C.sub.2- to C.sub.8-hydrocarbon radical or an —OR.sup.7-radical, R.sup.7 represents a divalent linear or branched C.sub.2- to C.sub.8-hydrocarbon radical, Q represents a group of general formula (VII)
—R.sup.2—[NR.sup.9(CH.sub.2).sub.n].sub.iN(R.sup.9).sub.2 (VII), wherein i and n are as defined above, R.sup.9 may be identical or different and represents a hydrogen atom, an optionally fluorine-, chlorine-, bromine-, hydroxy- or C.sub.1-to C.sub.5-alkoxy-substituted C.sub.1- to C.sub.18-hydrocarbon radical or an acyl radical, Y represents a radical of general formula (VIII) and/or (IX),
—OR.sup.1(VIII) and/or —[O(CHR.sup.10).sub.p].sub.mOR.sup.11 (IX), wherein m is 0 or an integer from 1 to 100, preferably 1 to 20, and p is 2, 3 or 4, R.sup.1 represents a hydrogen atom or a C.sub.1- to C.sub.4-alkyl radical, R.sup.10 represents a hydrogen atom or a C.sub.1- to C.sub.8-hydrocarbon radical, R.sup.11 represents a hydrogen atom, a C.sub.1- to C.sub.10-hydrocarbon radical, preferably a C.sub.4- to C.sub.10-hydrocarbon radical, or a group of formula —(C═O)—R.sup.12, R.sup.12 represents a C.sub.1- to C.sub.10-hydrocarbon radical or an —OR.sup.13-radical, and R.sup.13 represents a c.sub.1- to C.sub.10-hydrocarbon radical, with the proviso that at least a portion of the radicals Y are radicals of formula (IX), with the proviso that impurities of octamethylcyclotetrasiloxane (D4 cyclics), decamethylcyclopentasiloxane (D5 cyclics) and dodecamethylcyclohexasiloxane (D6 cyclics) are present in proportions of less than 0.1% by weight in each case and after a storage time of 20 days at a temperature of 50° C. the proportions of D4 cyclics, representative of D4, D5 and D6, remain below 0.1% by weight in each case, based in each case on the total weight of the derivatives of amino-functional organopolysiloxanes.
17. The use as claimed in claim 16, wherein the compositions according to the invention employ derivatives of amino-functional organopolysiloxanes of general formula (X)
YR.sub.2SiO—(R.sub.2SiO).sub.k—(RZSiO).sub.l—(RQSiO).sub.o—R.sub.2SiY (X), wherein R, Y, Z and Q are as defined in claim 16, k is an integer from 50 to 700, l is an integer from 1 to 30 and o is an integer from 0 to 30, with the proviso that at least a portion of the radicals Y are radicals of formula (IX).
18. The use as claimed in claim 16, wherein a portion of the radicals Y corresponds to (iso)oxyalkyl radicals of formula (IX), wherein C.sub.4-C.sub.10-alkoxy radicals or C.sub.4-C.sub.10-monoalkyl glycol ether radicals are concerned, in addition to radicals of formula (VIII) which are hydroxyl or methoxy radicals.
19. The use as claimed in claim 16, wherein the compositions employed are aqueous emulsions containing the low-cyclics derivatives of amino-functional organopolysiloxanes (A), emulsifiers (B) and/or co-emulsifiers (B′) and water (C).
20. A process for washfast treatment of fibrous substrates as claimed in claim 16, wherein the compositions are applied to the fibrous substrates and the thus-treated fibrous substrates are allowed to dry at temperatures of preferably 20° C. to 200° C.
21. The process as claimed in claim 20, wherein the fibrous substrates are textiles.
22. A process for producing the low-cyclics derivatives of amino-functional organopolysiloxanes employed in the compositions as claimed in claim 16, by reacting amino-functional organopolysiloxanes (1) containing amino-functional siloxane units of general formula (II)
H—[O(CHR.sup.10).sub.p].sub.mOR.sup.11 (XIII), wherein R.sup.10, R.sup.11, m and p are as defined in claim 16, with the proviso that in the obtained derivatives of amino-functional organopolysiloxanes the content of D4, D5 and D6 cyclics is less than 0.1% by weight in each case as a result of effecting distillative removal of the cyclics before, during or after the reaction.
23. The process as claimed in claim 22, wherein amino-functional organopolysiloxanes (1) containing amino-functional siloxane units of general formula (II) and siloxane units of general formula (XII) are simultaneously reacted with compounds (2) of general formula (XI) and compounds (3) of general formula (XIII).
24. The process as claimed in claim 22, wherein amino-functional organopolysiloxanes (1) containing amino-functional siloxane units of general formula (II) and siloxane units of general formula (XII) are reacted with compounds (2) of general formula (XI) in a first reaction step and the reaction products formed therefrom are subsequently reacted with compounds (3) of general formula (XIII) in a further reaction step.
25. The process as claimed in claim 22, wherein amino-functional organopolysiloxanes (1) containing amino-functional siloxane units of general formula (II) and siloxane units of general formula (XII) are reacted with compounds (3) of general formula (XIII) in a first reaction step and the reaction products formed therefrom are subsequently reacted with compounds (2) of general formula (XI) in a further reaction step.
26. A process for producing the low-cyclics derivatives of amino-functional organopolysiloxanes employed in the composition of claim 16, by reacting amino-functional organopolysiloxanes (1) containing amino-functional siloxane units of general formula (II)
H—[O(CHR.sup.10).sub.p].sub.mOR.sup.11 (XIII), wherein R.sup.10,R.sup.11, m and p are as defined in claim 1, with the proviso that in the obtained derivatives of amino-functional organopolysiloxanes the content of D4, D5 and D6 cyclics is less than 0.1% by weight in each case.
27. The process as claimed in claim 22, wherein the amino-functional organopolysiloxanes (1) employed are those of general formula (XIV),
R.sup.1OR.sub.2SiO—(R.sub.2SiO).sub.k—(RQSiO).sub.l+o—SiR.sub.2OR.sup.1 (XIV), wherein R may be identical or different and represents a hydrogen atom or a monovalent, optionally fluorine-, chlorine- or bromine-substituted, C.sub.1- to C.sub.18-hydrocarbon radical, R.sup.1 represents a hydrogen atom or a C.sub.1- to C.sub.4-alkyl radical, k is an integer from 50 to 700, l is an integer from 1 to 30, and o is an integer from 0 to 30.
28. The process as claimed in claim 22, wherein the compounds (2) of general formula (XI) employed are lactones or cyclic carbonic esters.
29. The process as claimed in claim 22, wherein the compounds (3) of general formula (XIII) employed are a C.sub.4- to C.sub.10-alcohol or a C.sub.4- to C.sub.10-monoalkyl glycol ether.
30. The process as claimed in claim 22, wherein the compounds (2) of general formula (XI) employed are y-butyrolactone or propylene carbonate.
Description
EXAMPLE OF PURIFICATION OF AN AMINO-FUNCTIONAL POLYDIMETHYLSILOXANE FOR USE IN EXAMPLES 2 TO 7
[0161] 5000 g of an unpurified silanol- and methoxy-terminated laterally aminoethylaminopropyl-functional polydimethylsiloxane having a viscosity of 823 mPa.Math.s and an amine content of 0.288 meq/g was heated in a KDL 1 laboratory short-path distillation apparatus from UIC at a temperature of 180° C. and a pressure of 0.03 mbar at a feed rate of 400 g/h. A distillate amount of 52 g was formed. The bottoms material had a viscosity of 973 mPa.Math.s and an amine content of 0.291 meq/g. This was used as raw material for the low-cyclics derivatives of amino-functional polydimethylsiloxanes in Examples 2 to 7.
Example 1 (Production of a Monohydroxyamidoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Inventive)
[0162] In a 1000 ml 3-necked flask fitted with a thermocouple, KPG stirrer and reflux condenser 500 g of an unpurified silanol- and methoxy-terminated laterally aminoethylaminopropyl-functional polydimethylsiloxane having a viscosity of 939 mPa.Math.s and an amine content of 0.288 meq/g (144 mmol of amine) were initially charged and blanketed with nitrogen. At room temperature 6.49 g (75 mmol) of γ-butyrolactone, obtainable from Imhoff & Stahl GmbH, Mannheim, were added with stirring. The clear reaction mixture was subsequently heated to 100° C. and stirred for 5 hours at this temperature. The amine number of the reaction mixture decreased to 0.155 meq/g. The reaction mixture was heated in the KDL 1 laboratory short-path distillation apparatus from UIC at a temperature of 180° C. and a pressure of 0.03 mbar at a feed rate of 250 g/h. A distillate amount of 5.15 g was formed. The bottoms material was recycled to a stirred 3-necked flask apparatus and cooled with stirring. At a temperature of 130° C. 25.5 g of diethylene glycol monobutyl ether, obtainable from Stockmeier Chemie GmbH in Bielefeld, were added and the mixture was slowly cooled to room temperature over 2 h. An almost colorless oil having a viscosity of 2592 mPa.Math.s, a residual amine content of 0.147 meq/g and a hazen color number of 3 was obtained. According to GC determination (cool-on-column method) the cyclics proportions were 123 ppm of D4, 96 ppm of D5 and 148 ppm of D6. After 20 days of storage at 50° C., the value of D4 increased to 164 ppm. Relative to the amino-functional precursor the derivatized product has a new signal in the .sup.29Si NMR spectrum at a chemical shift of −12.9 ppm which is assignable to the terminal diethylene glycol monobutyl ether-bonded silicon atom.
Example 2 (Production of a Monohydroxycarbamatoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Inventive)
[0163] In a 1000 ml 3-necked flask fitted with a thermocouple, KPG stirrer and reflux condenser 600 g (184 mmol of amine) of a low-cyclics silanol- and methoxy-terminated laterally aminoethylaminopropyl-functional polydimethylsiloxane from the purification example having a viscosity of 959 mPa.Math.s and an amine content of 0.306 meq/g were initially charged and blanketed with nitrogen. According to GC determination (cool-on-column method) the cyclics proportions were 230 ppm of D4, 330 ppm of D5 and 380 ppm of D6. At room temperature, 30.0 g of diethylene glycol monobutyl ether and 9.38 g (92 mmol) of propylene carbonate, obtainable from Huntsman Holland BV, Rotterdam, were added with stirring. The clear reaction mixture was subsequently heated to 80° C. and stirred at this temperature for 3 hours. An almost colorless oil having a viscosity of 1907 mPa.Math.s, a residual amine content of 0.153 meq/g and a hazen color number of 2 was obtained. According to GC determination (cool-on-column method) the cyclics proportions were 286 ppm of D4, 330 ppm of D5 and 283 ppm of D6. After 20 days of storage at 50° C., the value of D4 increased to 323 ppm. Relative to the amino-functional precursor the derivatized product has a new signal in the .sup.29Si NMR spectrum at a chemical shift of −12.9 ppm which is assignable to the terminal diethylene glycol monobutyl ether-bonded silicon atom.
Example 3 (Production of a Monohydroxycarbamatoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Inventive)
[0164] In a 1000 ml 3-necked flask fitted with a thermocouple, KPG stirrer and reflux condenser 600 g (184 mmol of amine) of the amino-functional polydimethylsiloxane precursor from example 2 were initially charged and blanketed with nitrogen. At room temperature, 9.38 g (92 mmol) of propylene carbonate were added with stirring. The reaction mixture was then heated to 80° C. The initially turbid mixture became clear upon attaining 80° C. and was stirred at this temperature for 3 hours. 30.0 g of diethylene glycol monobutyl ether were then stirred in and the mixture was slowly cooled to room temperature over 2 hours. An almost colorless oil having a viscosity of 1278 mPa.Math.s, a residual amine content of 0.160 meq/g and a hazen color number of 3 was obtained. According to GC determination (cool-on-column method) the cyclics proportions were 108 ppm of D4, 77 ppm of D5 and 124 ppm of D6. After 20 days of storage at 50° C., the value of D4 increased to 146 ppm. Relative to the amino-functional precursor the derivatized product has a new signal in the .sup.29Si NMR spectrum at a chemical shift of −12.9 ppm which is assignable to the terminal diethylene glycol monobutyl ether-bonded silicon atom.
Example 4 (Production of an Acetamidoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Noninventive)
[0165] In a 2000 ml 3-necked flask fitted with a thermocouple, KPG stirrer, dropping funnel and reflux condenser 935.58 g (286 mmol of amine) of the amino-functional polydimethylsiloxane precursor from example 2 were initially charged, blanketed with nitrogen and heated to 55° C. 25.17 g of diethylene glycol monobutyl ether were then stirred in and the resulting mixture stirred at 55° C. for a further 30 minutes. 14.08 g (138 mmol) of acetic anhydride, obtainable from Sigma-Aldrich Chemie GmbH, Steinheim, were then slowly added dropwise with stirring. As a result of the exothermicity the temperature increased to 65° C. Subsequently, the clear reaction mixture was heated to 80° C. and stirred at this temperature for 30 minutes. A further 25.17 g of diethylene glycol monobutyl ether were then stirred in and the resulting mixture stirred at 80° C. for a further hour. A yellow oil having a viscosity of 2672 mPa.Math.s, a residual amine content of 0.152 meq/g and a hazen color number of 9 was obtained. According to GC determination (cool-on-column method) the D4 cyclics proportion was 148 ppm. After 20 days of storage at 50° C., the cyclics proportion increased to 1312 ppm.
[0166] Example 5 (Production of a Pentahydroxyamidoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Noninventive)
[0167] In a 500 ml 3-necked flask fitted with a thermocouple, KPG stirrer, dropping funnel, reflux cooler, distillation bridge and vacuum pump with control means 180 g (55 mmol of amine) of the amino-functional polydimethylsiloxane precursor from example 2 together with 180 g of isopropanol were initially charged and blanketed with nitrogen. At room temperature and standard pressure 4.73 g (55 mmol) of gluconolactone, obtainable from Sigma-Aldrich Chemie GmbH, Steinheim, were added with stirring. The turbid reaction mixture was then heated to 80° C. The mixture was stirred at this temperature for 3 hours, during which time it became increasingly clear. A vacuum of 350 mbar was then applied at this temperature setting and isopropanol was distilled off. Simultaneously, 16.2 g of diethylene glycol monobutyl ether were stirred in via the dropping funnel and the vacuum was improved to 180 mbar over 2 hours. Depending on the distillation rate, the temperature of the mixture fell to 65° C. to 55° C. 160 g of distillate were obtained. The contents of the flask became increasingly viscous and yellowish with slight turbidity. A homogeneous, viscous and yellowish oil having a viscosity of 7180 mPa.Math.s, a residual amine content of 0.075 meq/g and a hazen color number of 9 was obtained.
Example 6 (Production of a Dihydroxycarbamatoamino-Functional Polydimethylsiloxane With Butyl Diglycol, Noninventive)
[0168] In a 1000 ml 3-necked flask fitted with a thermocouple, KPG stirrer and reflux condenser 500 g (153 mmol of amine) of the amino-functional polydimethylsiloxane precursor from example 2 were initially charged and blanketed with nitrogen. At room temperature, 25.0 g of diethylene glycol monobutyl ether and 8.71 g (74 mmol) of glycerol carbonate, obtainable from Huntsman Holland BV, Rotterdam, were added with stirring. The turbid reaction mixture was subsequently heated to 80° C. and stirred at this temperature for 3 hours. A clear, slightly yellowish, viscous oil having a viscosity of 17800 mPa.Math.s, a residual amine content of 0.152 meq/g and a hazen color number of 5 was obtained.
Example 7 (Production of a Monohydroxycarbamatoamino-Functional Polydimethylsiloxane With Isotridecanol, Noninventive)
[0169] In a 500 ml 3-necked flask fitted with a thermocouple, KPG stirrer and reflux condenser 300 g (92 mmol of amine) of the amino-functional polydimethylsiloxane precursor from example 2 were initially charged and blanketed with nitrogen. At room temperature, 15.0 g of isotridecanol (available from ABCR GmbH, Karlsruhe) and 4.69 g (46 mmol) of propylene carbonate were added with stirring. The reaction mixture was heated to 80° C. and stirred at this temperature for 3 hours. The contents of the flask became clear upon attaining 75° C. An almost colorless, viscous oil having a viscosity of 9500 mP.Math.s and a residual amine content of 0.176 meq/g was obtained. Relative to the amino-functional precursor the derivatized product has several new signals in the .sup.29Si NMR spectrum at a chemical shift in the region of −13.8 ppm which are assignable to the terminal isotridecanol-bonded silicon atoms.
Example 8 (Production of an Emulsion From the Inventive Monohydroxyamidoamino-Functional Polydimethylsiloxane From Example 1)
[0170] 21.0 g of demineralized water, 12.0 g of tridecyl alcohol ethoxylate with 5 EO, 8.5 g of tridecyl alcohol ethoxylate with 8 EO (obtainable as LUTENSOL® TO 5 and LUTENSOL® TO 8 respectively from BASF SE, Ludwigshafen), 4.0 g of diethylene glycol monobutyl ether and 2.0 g of laureth-11 carboxylic acid (obtainable as Akypo RLM 100 from Kao Chemicals GmbH, Emmerich) were mixed in a laboratory dissolver (Dispermat CN 30 from VMA-Getzmann GmbH, Reichshof) at a speed of 800 rpm. 35.0 g of the monohydroxyamidoamino-functional polydimethylsiloxane from example 1 were then incorporated in three approximately equal portions at a speed of 1000 rpm. The thick, creamy mixture was diluted initially with 4.87 g and then with 12.5 g of demineralized water. The almost colorless microemulsion had a solids content of 62%, a pH of 6.0 and a turbidity of 4 ppm of SiO2.
Example 9 (Production of an Emulsion From the Inventive Monohydroxycarbamatoamino-Functional Polydimethylsiloxane From Example 2)
[0171] 35.0 g of the monohydroxycarbamatoamino-functional polydimethylsiloxane from example 2 were emulsified according to example 8 to afford an almost colorless microemulsion having a solids content of 61%, a pH of 6.0 and a turbidity of 1 ppm of SiO.sub.2.
Example 10 (Production of an Emulsion From the Noninventive Monohydroxyamidoamino-Functional Polydimethylsiloxane From Example 4)
[0172] 35.0 g of the acetamidoamino-functional polydimethylsiloxane from example 4 were emulsified according to example 8 to afford a yellow microemulsion having a solids content of 61%, a pH of 4.5 and a turbidity of 3 ppm of SiO.sub.2.
Example 11 (Production of an Emulsion From the Noninventive Pentahydroxyamidoamino-Functional Polydimethylsiloxane From Example 5)
[0173] 21.0 g of demineralized water, 12.0 g of tridecyl alcohol ethoxylate with 5 EO, 8.5 g of tridecyl alcohol ethoxylate with 8 EO and 2.0 g of laureth-11 carboxylic acid (obtainable as Akypo RLM 100 from Kao Chemicals GmbH, Emmerich) were mixed in a laboratory dissolver at a speed of 800 rpm. 35.0 g of the pentahydroxyamidoamino-functional polydimethylsiloxane from example 5 were then incorporated in three approximately equal portions at a speed of 1000 rpm. The highly viscous mixture was diluted initially with 4.87 g and then with 12.5 g of demineralized water. The turbid, viscous emulsion had a solids content of 62%, a pH of 5.5 and a turbidity of 250 ppm of SiO.sub.2. The missing proportion of diethylene glycol monobutyl ether was compensated by the increased proportion thereof in the pentahydroxyamidoamino-functional polydimethylsiloxane.
Example 12 (Production of an Emulsion From the Noninventive Dihydroxycarbamatoamino-Functional Polydimethylsiloxane From Example 6)
[0174] 35.0 g of the dihydroxycarbamatoamino-functional polydimethylsiloxane from example 6 were emulsified according to example 8 to afford a turbid emulsion having a solids content of 60%, a pH of 6.5 and a turbidity of 140 ppm of SiO.sub.2.
Example 13 (Production of an Emulsion From the Noninventive Monohydroxycarbamatoamino-Functional Polydimethylsiloxane From Example 7)
[0175] 35.0 g of the monohydroxycarbamatoamino-functional polydimethylsiloxane from example 7 were emulsified according to example 8 to afford an almost colorless but diffusely turbid emulsion having a solids content of 62%, a pH of 5.5 and a turbidity of 253 ppm of SiO2. Separation into 2 phases began after 3 weeks of storage.
Example 14 (Production of an Emulsion From the Amino-Functional Polydimethylsiloxane Raw Material From Examples 2 to 7; Softness Reference)
[0176] 21.0 g of demineralized water, 12.0 g of tridecyl alcohol ethoxylate with 5 EO, 8.5 g of tridecyl alcohol ethoxylate with 8 EO, 4.0 g of diethylene glycol monobutyl ether, 2.0 g of laureth-11 carboxylic acid and 0.32 g of glacial acetic acid were mixed in a laboratory dissolver at a speed of 800 rpm. 35.0 g of the low-cyclics silanol- and methoxy-terminated laterally aminoethylaminopropyl-functional polydimethylsiloxane raw material having a viscosity of 959 mPa.Math.s and an amine content of 0.306 meq/g from examples 2 to 7 were then incorporated in three approximately equal portions at a speed of 1000 rpm.
[0177] The thick, creamy mixture was diluted initially with 4.87 g and then with 12.5 g of demineralized water. The colorless, opalescent microemulsion had a solids content of 61%, a pH of 5.0 and a turbidity of 42 ppm of SiO2.
Example 15 (Production of a Silicone-Polyether Copolymer According to Example 4 in US 2008/0075683 A1 For Hydrophilic Reference Emulsion)
[0178] 635g of an α,ω-dihydrogenpolydimethylsiloxane with 0.052% by weight of Si-bonded hydrogen were mixed with 205 g of a polyether of formula H.sub.2C═CH—CH.sub.2—(OCH.sub.2CH.sub.2).sub.9,5—OH. The mixture was heated to 100° C. and 0.28 g of a 2.7% by weight (based on elemental platinum) solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in an α,ω-divinyldimethylpolysiloxane having a viscosity of 1000 mPa.Math.s at 25° C., a solution of the so-called Karstedt catalyst (the production of which is described in U.S. Pat. No. 3,775,452), was added to the mixture, whereupon the temperature of the reaction mixture increased by 19° C. and a clear product was formed. After one hour at 100° C. to 110° C. complete conversion of the Si-bonded hydrogen was achieved. The polyether-polysiloxane intermediate had an OH concentration of 0.512 meq/g and contained 177 ppm water.
[0179] 200 g of this intermediate were mixed with 10.3 g of bis(dimethylaminopropyl)amine and heated to 84° C.; 13.2 g of hexamethylene diisocyanate were added.
[0180] The ratio of the NCO groups to the sum of the organic functions reactive therewith was 0.998, and 0.97 including water.
[0181] Without further catalysis complete conversion of the isocyanate groups was achieved in one hour at about 90° C. by slightly exothermic reaction. The polymer blend contained 0.49 meq/g of basic nitrogen.
[0182] 32 g of this polymer was neutralized with a solution of 1.04 g of acetic acid in 8 g of diethylene glycol monobutyl ether.
Example 16 (Production of an Emulsion From the Silicone-Polyether Copolymer in Example 15; Hydrophilicity Reference)
[0183] 21.0 g of demineralized water, 12.0 g of tridecyl alcohol ethoxylate with 5 EO, 8.5 g of tridecyl alcohol ethoxylate with 8 EO and 2.0 g of laureth-11 carboxylic acid were mixed in a laboratory dissolver at a speed of 800 rpm. 35.0 g of the silicone-polyether copolymer from example 15 were then incorporated in three approximately equal portions at a speed of 1000 rpm. The flowable mixture was diluted initially with 4.87 g and then with 12.5 g of demineralized water. The milky emulsion had a solids content of 54% and a pH of 6.0.
Performance Tests
[0184] An untreated 100% CO interlock knitted fabric having a basis weight of 190 g/m.sup.2 was used for textile treatment.
[0185] A fabric padded with water and dried (=blank value) was used as a reference.
[0186] The fabric was impregnated with the respective liquor, squeezed off with a two-roll pad mangle to a wet pickup of 77%, stretched out and dried in a MATHIS laboratory tenter at 150° C. for three minutes. The fabric was then acclimatized for at least 12 hours in a conditioning chamber at 23° C. and 62% humidity.
[0187] Determination methods for results of the use examples:
[0188] Determination of softness(hand assessment):
[0189] Since the softness of textiles is strongly dependent on the subjective perception of the test persons, only the boundary conditions, but not the assessment, can be standardized. In order nevertheless to ensure reproducibility, the treated samples were assessed and ranked in terms of their softness. To this end points were awarded by four persons in accordance with the number of tested samples, wherein the magnitude of the score awarded correlates with softness. The softest sample receives the maximum score, while the least soft sample receives 0 points. The hand assessment of a sample is thus calculated as the average of the points awarded to this sample in each case.
[0190] Determination of droplet absorption time:
[0191] Following application of the silicone product the treated sample was stored for eight hours in a conditioning chamber at a temperature of 23° C. and an atmospheric humidity of 62% for accclimatization and then a droplet of deionized water was placed on the taut fabric surface from a height of 1 cm and the time taken for the fabric to absorb the water droplet was determined up to a maximum of three minutes (180 seconds).
[0192] Five determinations were performed and the average calculated.
[0193] Determination of washfastness:
[0194] To examine washfastness, all of the treated textiles were washed together with about 3 kg of ballast in a Siemens SIWAMAT 6143 domestic washing machine on the colors cycle at 60° C. and subjected to a spin at 1400 rpm. As the laundry surfactant, 36 g of Henkel “Spee Feincolor” liquid washing detergent were used. Altogether 2 washing cycles of 90 minute duration in each case were performed without intermediate drying. The fabric was then dried and acclimatized for at least 12 hours in a conditioning chamber at 23° C. and 62% humidity. The fabric samples were then re-subjected to a softness comparison.
[0195] The table below summarizes the results of the fabric treated using the padding process for several use examples.
TABLE-US-00001 TABLE Solids Usage Droplet Softness Softness Examples content amount test before after 2 and comparison in [%] in [g/l] in [s] washing washes Example 8 62 10.0 4 4.75 5.13 Example 9 61 10.0 3 5.25 5.62 Example 10 61 10.0 17 4.25 4.63 (Comparison) Example 11 62 10.0 28 2.88 3.50 (Comparison) Example 12 60 10.0 16 3.25 3.87 (Comparison) Example 13 62 10.0 9 3.62 4.25 (Comparison) Example 14 61 10.0 85 7.75 8 (hand reference) Example 16 54 11.3 1 4.25 1 (hydrophilicity reference) Blank value 0 0 0
[0196] The textiles treated according to the invention with monohydroxyamido- or monohydroxycarbamato-containing amino-functional polydimethylsiloxanes (derivatization with γ-butyrolactone and propylene carbonate, examples 8 and 9 respectively) show a markedly shorter droplet absorption time compared to textiles treated with acetamido-, pentahydroxyamido and dihydroxycarbamato-containing amino-functional polydimethylsiloxanes (derivatization with acetic anhydride, gluconolactone and glycerol carbonate, comparative examples 10, 11 and 12 respectively) and to underivatized amino-functional polydimethylsiloxanes (comparative example 14). A person skilled in the art would expect that due to a higher proportion of hydroxy groups, more polar functional groups should provide the fibrous substrates with more hydrophilic properties. However, it is surprisingly the inventive monohydroxy-containing derivatives that are most hydrophilic in the group of non-polyether-containing amino-functional polydimethylsiloxanes. In addition to a clearer appearance and better stability, the emulsion of the inventive diethylene glycol monobutyl ether-terminated monohydroxycarbamato-containing amino-functional polydimethylsiloxane (example 9) also has hydrophilicity advantages compared to the comparable but noninventive emulsion of the isotridecanal-terminated polydimethylsiloxane oil (comparative example 13). Compared to the silicone-polyether copolymer produced by hydrosilylation and isocyanate bridging (comparative example 16), the inventive monohydroxy-containing aminosilicone derivatives (examples 8 and 9) are very washfast in terms of softness despite featuring good hydrophilic properties. The purely amino-functional hand reference (comparative example 14) has very good softness properties before and after washing but cannot be employed in hydrophilic treatment.
[0197] As shown by examples 1 to 4 and as opposed to noninventive acetamido-containing aminosilicone derivatives (comparative example 4) the inventive aminohydroxy-containing aminosilicone-derivatives of examples 1 to 3 do not re-form higher amounts of D4 cyclics in demanding storage at 50° C., so that good storage stability in respect of low-cyclics properties and accordingly unnecessary SVHC (substances of very high concern) classifications can be assumed. The viscosities of the inventive derivatives of amino-functional polydimethylsiloxanes are all in the range below 5000 mPa.Math.s at 25° C.