OEM TEXTILE FINISHING COMPOSITIONS

Abstract

Crosslinked aminosiloxanes obtainable by reaction of identical or different aminosiloxanes with identical or different epoxide components which are water-soluble hydrocarbons, the hydrocarbons comprising oxygen as well as carbon, and optionally further elements selected from nitrogen, sulphur and phosphorus, the hydrocarbon having on average more than one terminal epoxy group, the epoxy group being a carbooxirane radical, and, further, not more than 50% of all the amino groups having undergone reaction with an epoxide group.

Claims

1. A crosslinked aminosiloxane obtainable by reaction of identical or different amine-substituted siloxanes with identical or different epoxide components which are water-soluble hydrocarbons, the hydrocarbons comprising oxygen and carbon, the hydrocarbon having on average more than one terminal epoxy group, the epoxy group being a carbooxirane radical, and, further, not more than 50% of all the amino groups having undergone reaction with an epoxide group.

2. The crosslinked aminosiloxane according to claim 1, wherein the amine-substituted siloxanes conform to the formula (I)
MaMAbDcDAdTeTAfQg  (I) where M=[R13SiO1/2] MA=[R2R12SiO1/2] D=[R12SiO2/2] DA=[R2R1SiO2/2] T=[R1SiO3/2] TA=[R2SiO3/2] Q=[SiO4/2], where R1 independently at each occurrence is identical or different, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 30 carbon atoms or else aromatic hydrocarbon radicals having 6 to 30 carbon atoms, R2 independently at each occurrence is a hydrocarbon radical which is substituted by at least one nitrogen atom and has 1 to 30 carbon atoms, a=0 to 20, b=0 to 10, c=10 to 5000, d=0 to 50, e=0 to 20, f=0 to 500, g=0 to 20.

3. The crosslinked aminosiloxane according to claim 1, wherein the epoxide components are water-soluble hydrocarbons, the hydrocarbons comprising oxygen as well as carbon, the hydrocarbon having at least one chain which in turn has at least two oxygen atoms separated by at least one carbon atom, and the hydrocarbon having on numerical average more than one terminal epoxy group.

4. The crosslinked aminosiloxane according to claim 1, wherein the epoxide components are epoxy-substituted polyethers of the formula (II)
R3-X-M1h-M2j-M3k-M4l-M5m-R3  (II) h=greater than 0 to 50; j=0 to 10; k=0 to 10; l=greater than 1 to 10; m=0 to 10; where the sum of the indices h, j, k, l+m is at least 3, X=oxygen, R3=independently at each occurrence hydrogen, a hydrocarbon having 1 to 8 carbon atoms, and/or the gycidyl radical M1=, M2=and/or M3=, where in M3, the radicals X1 to X4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 up to 50 C atoms, with the proviso that X1 to X4 are not selected such that M3 is the same as M1 or M2, M4=and/or where R4 in M4 independently at each occurrence is a hydrocarbon radical having 2 to 20 carbons, and may be interrupted by heteroatoms, preferably M4 is a glycidyl ether=, M5= where R5 in M5 independently at each occurrence is not present or is a divalent hydrocarbon having 1 to 10 carbon atoms.

5. The crosslinked aminosiloxane according to claim 1, wherein the epoxy-substituted polyethers of the formula (II) have a molar mass of 200 to 1500 g/mol.

6. The crosslinked aminosiloxane according to claim 1, wherein the epoxy-substituted polyethers of formula (II) are colorless.

7. The crosslinked aminosiloxane according to claim 1, wherein the crosslinked aminosiloxanes have less than 10 wt %, but at least 0.01 wt %, polyether fraction.

8. The crosslinked aminosiloxane according to claim 1, wherein at least 50% of the primary amino groups of the crosslinked siloxanes have not undergone reaction by crosslinking with epoxide groups.

9. The process for preparing the crosslinked aminosiloxane according to claim 1.

10. A composition comprising the crosslinked aminosiloxane of claim 1.

11. The composition according to claim 10, wherein they comprise from 0.1 wt % to 5 wt %, based on the mass of the crosslinked aminosiloxane, of an acid.

12. A formulation comprising the composition according to claim 10, wherein the formulation is emulsifier-free.

13. A household product including fabric softener and hair conditioner wherein the household product comprised the crosslinked aminosiloxane of claim 1.

14. The crosslinked aminosiloxane according to claim 1 wherein the hydrocarbons may further consist of elements selected from the group consisting of nitrogen, sulphur and phosphorus.

15. The crosslinked aminosiloxane according to claim 1 wherein the epoxide components the hydrocarbon having at least one chain which in turn has at least two oxygen atoms separated by at least two carbon atoms, and the hydrocarbon having on numerical average more than two terminal epoxy groups.

16. The crosslinked aminosiloxane according to claim 1, wherein the epoxide components are epoxy-substituted polyethers of the formula (II)
R3-X-M1h-M2j-M3k-M4l-M5m-R3  (II) h=from 4 to 15; j=0 to 5; k=0; l=from 2 to 5; m=0; where the sum of the indices h, j, k, l+m is at least 5, X=oxygen, R3=independently at each occurrence hydrogen, a hydrocarbon having 1 to 8 carbon atoms, and/or the gycidyl radical M1=, M2=and/or M3=, where in M3, the radicals X1 to X4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 2 up to 20 C atoms, with the proviso that X1 to X4 are not selected such that M3 is the same as M1 or M2, M4=and/or where R4 in M4 independently at each occurrence is a hydrocarbon radical having 2 to 20 carbons, and may be interrupted by heteroatoms, preferably M4 is a glycidyl ether=, M5= where R5 in M5 independently at each occurrence is not present or is a divalent hydrocarbon having 1 to 6 carbon atoms.

17. The crosslinked aminosiloxane according to claim 2, wherein the epoxide components are epoxy-substituted polyethers of the formula (II)
R3-X-M1h-M2j-M3k-M4l-M5m-R3  (II) h=from 4 to 15; j=0 to 5; k=0; l=from 2 to 5; m=0; where the sum of the indices h, j, k, l+m is at least 5, X=oxygen, R3=independently at each occurrence hydrogen, a hydrocarbon having 1 to 8 carbon atoms, and/or the gycidyl radical M1=, M2=and/or M3=, where in M3, the radicals X1 to X4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 2 up to 20 C atoms, with the proviso that X1 to X4 are not selected such that M3 is the same as M1 or M2, M4=and/or where R4 in M4 independently at each occurrence is a hydrocarbon radical having 2 to 20 carbons, and may be interrupted by heteroatoms, preferably M4 is a glycidyl ether=, M5= where R5 in M5 independently at each occurrence is not present or is a divalent hydrocarbon having 1 to 6 carbon atoms.

18. The crosslinked aminosiloxane according to claim 3, wherein the epoxide components are epoxy-substituted polyethers of the formula (II)
R3-X-M1h-M2j-M3k-M4l-M5m-R3  (II) h=from 4 to 15; j=0 to 5; k=0; l=from 2 to 5; m=0; where the sum of the indices h, j, k, l+m is at least 5, X=oxygen, R3=independently at each occurrence hydrogen, a hydrocarbon having 1 to 8 carbon atoms, and/or the gycidyl radical M1=, M2=and/or M3=, where in M3, the radicals X1 to X4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 2 up to 20 C atoms, with the proviso that X1 to X4 are not selected such that M3 is the same as M1 or M2, M4=and/or where R4 in M4 independently at each occurrence is a hydrocarbon radical having 2 to 20 carbons, and may be interrupted by heteroatoms, preferably M4 is a glycidyl ether=, M5= where R5 in M5 independently at each occurrence is not present or is a divalent hydrocarbon having 1 to 6 carbon atoms.

19. The crosslinked aminosiloxane according to claim 1, wherein the epoxide components are epoxy-substituted polyethers of the formula (II)
R3-X-M1h-M2j-M3k-M4l-M5m-R3  (II) h=from 4 to 15; j=from 0 to 2; k=0; l=from 2 to 5; m=0; where the sum of the indices h, j, k, l+m is at least 7, X=oxygen, R3=independently at each occurrence hydrogen, a hydrocarbon having 1 to 8 carbon atoms, and/or the gycidyl radical M1=, M2=and/or M3=, where in M3, the radicals X1 to X4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 2 up to 20 C atoms, and contain halogen atoms, with the proviso that X1 to X4 are not selected such that M3 is the same as M1 or M2, M4=and/or where R4 in M4 independently at each occurrence is a hydrocarbon radical having 2 to 20 carbons, and may be interrupted by heteroatoms, preferably M4 is a glycidyl ether=, M5= where R5 in M5 independently at each occurrence is not present or is a divalent hydrocarbon having from 2 to 4 carbon atoms.

20. The crosslinked aminosiloxane according to claim 2, wherein the epoxy-substituted polyethers of the formula (II) have a molar mass of 200 to 1500 g/mol.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0106] FIG. 1: Schematic representation of elongation in accordance with ISO 13936. The line in the middle is the seam; the direction of tension is vertical.

EXAMPLES

General Methods and Materials

Spectroscopic Analyses:

[0107] The chain length of the crosslinked aminosiloxanes and of the amino-substituted siloxanes was determined using .sup.29Si NMR. The recording and interpretation of NMR spectra is known to the skilled person. References include the book “NMR Spectra of Polymers and Polymer Additives”, A. Brandolini and D. Hills, 2000, Marcel Dekker, Inc. The spectra were recorded at room temperature with a Bruker Spectrospin spectrometer, with measurement frequencies when recording the proton spectra of 399.9 MHz, when recording the .sup.13C spectra of 100.6 MHz and when recording the .sup.29Si spectra of 79.5 MHz.

[0108] Determination of molar masses, in particular the weight-average molar masses Mw:

[0109] The gel permeation chromatographic analyses (GPC) were performed with a type 1100 instrument from Hewlett-Packard using an SDV column combination (1000/10000 Å, each 65 cm, internal diameter 0.8 cm, temperature 30° C.), THF as mobile phase with a flow rate of 1 ml/min and an RI detector (Hewlett-Packard). The system was calibrated against a polystyrene standard in the range from 162 to 2 520 000 g/mol for the determination of the molar masses of the crosslinked aminosiloxanes and of the amino-substituted siloxanes, and against a polypropylene glycol standard in the range from 162 to 2 520 000 g/mol for determining the molar masses of the epoxide components.

[0110] The nitrogen content is determined by potentiometric titration in a method based on DIN EN ISO 9702. The total nitrogen was determined as per 2.1.1, and the sum total of secondary and tertiary nitrogen was determined as per 2.2.3, and the primary nitrogen was calculated from these results by formulation of the difference. The aprotic solvent used was dioxane, and the acid was perchloric acid.

[0111] The viscosity is determined using a rotary viscometer according to DIN 53018 Part 1 in a plate/plate method. An ES-CPS-Plus rheometer from Brookfield was used, with the RP 75 measuring plate, gap width 1 mm. The measurements were conducted at 25° C.

Example 1: Synthesis

[0112] 1.1: Preparation of Amino-Substituted Siloxanes in Accordance with DE 102011110100 A1

[0113] The preparation of amino-substituted siloxanes was carried out in accordance with DE 102011110100. The amounts of each of the raw materials used are derived directly from the stoichiometry of the polymer composition. Figures in wt % are always based on the sum total of all the initial masses.

[0114] In a four-necked round-bottomed flask equipped with stirrer, internal thermometer and distillation bridge, dihydroxy-functional polydimethylsiloxane with known chain length, determined by .sup.29Si NMR, hexamethyldisilazane and 0.07 wt % of an 85 percent strength by weight phosphoric acid are heated with stirring for 85° C. and stirred at that temperature for 30 minutes. Then aminopropylmethyl diethoxysilane and a further 0.07 wt % of an 85 percent strength by weight phosphoric acid are added, and the mixture is distilled at 85° C. at 14 to 20 mbar for an hour, and also at 120° C. for a further 2 hours. Filtration through a pressure filter press produces transparent, colorless aminopropylsiloxanes. Examples are reported in Table 1.

TABLE-US-00001 TABLE 1 Aminopropylsiloxanes of Example 1.1; the chain length relates to the number of siloxane units Mw Aminopropylsiloxane Chain length Nitrogen, [wt %] [g/mol] AS1 81 0.32 12628 AS2 210 0.76 35665 AS3 246 0.73 45462 AS4 202 0.98 40090 AS5 75 0.98 11147 AS6 68 1.00 11818 AS7 75 0.32 12618 AS8 216 0.93 45710 AS9, not inventive 277 0.39 36163

1.2: Preparation of Inventive Crosslinked Aminosiloxanes

[0115] An aminopropylsiloxane is charged to a four-necked round-bottomed flask equipped with stirrer, internal thermometer and distillation bridge and is admixed with 20 wt % of 2-propanol and also with the epoxide component in the amount required in each case according to Table 2. The quantity figures in wt % relate to the sum total of the initial masses of aminosiloxane, solvent and epoxide component. The sum total makes up 100 wt %.

[0116] The charge is heated to 80° C. with stirring and is stirred at this temperature for 6 hours. Following removal of the solvent by distillation at 80° C. under a reduced pressure of <20 mbar, the crosslinked aminopropylsiloxanes are obtained. Examples are set out in Table 2.

TABLE-US-00002 TABLE 2 Crosslinked aminopropylsiloxanes of Example 1.2 Amino- Crosslinked substituted Epoxide component 1 * Nitrogen [wt %] Mw aminosiloxane siloxane [wt %] primary tertiary [g/mol] HS1 AS3 0.67 0.72 108776 HS2 AS5 3.22 n.d. 144311 HS3 AS1 1.07 0.29 0.02 17463 HS4 AS6 0.68 0.99 50264 HS5 AS7 2.61 0.28 0.04 31289 HS6 AS8 0.87 0.88 244066 HS7 AS8 0.44 0.89 86860 HS8 AS9 1.2 0.38 0.01 76978 [00007]

[0117] From the values reported it is apparent that at least 80% of the primary amino groups were still present unchanged after the reaction with the epoxy compound.

Example 2: Compositions and Formulations

[0118] Typical compositions of the invention contain 20 wt % of crosslinked aminosiloxane, 15 wt % of diethylene glycol monobutyl ether (BDG), 0.3 wt % of an organic acid and 64.7 wt % of water.

[0119] The compositions are prepared by simple stirring together at room temperature. Stirring is continued until the mixture is a homogeneous single-phase mixture, i.e. has no visible second phase. In general the formulations are homogeneous within 10 minutes of stirring. Depending on the viscosity of the crosslinked aminosiloxane, a KPG stirrer is used, or a magnetic stirrer is sufficient. The compositions of the invention are clear, transparent or else milkily turbid.

[0120] They remain homogeneous after the stirrer is shut off, and exhibit neither phase separation nor yellowing even on two-week storage at 22° C.

[0121] In a formulation of this kind, non-inventive aminosiloxanes, not hydrophilized by crosslinking, exhibit rapid phase separation since they lack the emulsifier.

TABLE-US-00003 TABLE 3 Formulations of Table 2 of the crosslinked aminosiloxanes of Example 1.2, all containing 15 wt % BDG and 64.7 wt % water Crosslinked aminosiloxane Acid Formulation [wt %] [wt %] Appearance acetic acid FHS1 20 (HS1) 0.3 clear, homogeneous, colorless FHS2 20 (HS2) 0.3 turbid, homogeneous, colorless FHS3 20 (HS3) 0.3 turbid, homogeneous, colorless FHS4 20 (HS4) 0.3 turbid, homogeneous, colorless FHS5 20 (HS5) 0.3 slightly turbid, homogeneous, colorless FHS6 20 (HS6) 0.3 clear, homogeneous, colorless FHS7 20 (HS7) 0.3 clear, homogeneous, colorless FHS8 20 (HS8) 0.3 turbid, homogeneous, colorless lactic acid FHS9* 20 (HS1) 0.3 clear, homogeneous, colorless glycolic acid FHS10 20 (HS1) 0.3 clear, homogeneous, colorless *FHS9 was prepared by stirring at 50° C.

[0122] The formulations were tested for their dilutability with water, by the addition to 1 g of the formulation of 6 g of water, followed by brief stirring together with a magnetic stirrer. The appearance was tested for homogeneity, and remains comparable in all cases with the appearance of the concentrated formulation from Table 3.

TABLE-US-00004 TABLE 4 Water-dilutability of the formulations from Table 3 Starting formulation Appearance FHS1 clear, homogeneous, colorless FHS2 turbid, homogeneous, colorless FHS4 turbid, homogeneous, colorless FHS5 slightly turbid, homogeneous, colorless FHS6 clear, homogeneous, colorless FHS7 clear, homogeneous, colorless FHS8 slightly turbid, homogeneous, colorless

[0123] Phase separation was not observed for any of the formulations of Example 2.

Example 3: Application Tests

Pretreatment of the Test Fabric:

[0124] The standard fabric is first of all pretreated. It is washed initially once with 32 g of test detergent, and then once without test detergent.

[0125] The washing operations took place in a commercial Miele Novotronic W 918 washing machine with colored laundry, without prewashing at 40° C., using wfk standard laundry detergent IECA-Base and 3 kg of cotton ballast fabric. Lastly, the fabric thus treated was dried at room temperature for 12 hours. The test fabrics are cut into pieces measuring 30×40 cm.

A1:

[0126] For the testing, polyester fabrics from wfk Testgewebe GmbH (Christenfeld 10 41379 Brüggen) with wfk code 30A, basis weight 170 g/m.sup.2, woven goods with 1/1 weave and three dyed taffetas (woven polyester goods with 1/1 weave) with different basis weights were used, and were immersed at 25° C. in a 0.08% (based on active substance) liquor with a liquor-to-goods ratio of 12 to 1 for 20 minutes with gentle mixing, after which they were wrung out gently and dried in a Matthis Labdryer LTE. The drying conditions were 2 minutes at 105° C. followed by 1 minute at 180° C.

[0127] Compositions FHS1 to FHS8 were diluted with cold mains water to form a rinsing solution which contains 0.08 wt % of inventive compound.

[0128] Comparative samples were conducted using alternative softeners, a non-crosslinked amino silicone AS9 (Table 1) (Comparative 2) and a linearly polymerized ABn silicone (Momentive SRS, molar mass about 50 000 g/mol) (Comparative 1) in the same way as for the inventive experiments.

V1, Soft Hand:

[0129] To assess the soft hand, an experienced team of eight individual testers was assembled, who used a hand panel test to evaluate the anonymized hand specimens of the polyester fabrics finished using the formulations. In this test, each tester receives their own cloth. For the hand specimens, additionally, an untreated sample without obvious marking (blank value) was always added on.

[0130] Assessment took place on a scale from 0 (hard and unpleasant to handle) to 5 (soft and pleasant to handle) with the possibility of whole-number values in between. For the assessment of the soft hand, the individual evaluations were added up, meaning that, with 8 testers, a maximum soft hand value of 40 was possible. The results are listed in Table #5. Not all of the compositions were tested.

TABLE-US-00005 TABLE #5 Soft hand assessment of Example 3 after application A1 of the compositions of Example 2 to knitted polyester goods Soft hand/material PES black PES blue PES red Composition 210 g/m.sup.2 170 g/m.sup.2 170 g/m.sup.2 PES Wfk FHS 1 20.5 12 17 32 FHS 2 23 29 FHS 3 35 37 FHS 4 17 30.5 29 FHS 5 24 FHS 7 26 21 18.5 24 FHS 8 28 14.5 37 Comparative 1 20 28 24 32 Comparative 2 19 21 26.5 29

[0131] The inventive compositions are comparable with the prior art.

V2: Deformation

[0132] Tensile tests with samples of woven fabric (A1) were carried out according to ISO 13936. The material used was exclusively taffeta. The tensile tests were carried out in the direction of the warp threads. In the diagrams, the warp threads run vertically. Samples were pretreated according to A1 and then two pieces were stitched together with the test thread.

[0133] The seam width in the tensile test of the untreated sample is on average 2 mm across the entire breadth, with an applied force of 120 N. The average values after application of the inventive compositions are reported in Table #6.

TABLE-US-00006 TABLE #6 Tensile test according to V2, ISO 13936 Part 1, force at defined seam opening (weft thread): Formulation Seam opening (weft) [mm] Force [N] untreated 2 120 FHS1 6 120 FHS4 5 120 FHS6 5 120 FHS8 5 120 Comparative 1 6 120 Comparative 2 7 120

[0134] Table #7 shows the force values needed for a seam opening of 6 mm. Since the maximum force was 199 N, the value of the untreated sample shows only a seam opening of 2.9 mm.

TABLE-US-00007 TABLE #7 Tensile test according to V2, ISO 13936 Part 2, force at defined seam opening (weft thread): Formulation Seam opening (weft) [mm] Force [N] untreated 2.9 199 FHS1 6 199 FHS4 6 199 FHS6 6 199 FHS8 6 199 Comparative 1 6 164 Comparative 2 6 143

[0135] Advantageous values are a smaller seam opening for a given force and/or a greater force for a given seam opening. In both cases it is apparent that the deformation after inventive finishing was better than after application of the comparative compositions of the prior art.

V3: Heat Resistance:

[0136] Samples of Example 2 (Table 3) were adjusted at room temperature to a pH of between 4 and 4.5, with addition of acetic acid where necessary, and were stirred gently with a double-paddle stirrer. The temperature was raised to 100° C. for 30 minutes, after which the samples were cooled to room temperature. The stirrer was shut off and the sample was left to stand at rest for 10 minutes, after which it was inspected.

[0137] All inventive samples show no signs of phase separation, and in particular do not exhibit any droplet formation at the meniscus with the glass wall. The non-crosslinked amino silicone (corresponding to Comparative 2) exhibited droplet formation after treatment above.