Functional thermo-regulating textile additives and uses thereof
11486087 · 2022-11-01
Assignee
Inventors
Cpc classification
International classification
Abstract
Provided herein is a formulation containing a PPG/PEG block-copolymer (I) on average having PEG-blocks in the range of 37-45 terminated on both sides with on average in the range of 6-11 PPG blocks. The PPG/PEG block-copolymer can be end capped with hydrocarbon systems like for example n-butyl. The PPG/PEG block-copolymer (I) is chosen to have a DSC-melting point according to DIN ISO 11357 in the range of 15-37° C. to provide for a cool touch effect and can be applied without encapsulation. Furthermore uses of such a formulation and textiles treated with such a formulation are proposed.
Claims
1. A textile treatment formulation comprising a PPG/PEG block-copolymer of Formula (I) or a mixture thereof: ##STR00002## wherein an average value of x is in a range of 38-42; an average value of y is in a range of 6-11, wherein a value of y in the left and in the right structural moiety as represented above can be different but within that range; R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, and saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, and sulfur; and wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point (peak value) according to DIN ISO 11357 in a range of 15-37° C.
2. The textile treatment formulation according to claim 1, wherein the average value of y is in the range of 7-10.
3. The textile treatment formulation according to claim 1, wherein R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, and saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-6 carbon atoms.
4. The textile treatment formulation according to claim 1, wherein R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen and n-butyl.
5. The textile treatment formulation according to claim 1, wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point according to DIN ISO 11357 in the range of 20-35° C., and/or wherein the onset of the peak in the DSC is below 0° C., and/or wherein the end of the peak in the DSC is below 50° C., and/or wherein the full width at half height of the peak is smaller than 20° C., and/or wherein the peak in the DSC is bimodal or monomodal.
6. The textile treatment formulation according to claim 1, wherein the total average molecular weight of the PPG/PEG block-copolymer of Formula (I) is in the range of 2500-3200 Da.
7. The textile treatment formulation according to claim 1, wherein the PPG/PEG block-copolymer of Formula (I) is present in the formulation in an unencapsulated form.
8. The textile treatment formulation according to claim 1, wherein the PPG/PEG block-copolymer of Formula (I) is present in the formulation in a concentration in the range of 50-850 g/l, and/or wherein the formulation is free from curing agents so that after drying of a correspondingly coated fiber no curing step is necessary.
9. A method of using a formulation according to claim 1 or of using a treatment liquor comprising a formulation according to claim 1 for coating of fibers and/or textiles, comprising coating fibers or textiles with the formulation or the treatment liquor.
10. The method according to claim 9, wherein before treatment with the formulation, the fibers and/or textiles are treated with a softener formulation and/or cationic fixer formulation.
11. A method of treating fibers and/or textiles, comprising applying a textile treatment formulation according to claim 1 or a treatment liquor comprising a formulation according to claim 1 to fibers and/or textiles.
12. The method according to claim 11, wherein the fibers and/or textiles are treated for 10 to 40 minutes at a temperature in the range of 20 to 60° C. or by forced application.
13. The method according to claim 11, wherein subsequent to the treatment with the formulation according to claim 1, the fibers and/or textiles are dried and subjected to at least one of the following post-treatments after drying: compacting, calendaring, decatizing, raising, emerizing, and condensation of crosslinkers or self-cros slinking polymers.
14. A fiber or textile treated with a formulation according to claim 1.
15. The textile treatment formulation according to claim 1, wherein the average value of x is in the range of 39-41.
16. The textile treatment formulation according to claim 1, wherein the average value of y is in the range of 8-9, and wherein the values of y in the left and in the right structural moiety as represented above are the same.
17. The textile treatment formulation according to claim 1, wherein x is 41 and y is 9.
18. A textile treatment formulation comprising a PPG/PEG block-copolymer of Formula (I) or a mixture thereof: ##STR00003## wherein an average value of x is in a range of 27-63; an average value of y is in a range of 6-11, wherein a value of y in the left and in the right structural moiety as represented above can be different but within that range; R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, and saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, and sulfur; wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point (peak value) according to DIN ISO 11357 in a range of 15-37° C., and wherein R′ and R″ are selected from the group consisting of: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3- methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, and 2,2-dimethylpropyl.
19. The textile treatment formulation according to claim 18, wherein the average value of x is in the range of 38-42.
20. The textile treatment formulation according to claim 1, wherein R′ is selected to be n-butyl and R″ is selected to be hydrogen.
21. The textile treatment formulation according to claim 1, wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point according to DIN ISO 11357 in the range of 25-33° C., and/or wherein the end of the peak in the DSC is below 45° C.; and/or wherein the full width at half height of the peak is smaller than 15° C.
22. A textile treatment formulation comprising a PPG/PEG block-copolymer of Formula (I) or a mixture thereof: ##STR00004## wherein an average value of x is in a range of 27-63; an average value of y is in a range of 6-11, wherein a value of y in the left and in the right structural moiety as represented above can be different but within that range; R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, and saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, and sulfur; wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point (peak value) according to DIN ISO 11357 in a range of 15-37° C., and wherein the total average molecular weight of the PPG/PEG block-copolymer of Formula (I) is in the range of 2750-3000 Da, and wherein when R′ is selected to be n-butyl and R″ is selected to be hydrogen, the average molecular weight is in the range of 2750-2950 Da, and when R′=R″ and selected to be n-butyl the average molecular weight is in the range of 2800-3000 Da.
23. The textile treatment formulation according to claim 1, wherein the PPG/PEG block-copolymer of Formula (I) is present in the formulation, in the form of an aqueous dispersion and/or solution, in a concentration in the range of 100-810 g/l.
24. The method according to claim 9, wherein the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and/or blend thereof, to impart a cool touch effect.
25. The method according to claim 9, wherein before treatment with the formulation, the fibers and/or textiles, comprise cotton and are treated with a softener formulation and/or cationic fixer formulation, based on quaternary polyamine systems.
26. The method according to claim 11, wherein the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and/or blend thereof.
27. The method according to claim 11, wherein the fibers and/or textiles are treated during a time span of 15 to 30 minutes, at a temperature in the range of 30 to 50° C.
28. The fiber or textile according to claim 14, wherein the fiber or textile is in the form of a garment, or article of clothing.
29. A textile treatment formulation comprising a PPG/PEG block- copolymer of Formula (I) or a mixture thereof: ##STR00005## wherein an average value of x is in a range of 27-63; an average value of y is in a range of 6-11, wherein a value of y in the left and in the right structural moiety as represented above can be different but within that range; R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, and saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, and sulfur; with the proviso that both R′ and R″ cannot at the same time be selected as hydrogen; and wherein the PPG/PEG block-copolymer of Formula (I) has a DSC-melting point (peak value) according to DIN ISO 11357 in a range of 15-37° C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
DESCRIPTION OF PREFERRED EMBODIMENTS
(10) Preferred embodiments of the invention are described in the following with reference to the examples, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same.
(11) Experiments 1:
Formulation 1 (Comparative Example)
(12) 800 g of a PPG/PEG block-copolymer of 20EO-17PO-20EO, molten at 40° C., is added to 200 g of warm (25 to 30° C.) water. After stirring a homogeneous, transparent solution is obtained. The DSC of the PPG/PEG block-copolymer of 20EO-17PO-20EO as such is given in
Formulation 2
(13) 800 g of a PPG/PEG block-copolymer of 9PO-41EO-9PO (corresponding essentially to a Meroxapol 106), molten at 40° C., is added to 200 g of warm (25 to 30° C.) water. After stirring a homogeneous, transparent solution is obtained. The DSC of the PPG/PEG block-copolymer of 9PO-41EO-9PO as such is given in
Formulation 3
(14) 800 g of a PPG/PEG block-copolymer of 9PO-41EO-9PO (corresponding essentially to a Meroxapol 106), one side end-capped with butanol, molten at 40° C., is added to 200 g of warm (25 to 30° C.) water. After stirring a homogeneous, transparent solution is obtained. The DSC of the PPG/PEG block-copolymer of 9PO-41EO-9PO one side end-capped with butanol as such is given in
Formulation 4
(15) 600 g of Formulation 2 is added to 400 g of a low formaldehyde glyoxal resin of 60% solid content. After stirring a homogeneous, transparent solution is obtained.
Formulation 5
(16) 700 g of Formulation 2 is added to 300 g of a blocked isocyanate emulsion. After stirring a homogeneous, white solution/emulsion is obtained.
(17) Textile Treatment 1:
(18) A polyester woven fabric is padded with a treatment liquor containing 150 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. No cool touch feel is obtained (−/o on a scale of −−/−/o/+/++).
(19) Textile Treatment 2:
(20) A polyester woven fabric is padded with a treatment liquor containing 150 g/l Formulation 2 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. A strong cool touch feel is obtained (++ on a scale of −−/−/o/+/++).
(21) Textile Treatment 3:
(22) A polyester knitted fabric is padded with a treatment liquor containing 150 g/l Formulation 3 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. A strong cool touch feel is obtained (+/++ on a scale of −−/−/o/+/++).
(23) Textile Treatment 4:
(24) T-shirts made of polyester are immersed in a treatment liquor containing 15% Formulation 2 and 0.3 mill acetic acid 25% and treated at 40° C. for 20 minutes and a liquor ratio of 1 to 8. Then the T-shirts are hydroextracted and dried at 80° C. in a tumble drier. A very strong cool touch feel is obtained (++ on a scale of −−/−/o/+/++).
(25) Textile Treatment 5:
(26) A cotton knitted fabric is padded with a treatment liquor containing 150 g/l Formulation 2 and 1 ml/l acetic acid 25%, squeezed to 65% pick-up and dried for 2 minutes at 120° C. No cool touch feel is obtained (−/o on a scale of −−/−/o/+/++).
(27) Textile Treatment 6:
(28) A cotton knitted fabric that has been treated with 4% quaternary polyamine fixative (Hydrocol SUN, Rudolf Chemie, Geretsried, Germany) at 40° C. for 30 minutes at a pH of 4 and a liquor ratio of 1:8, rinsed, hydroextracted and dried at 120° C. for 2 minutes, is padded with a treatment liquor containing 150 g/l Formulation 2 and 1 ml/l acetic acid 25%, squeezed to 65% pick-up and dried for 2 minutes at 120° C. A cool touch feel is obtained (+/++ on a scale of −−/−/o/+/++).
(29) Textile Treatment 7:
(30) A cotton knitted fabric is padded with a treatment liquor containing 150 g/l Formulation 3 and 1 ml/l acetic acid 25%, squeezed to 65% pick-up and dried for 2 minutes at 120° C. A strong cool touch feel is obtained (+/++ on a scale of −−/−/o/+/++).
(31) Textile Treatment 8:
(32) A cotton woven fabric is padded with a treatment liquor containing 250 g/l Formulation 3, 25 g/l Magnesium chloride hexahydrate, 20 g/l silicone microemulsion softener (HeiQ Soft CSE) and 1 ml/l acetic acid 25%, squeezed to 65% pick-up and dried for 2 minutes at 120° C. and cured for 5 min at 150° C. A strong cool touch feel is obtained (+/++ on a scale of −−/−/o/+/++).
(33) The fabric is washed 5 and 10 times as per ISO 6330:2012 4N (40° C. wash with mechanic), line dried; then the cool effect is checked again and is still present (+/++ resp. + on a scale of −−/−/o/+/++).
(34) Textile Treatment 9:
(35) A cotton woven fabric is padded with a treatment liquor 200 g/l Formulation 3, 20 g/I silicone microemulsion softener (HeiQ Soft CSE) and 1 ml/l acetic acid 25%, squeezed to 65% pick-up and dried for 2 minutes at 120° C. and cured for 2 min at 160° C. A strong cool touch feel is obtained (+/++ on a scale of −−/−/o/+/++).
(36) The fabric is washed 5 and 10 times as per ISO 6330:2012 4N (40° C. wash with mechanic), line dried; then the cool effect is checked again and is still present (+/++ resp. + on a scale of −−/−/o/+/++).
(37) The measurements were taken in accordance with the following standard and on the following test specimens.
(38) The melting points (Tm) were determined to ISO 11357. The heating rate used for differential scanning calorimetry (DSC) was 10K/min. The temperature for the maximum peak is specified for the melting point (Tm).
(39) Cool-touch effect: the effect was determined using hand feel. Surprisingly the melting effect seen in the DSCs of the products alone or even applied on polyester garments does not correlate to the hand feel! On cellulose fibers no effect was noticeable with DSC at all.
(40) Experiments 2:
(41) Formulation 1 (Concentrated Version):
(42) 800 g of a PPG/PEG block-copolymer of 9PO-41EO-9PO (corresponding essentially to a Meroxapol 106), one side end-capped with butanol (=Adaptive AC-06 AS; AS=Active Substance), molten at 40° C., is added to 200 g of warm (25 to 30° C.) water. After stirring a homogeneous, transparent solution is obtained.
(43) Formulation 2 (Diluted Version=Adaptive AC-06):
(44) 250 g of Formulation 1 is added to 748.5 g of demineralized water, stirring for 5 minutes, adding 1.5 g Acticide MBS 50/50 (preservative, active ingredients: 1,2-Benzisothiazolin-3-one, 2.5%; 2-Methyl-4-isothiazolin-3-one, 2.5%). After stirring a homogeneous, transparent solution is obtained.
(45) Textile Treatment 1, LS18-00696-4-1:
(46) A polyester knitted fabric is padded with a treatment liquor containing 750 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. (corresponds to 30% active substance on the fabric after the application)
(47) Textile Treatment 2, LS18-00696-5-1:
(48) A polyester knitted fabric is padded with a treatment liquor containing 500 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. (corresponds to 20% active substance on the fabric after the application)
(49) Textile Treatment 3, LS18-00696-6-1:
(50) A polyester knitted fabric is padded with a treatment liquor containing 250 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. (corresponds to 10% active substance on the fabric after the application)
(51) Textile Treatment 4, LS18-00696-7-1:
(52) A polyester knitted fabric is padded with a treatment liquor containing 83.3 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. (corresponds to 3% active substance on the fabric after the application)
(53) Textile Treatment 5, LS18-00696-8-1:
(54) A polyester knitted fabric is padded with a treatment liquor containing 25 g/l Formulation 1 and 1 ml/l acetic acid 25%, squeezed to 50% pick-up and dried for 2 minutes at 120° C. (corresponds to 1% active substance on the fabric after the application).
(55) Cotton jersey samples were treated analogously leading to samples LS18-00695-6-1-LS18-00695-10-1.
(56) Cotton jersey cationized samples were treated analogously leading to samples LS18-00695-11-1-LS18-00695-15-1.
(57) UT stands for untreated textiles.
(58) The samples are summarized in the following table:
(59) TABLE-US-00001 1 HeiQ Adaptive Liquid Adaptive AC-06 formulation for textile AC-06 treatment 2 Active in Solid Active component in Adaptive AC-06 Adaptive AC-06 3 LS18-00696-3-1 Fabric JE1400 100% PES jersey knit - UT 4 LS18-00696-4-1 Fabric JE1400 100% PES jersey knit + 30% Polymer 5 LS18-00696-5-1 Fabric JE1400 100% PES jersey knit + 20% Polymer 6 LS18-00696-6-1 Fabric JE1400 100% PES jersey knit + 10% Polymer 7 LS18-00696-7-1 Fabric JE1400 100% PES jersey knit + 3% Polymer 8 LS18-00696-8-1 Fabric JE1400 100% PES jersey knit + 1% Polymer 9 LS18-00695-1-1 Fabric 2417 100% cotton jersey (136 gsm); UT 10 LS18-00695-5-1 Fabric 2417 100% cotton jersey (136 gsm) - cationized; UT 11 LS18-00695-6-1 Fabric 2417 100% cotton jersey - 30% polymer 12 LS18-00695-7-1 Fabric 2417 100% cotton jersey - 20% polymer 13 LS18-00695-8-1 Fabric 2417 100% cotton jersey - 10% polymer 14 LS18-00695-9-1 Fabric 2417 100% cotton jersey - 3% polymer 15 LS18-00695-10-1 Fabric 2417 100% cotton jersey - 1% polymer 16 LS18-00695-11-1 Fabric 2417 100% cotton jersey - cationized - 30% polymer 17 LS18-00695-12-1 Fabric 2417 100% cotton jersey - cationized - 20% polymer 18 LS18-00695-13-1 Fabric 2417 100% cotton jersey - cationized - 10% polymer 19 LS18-00695-14-1 Fabric 2417 100% cotton jersey - cationized - 3% polymer 20 LS18-00695-15-1 Fabric 2417 100% cotton jersey - cationized - 1% polymer
Methods Testing was performed using a DSC Q200 system (TA instruments). An empty pan was used as the reference. DSC tests were conducted in single-pass mode (heating) with a temperature range of −10° C. to 60° C. under an inert (nitrogen) atmosphere. The heating rate was 10° C./minute. All samples were tested using hermetically sealed aluminium pans. DSC curves were acquired during a single cool-heat cycle.
Results The active component (sample #2) and the formulated active (sample #1; HeiQ Adaptive AC-06) were tested. DSC traces are shown in
Polyester Fabrics DSC traces for the 100% polyester knit fabrics are shown in
Cotton Fabrics (Non-Cationized) DSC traces for the 100% cotton knit fabrics (non-cationized) are shown in
Cationized Cotton Fabrics DSC traces for the 100% cotton knit fabrics (cationized) are shown in