CA2665628A1 - Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives - Google Patents
Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives Download PDFInfo
- Publication number
- CA2665628A1 CA2665628A1 CA002665628A CA2665628A CA2665628A1 CA 2665628 A1 CA2665628 A1 CA 2665628A1 CA 002665628 A CA002665628 A CA 002665628A CA 2665628 A CA2665628 A CA 2665628A CA 2665628 A1 CA2665628 A1 CA 2665628A1
- Authority
- CA
- Canada
- Prior art keywords
- pei
- textile substrate
- hyperbranched polyethyleneimine
- hyperbranched
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 52
- 239000004753 textile Substances 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000011282 treatment Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 125000004665 trialkylsilyl group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 230000037303 wrinkles Effects 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 abstract description 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000975 dye Substances 0.000 description 14
- 238000004900 laundering Methods 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000000988 sulfur dye Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- RTNUTCOTGVKVBR-UHFFFAOYSA-N 4-chlorotriazine Chemical class ClC1=CC=NN=N1 RTNUTCOTGVKVBR-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001539 azetidines Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/06—After-treatment with organic compounds containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present disclosure is directed to cellulosic textiles treated with h-PEI derivatives, such derivatives possessing the general structure shown below: (R)x - h-PEI - (A)y where R is a non-hyperbranched hydrocarbon group (for example, such as alkyl, alkenyl, arylalkyl, and arylalkenyl groups, where the number of carbon atoms in the linear portion of the hydrocarbon is between 5 and 30 carbon atoms), where x is a number from 1 to about 10,000 (depending on the Mn of the h-PEI), where h-PEI is a hyperbranched polyethyleneimine, where A is a small organic "capping" compound having from 1 to 4 carbon atoms, where y is a number from 0 to 10,000, and wherein R is present in an approximate amount of between about 20% and about 75% by weight of the h-PEI derviative. The chemical treatment imparts durable colorfastness, softness, wrinkle resistance, and reduced drying time to substrates treated therewith.
Description
CELLULOSIC TEXTILES TREATED WITH
HYPERBRANCHED POLYETHYLENEIMINE DERIVATIVES
TECHNICAL FIELD
The present disclosure is directed to the field of hyperbranched polyethyleneimine derivatives useful for treating textile substrates. More specifically, this disclosure relates to treatments used to provide substantially permanent retention of dye color in textiles (that is, colorfastness), particularly in cellulosic textile substrates. In addition to improving the colorfastness of these substrates, the present chemical treatment further enhances the substrate by increasing softness and reducing drying time and wrinkling.
The present disclosure is directed to a molecule having a hyperbranched polyethyleneimine core to which is attached, at a minimum, one or more hydrocarbon groups. Optionally, linking compounds may connect the hydrocarbon groups to the hyperbranched polyethyleneimine core. Additionally, other organic compounds may also be used to "cap" the branches of the hyperbranched polyethyleneimine that are unreacted with hydrocarbon groups.
BACKGROUND
Poor washfastness (that is, the leaching and bleeding of dye stuffs from fabrics), along with poor crockfastness (the removal of dye from fabric when it is abraded), are two significant problems that to one degree or another must be overcome for any dyed or printed good to be used commercially. Some loss of dye is expected to take place from dyed textiles during washing and/or abrasion with all categories of dyes, including sulfur dyes, direct dyes, vat dyes (for example, indigo), and reactive dyes. Sulfur dyes, which are used to produce black denim products, are notoriously poor at retaining their intended color.
One area where colorfastness is of particular concern is the denim market.
Color loss in denim apparel due to laundering is a significant issue to denim manufacturers and consumers, particularly with black denim products.
Considerable efforts have been devoted to modifying existing manufacturing processes and chemical treatments to mitigate this long-standing problem, although with limited success thus far. A number of chemical compositions used in the process of denim have been found ineffective at preserving the colorfastness of the dyed substrates and, in some cases, have contributed to other undesirable effects, such as stiffness.
Typically, manufacturers use one or more quaternary salts attached to long-chain hydrocarbons to treat dyed denim fabrics. While these kinds of quaternary salts provide the treated fabric with a soft feel (also known as "hand"), they generally are not durable to laundering and are ineffective at preserving colorfastness.
Polymeric cationic materials previously have been used as dye fixing agents.
Typically, these are linear molecules with positive charges distributed along the length of the molecular chain. Examples of these cationic fixing agents include BURCOFIXTM FM and BURCOFIXTM 195 (available from M. Dohmen USA of Greenville, South Carolina); MERQUAT 100 (available from Nalco of Naperville, Illinois); and CASSOFIX FRN, CARTAFIXO SWE Liq., and SANDOFIXO TP (all available from Clariant Corporation of Charlotte, North Carolina). The issues with these kinds of products are that either they contain formaldehyde, which may be dangerous at certain levels, or they impart stiffness to the substrate, which is undesirable for apparel applications. Generally, they have only limited ability to preserve colorfastness to laundering.
More recently, dye fixatives, which are based on the cross-linking of hyperbranched polyethyleneimine (h-PEI) to the dye stuffs and/or the substrate, have been developed. Such fixatives are described in US Patent 6,497,733 and US Patent 6,679,924 (both assigned to Nano-Tex, LLC), the disclosures of which are hereby incorporated by reference. It has been found that the h-PEI
compounds described in these patents have limited capability to preserve colorfastness, because the compounds are very hydrophilic and will actually cause color bleeding during processing. In addition, these compounds also attract hydrophilic detergents to the substrate surface during laundering, which tend to strip dyes away from the textile surface. Finally, another problem with these h-PEI compounds is that they contribute stiffness to the substrate.
Yet another use for polyethyleneimine-based compounds in treating textile substrates is described in US Patent No. 7,141,077 to Detering et al., the disclosure of which is hereby incorporated by reference. In this patent, hydrophobically modified polyethyleneimines and polyvinylamines are used to impart wrinkle resistance to cellulose-containing substrates. In this instance, the polyethyleneimines are water-soluble or water-dispersible polyamines. Because the compounds have been modified to introduce only a limited amount of hydrophobicity (i.e., because they are intended to be hydrophilic enough to maintain water solubility), the treatment lacks wash durability and offers little benefit to the washfastness of the substrate. In fact, the compounds actually may lead to significant color bleeding during fabric processing. Additionally, because the treated substrate may lack the desired degree of softness for certain applications, a separate softening agent may be necessary.
Thus, a need exists for a wash-durable dye fixing agent-particularly for cellulosic substrates-that preferably imparts benefits such as softness and wrinkle resistance. The present treatment provides a solution to such needs providing a specific hyperbranched polyethyleneimine structure, which is linked to one or more hydrocarbon groups having linear portions of between 5 and 30 carbon atoms and which may additionally be linked to one or more organic "capping" compounds.
SUMMARY
This disclosure is directed to treatments for dyed textile goods that will improve their fastness properties. More particularly, this disclosure is directed to certain chemical treatments that; when placed on the dyed textile, allow the dye to be permanently or substantially permanently affixed to the fabric, while providing additional benefits in terms of wrinkle resistance and reduced drying time.
The present treatment comprises a hydrophobically modified hyperbranched polyethyleneimine compound, also known as a "hyperbranched polyethyleneimine derivative." The hyperbranched polyethyleneimine derivative comprises at least one hyperbranched polyethyleneimine (a "hydrophilic component") that has been linked to one or more hydrocarbon groups having between 5 and 30 carbon atoms linearly arranged ("hydrophobic component(s)", which may be linked to the hyperbranched polyethyleneimine using any of a number of different linkages). In another embodiment, the chemical treatment also comprises one or more additional organic "cap" compounds attached to the hyperbranched polyethyleneimine core.
Preferably, the hydrophobic components (that is, hydrocarbon groups and optional linking compounds) are electrophilic, so that they react with the nucleophilic hyperbranched polyethyleneimine molecule. Preferably, the hydrophobic components are present in an amount of from about 20% to about 75% of the weight of the final compound (that is, the hyperbranched polyethyleneimine derivative), thereby imparting softness to the treated substrates. Any of a number of acceptable linking groups may be used to link the hydrocarbon groups to the hyperbranched polyethyleneimine, as will be described herein, or the hydrocarbon groups may link directly to the hyperbranched polyethyleneimine molecule.
The disclosure is further directed to the process for treating dyed textiles and other webs with the present chemical treatment, wherein the chemical treatment is applied to at least a portion of the fiber, yarn, textile, or composite. In a presently preferred embodiment, the dyed fabric is placed into the chemical treatment (e.g, by dipping), then padded and dried in a single continuous process.
HYPERBRANCHED POLYETHYLENEIMINE DERIVATIVES
TECHNICAL FIELD
The present disclosure is directed to the field of hyperbranched polyethyleneimine derivatives useful for treating textile substrates. More specifically, this disclosure relates to treatments used to provide substantially permanent retention of dye color in textiles (that is, colorfastness), particularly in cellulosic textile substrates. In addition to improving the colorfastness of these substrates, the present chemical treatment further enhances the substrate by increasing softness and reducing drying time and wrinkling.
The present disclosure is directed to a molecule having a hyperbranched polyethyleneimine core to which is attached, at a minimum, one or more hydrocarbon groups. Optionally, linking compounds may connect the hydrocarbon groups to the hyperbranched polyethyleneimine core. Additionally, other organic compounds may also be used to "cap" the branches of the hyperbranched polyethyleneimine that are unreacted with hydrocarbon groups.
BACKGROUND
Poor washfastness (that is, the leaching and bleeding of dye stuffs from fabrics), along with poor crockfastness (the removal of dye from fabric when it is abraded), are two significant problems that to one degree or another must be overcome for any dyed or printed good to be used commercially. Some loss of dye is expected to take place from dyed textiles during washing and/or abrasion with all categories of dyes, including sulfur dyes, direct dyes, vat dyes (for example, indigo), and reactive dyes. Sulfur dyes, which are used to produce black denim products, are notoriously poor at retaining their intended color.
One area where colorfastness is of particular concern is the denim market.
Color loss in denim apparel due to laundering is a significant issue to denim manufacturers and consumers, particularly with black denim products.
Considerable efforts have been devoted to modifying existing manufacturing processes and chemical treatments to mitigate this long-standing problem, although with limited success thus far. A number of chemical compositions used in the process of denim have been found ineffective at preserving the colorfastness of the dyed substrates and, in some cases, have contributed to other undesirable effects, such as stiffness.
Typically, manufacturers use one or more quaternary salts attached to long-chain hydrocarbons to treat dyed denim fabrics. While these kinds of quaternary salts provide the treated fabric with a soft feel (also known as "hand"), they generally are not durable to laundering and are ineffective at preserving colorfastness.
Polymeric cationic materials previously have been used as dye fixing agents.
Typically, these are linear molecules with positive charges distributed along the length of the molecular chain. Examples of these cationic fixing agents include BURCOFIXTM FM and BURCOFIXTM 195 (available from M. Dohmen USA of Greenville, South Carolina); MERQUAT 100 (available from Nalco of Naperville, Illinois); and CASSOFIX FRN, CARTAFIXO SWE Liq., and SANDOFIXO TP (all available from Clariant Corporation of Charlotte, North Carolina). The issues with these kinds of products are that either they contain formaldehyde, which may be dangerous at certain levels, or they impart stiffness to the substrate, which is undesirable for apparel applications. Generally, they have only limited ability to preserve colorfastness to laundering.
More recently, dye fixatives, which are based on the cross-linking of hyperbranched polyethyleneimine (h-PEI) to the dye stuffs and/or the substrate, have been developed. Such fixatives are described in US Patent 6,497,733 and US Patent 6,679,924 (both assigned to Nano-Tex, LLC), the disclosures of which are hereby incorporated by reference. It has been found that the h-PEI
compounds described in these patents have limited capability to preserve colorfastness, because the compounds are very hydrophilic and will actually cause color bleeding during processing. In addition, these compounds also attract hydrophilic detergents to the substrate surface during laundering, which tend to strip dyes away from the textile surface. Finally, another problem with these h-PEI compounds is that they contribute stiffness to the substrate.
Yet another use for polyethyleneimine-based compounds in treating textile substrates is described in US Patent No. 7,141,077 to Detering et al., the disclosure of which is hereby incorporated by reference. In this patent, hydrophobically modified polyethyleneimines and polyvinylamines are used to impart wrinkle resistance to cellulose-containing substrates. In this instance, the polyethyleneimines are water-soluble or water-dispersible polyamines. Because the compounds have been modified to introduce only a limited amount of hydrophobicity (i.e., because they are intended to be hydrophilic enough to maintain water solubility), the treatment lacks wash durability and offers little benefit to the washfastness of the substrate. In fact, the compounds actually may lead to significant color bleeding during fabric processing. Additionally, because the treated substrate may lack the desired degree of softness for certain applications, a separate softening agent may be necessary.
Thus, a need exists for a wash-durable dye fixing agent-particularly for cellulosic substrates-that preferably imparts benefits such as softness and wrinkle resistance. The present treatment provides a solution to such needs providing a specific hyperbranched polyethyleneimine structure, which is linked to one or more hydrocarbon groups having linear portions of between 5 and 30 carbon atoms and which may additionally be linked to one or more organic "capping" compounds.
SUMMARY
This disclosure is directed to treatments for dyed textile goods that will improve their fastness properties. More particularly, this disclosure is directed to certain chemical treatments that; when placed on the dyed textile, allow the dye to be permanently or substantially permanently affixed to the fabric, while providing additional benefits in terms of wrinkle resistance and reduced drying time.
The present treatment comprises a hydrophobically modified hyperbranched polyethyleneimine compound, also known as a "hyperbranched polyethyleneimine derivative." The hyperbranched polyethyleneimine derivative comprises at least one hyperbranched polyethyleneimine (a "hydrophilic component") that has been linked to one or more hydrocarbon groups having between 5 and 30 carbon atoms linearly arranged ("hydrophobic component(s)", which may be linked to the hyperbranched polyethyleneimine using any of a number of different linkages). In another embodiment, the chemical treatment also comprises one or more additional organic "cap" compounds attached to the hyperbranched polyethyleneimine core.
Preferably, the hydrophobic components (that is, hydrocarbon groups and optional linking compounds) are electrophilic, so that they react with the nucleophilic hyperbranched polyethyleneimine molecule. Preferably, the hydrophobic components are present in an amount of from about 20% to about 75% of the weight of the final compound (that is, the hyperbranched polyethyleneimine derivative), thereby imparting softness to the treated substrates. Any of a number of acceptable linking groups may be used to link the hydrocarbon groups to the hyperbranched polyethyleneimine, as will be described herein, or the hydrocarbon groups may link directly to the hyperbranched polyethyleneimine molecule.
The disclosure is further directed to the process for treating dyed textiles and other webs with the present chemical treatment, wherein the chemical treatment is applied to at least a portion of the fiber, yarn, textile, or composite. In a presently preferred embodiment, the dyed fabric is placed into the chemical treatment (e.g, by dipping), then padded and dried in a single continuous process.
This disclosure is further directed to the dyed fibers, yarns, fabrics, textiles, finished goods, or nonwovens (encompassed herein under the terms "textiles"
and "webs") treated with the subject hyperbranched polyethyleneimine derivatives. Such textiles and webs exhibit a greatly improved colorfastness and resistance to fading, even after multiple launderings. Further, such treated textiles also exhibit increased softness and reduced wrinkling and drying time.
DETAILED DESCRIPTION
The present chemical treatment is especially well-suited for use with cellulosic substrates. The term "cellulose" refers to those fibers made from the carbohydrates contained in the cell walls of plants. Most often, the term "cellulosic" refers to cotton substrates, although flax, ramie, linen, jute, hemp, bamboo, rayon, acetate, and triacetate substrates also fall into this classification.
Substrates containing combinations of cellulosic fiber types may be successfully treated with the present chemical treatment. Other natural fibers, such as wool and silk, may also benefit from the present chemical treatment.
Of principal utility in the present chemical treatment is the hyperbranched polyethyleneimine (h-PEI) molecule, which may also be referred to herein as the hydrophilic component of the compound. In schematic terms, the h-PEI
molecule can be described as having a central core surrounded by a plurality of molecular branches, with each branch projecting outward from the core and having a highly reactive end group. It is to be expected that partial linkage of the branches to themselves often occurs. The molecule typically exhibits a very high charge density per area, meaning that there are a high number of positive charges clustered densely together around the molecular core. This configuration makes the molecule very capable of interacting with a wide range of other molecules, many of which will be described herein. The number of molecules that may be attached to the h-PEI molecule depends on the number average molecular weight (Mõ) of the h-PEI, which reflects the number of branches available for attachment.
and "webs") treated with the subject hyperbranched polyethyleneimine derivatives. Such textiles and webs exhibit a greatly improved colorfastness and resistance to fading, even after multiple launderings. Further, such treated textiles also exhibit increased softness and reduced wrinkling and drying time.
DETAILED DESCRIPTION
The present chemical treatment is especially well-suited for use with cellulosic substrates. The term "cellulose" refers to those fibers made from the carbohydrates contained in the cell walls of plants. Most often, the term "cellulosic" refers to cotton substrates, although flax, ramie, linen, jute, hemp, bamboo, rayon, acetate, and triacetate substrates also fall into this classification.
Substrates containing combinations of cellulosic fiber types may be successfully treated with the present chemical treatment. Other natural fibers, such as wool and silk, may also benefit from the present chemical treatment.
Of principal utility in the present chemical treatment is the hyperbranched polyethyleneimine (h-PEI) molecule, which may also be referred to herein as the hydrophilic component of the compound. In schematic terms, the h-PEI
molecule can be described as having a central core surrounded by a plurality of molecular branches, with each branch projecting outward from the core and having a highly reactive end group. It is to be expected that partial linkage of the branches to themselves often occurs. The molecule typically exhibits a very high charge density per area, meaning that there are a high number of positive charges clustered densely together around the molecular core. This configuration makes the molecule very capable of interacting with a wide range of other molecules, many of which will be described herein. The number of molecules that may be attached to the h-PEI molecule depends on the number average molecular weight (Mõ) of the h-PEI, which reflects the number of branches available for attachment.
For the applications that are contemplated herein, hyperbranched polyethyleneimines having a number average molecular weight (Mõ) of between about 300 and about 2 million are preferred, with Mõ of between about 1,000 and about 75,000 being more preferred.
To the h-PEI molecule are attached at least one, and preferably more than one, hydrocarbon groups to increase the hydrophobicity of the resulting compound (i.e., the h-PEI derivative). These hydrocarbon groups, together with any linking compounds which may be used to attach them to the h-PEI molecule, are collectively referred to as the "hydrophobic components" of the dye-reactive molecule. These hydrocarbon groups may be linear molecules or may contain branched or aromatic portions, which have an electrophilic group capable of reacting with the nucleophilic h-PEI. Preferably, regardless of the structure of the hydrocarbon, the linear portion of the hydrocarbon group contains between about 5 and about 30 carbon atoms and, more preferably, contains between about 10 and about 24 carbon atoms. Mixtures of various length hydrocarbons may also be used.
Examples of electrophilic hydrocarbons include, without limitation, carboxylic acids, ketene dimers, formates, acetyl halides (such as acetyl chloride), esters, anhydrides, alkyl halides, epoxides, isocyanates, and the like. Preferred examples include stearic acid, hydroxy stearic acid, isostearic acid, and palmitic acid.
The weight ratio of h-PEI to hydrophobic groups is from about 5:1 to about 1:10 and, more preferably, is from about 2:1 to about 1:5, depending on the Mõ of the h-PEI. Most preferably, weight ratios of h-PEI to hydrophobic group from about 1:1 to about 1:4 are used.
The present h-PEI derivatives possess the structure shown below:
(R), - h-PEI - (A)y where R is a non-hyperbranched hydrocarbon group (for example, such as alkyl, alkenyl, arylalkyl, and arylalkenyl groups, where the number of carbon atoms in the linear portion of the hydrocarbon is between 5 and 30 carbon atoms), where x is a number from 1 to about 10,000 (depending on the Mõ of the h-PEI), where h-PEI is a hyperbranched polyethyleneimine, where A is a small organic "capping" compound having from 1 to 4 carbon atoms, where y is a number from 0 to 10,000, and wherein R is present in an approximate amount of between about 20% and about 75% by weight of the molecule.
It is understood that, in the synthesis of molecules such as fit the general structure provided above, the actual product exhibits a polydispersity (a distribution of ratios) and the molar ratio of each molecule will vary somewhat around the target ratio.
Optionally, small organic molecules (generically shown as "A" in the structure above) may be used to "cap" the unreacted branches of the hyperbranched polyethyleneimine. Generally speaking, the capping molecule "A" has between one and four carbon atoms. Any caps that will react with the amine (NH or NHZ) portion of the h-PEI molecule may be used, including, without limitation, epoxides, anhydrides, esters, acids, carbonates, sulfates, formates, isocyanates, and mixtures thereof. Specific examples of such caps include, without limitation, ethylene oxide, propylene oxide, methyl bromide, acetic acid, vinyl sulfonates, trifluoroacetic acid, and succinic anhydride. Mixtures of different "cap"
molecules may be used.
Ethylene oxide (EO) or propylene oxide (PO) chains are especially useful as capping compounds in the present treatment to prevent the treated substrate from yellowing when exposed to high manufacturing temperatures (for example, temperatures greater than 350 F). The addition of such chains is not required to achieve the colorfastness and other benefits of the present treatment, but merely to impart additional benefits.
To the h-PEI molecule are attached at least one, and preferably more than one, hydrocarbon groups to increase the hydrophobicity of the resulting compound (i.e., the h-PEI derivative). These hydrocarbon groups, together with any linking compounds which may be used to attach them to the h-PEI molecule, are collectively referred to as the "hydrophobic components" of the dye-reactive molecule. These hydrocarbon groups may be linear molecules or may contain branched or aromatic portions, which have an electrophilic group capable of reacting with the nucleophilic h-PEI. Preferably, regardless of the structure of the hydrocarbon, the linear portion of the hydrocarbon group contains between about 5 and about 30 carbon atoms and, more preferably, contains between about 10 and about 24 carbon atoms. Mixtures of various length hydrocarbons may also be used.
Examples of electrophilic hydrocarbons include, without limitation, carboxylic acids, ketene dimers, formates, acetyl halides (such as acetyl chloride), esters, anhydrides, alkyl halides, epoxides, isocyanates, and the like. Preferred examples include stearic acid, hydroxy stearic acid, isostearic acid, and palmitic acid.
The weight ratio of h-PEI to hydrophobic groups is from about 5:1 to about 1:10 and, more preferably, is from about 2:1 to about 1:5, depending on the Mõ of the h-PEI. Most preferably, weight ratios of h-PEI to hydrophobic group from about 1:1 to about 1:4 are used.
The present h-PEI derivatives possess the structure shown below:
(R), - h-PEI - (A)y where R is a non-hyperbranched hydrocarbon group (for example, such as alkyl, alkenyl, arylalkyl, and arylalkenyl groups, where the number of carbon atoms in the linear portion of the hydrocarbon is between 5 and 30 carbon atoms), where x is a number from 1 to about 10,000 (depending on the Mõ of the h-PEI), where h-PEI is a hyperbranched polyethyleneimine, where A is a small organic "capping" compound having from 1 to 4 carbon atoms, where y is a number from 0 to 10,000, and wherein R is present in an approximate amount of between about 20% and about 75% by weight of the molecule.
It is understood that, in the synthesis of molecules such as fit the general structure provided above, the actual product exhibits a polydispersity (a distribution of ratios) and the molar ratio of each molecule will vary somewhat around the target ratio.
Optionally, small organic molecules (generically shown as "A" in the structure above) may be used to "cap" the unreacted branches of the hyperbranched polyethyleneimine. Generally speaking, the capping molecule "A" has between one and four carbon atoms. Any caps that will react with the amine (NH or NHZ) portion of the h-PEI molecule may be used, including, without limitation, epoxides, anhydrides, esters, acids, carbonates, sulfates, formates, isocyanates, and mixtures thereof. Specific examples of such caps include, without limitation, ethylene oxide, propylene oxide, methyl bromide, acetic acid, vinyl sulfonates, trifluoroacetic acid, and succinic anhydride. Mixtures of different "cap"
molecules may be used.
Ethylene oxide (EO) or propylene oxide (PO) chains are especially useful as capping compounds in the present treatment to prevent the treated substrate from yellowing when exposed to high manufacturing temperatures (for example, temperatures greater than 350 F). The addition of such chains is not required to achieve the colorfastness and other benefits of the present treatment, but merely to impart additional benefits.
One potentially preferred R group has a C17H35 structure, which in the above structure forms a stearic amide. When using this R group and an h-PEI having an Mõ of 1200, representative molar ratios of h-PEI to R are 1:2, 1:4, 1:6, 1:8, 1:10, and 1:12. Similarly, when the Mõ of the h-PEI molecule is about 10,000, representative molar ratios of h-PEI to R are 1:25, 1:60, 1:80, and 1:100.
Finally, when the Mõ of the h-PEI molecule is about 75,000, representative molar ratios of h-PEI to R are 1:400, 1:500, and 1:600.
The chemical synthesis of the present treatment molecules is conducted by reacting the h-PEI molecule with a hydrophobic R-containing electrophilic molecule in the presence of nitrogen. It has been found that mechanical agitation of the reagents in a vessel under nitrogen at a temperature of about 150 C produces the h-PEI derivatives described herein. The time necessary to complete the reaction depends on the amount of reagents that are being reacted and the size of the reaction vessel. The resulting compounds, referred to herein as "h-PEI derivatives", are typically in the form of an oily liquid or waxy solid.
Preferably, h-PEI derivatives exhibit have hydrophobic agents present in an amount of at least 20%; more preferably, of at least 30%; and most preferably, of up to 75% of the weight of the h-PEI derivative.
To prepare a treatment bath for textiles using the h-PEI derivatives described herein, it is necessary to heat the h-PEI derivative to its melting point, so that it may be poured into a vessel where it is combined, via high speed and high shear agitation, with hot water. In this instance, the phrase "hot water" refers to water having a temperature equal to or greater than the melting point of the h-PEI
derivative. Suitable equipment for achieving high speed and high shear agitation includes propeller-type mixers, Jago -type agitators, homogenizers, roll mills, ball mills, microfluidizers, and the like. The dispersion that results from the forcible introduction of the h-PEI derivative into water is assisted and stabilized by addition of a solubilizing agent (e.g., an acid or a surfactant), the amount of which depends on the molecular weight of the h-PEI and the molar ratio of h-PEI
Finally, when the Mõ of the h-PEI molecule is about 75,000, representative molar ratios of h-PEI to R are 1:400, 1:500, and 1:600.
The chemical synthesis of the present treatment molecules is conducted by reacting the h-PEI molecule with a hydrophobic R-containing electrophilic molecule in the presence of nitrogen. It has been found that mechanical agitation of the reagents in a vessel under nitrogen at a temperature of about 150 C produces the h-PEI derivatives described herein. The time necessary to complete the reaction depends on the amount of reagents that are being reacted and the size of the reaction vessel. The resulting compounds, referred to herein as "h-PEI derivatives", are typically in the form of an oily liquid or waxy solid.
Preferably, h-PEI derivatives exhibit have hydrophobic agents present in an amount of at least 20%; more preferably, of at least 30%; and most preferably, of up to 75% of the weight of the h-PEI derivative.
To prepare a treatment bath for textiles using the h-PEI derivatives described herein, it is necessary to heat the h-PEI derivative to its melting point, so that it may be poured into a vessel where it is combined, via high speed and high shear agitation, with hot water. In this instance, the phrase "hot water" refers to water having a temperature equal to or greater than the melting point of the h-PEI
derivative. Suitable equipment for achieving high speed and high shear agitation includes propeller-type mixers, Jago -type agitators, homogenizers, roll mills, ball mills, microfluidizers, and the like. The dispersion that results from the forcible introduction of the h-PEI derivative into water is assisted and stabilized by addition of a solubilizing agent (e.g., an acid or a surfactant), the amount of which depends on the molecular weight of the h-PEI and the molar ratio of h-PEI
to hydrophobic components. Acetic acid is one potentially preferred acid for this purpose (excess acid being evaporated off during subsequent drying of the treated textile substrate). Amounts of greater than 0.1% acid, by weight of solution, may be used successfully. Preferably, the amount of acid will be in the range of about 0.1 % to about 20% of the weight of the h-PEI derivative.
The fiber, the yarn, the fabric, or the finished garment is dyed in the normal manner and is then exposed (by methods known in the art such as by soaking, spraying, dipping, padding, foaming, exhausting, and the like) to the aqueous dispersion of the treatment chemistry. In some instances, it may be possible to introduce the treatment chemistry onto a garment by replacing the softening chemistry (normally applied during the laundering process) with the treatment described herein.
The treated web is then removed from the solution and dried, preferably at temperatures between room temperature and 400 F; more preferably, at temperatures between about 100 F to about 380 F; and, most preferably, at temperatures between about 160 F and 220 F. The typical add-on weight of the h-PEI derivative is from about. 0.1 % of the weight of the fabric to about 10%
of the weight of the fabric and, preferably, is from about 0.2% of the weight of the fabric to about 5% of the weight of the fabric.
The treated substrates exhibit improved color retention after multiple launderings. Additionally, and surprisingly, the substrates also have durable softness, reduced wrinkling after laundering / drying, and reduced drying time in a conventional home dryer.
Without wishing to be bound by theory, it is hypothesized that the h-PEI
derivatives, because of their potentially high cationic charge density, are readily attracted to the anionic groups of the cellulose fibers or dyes, thereby forming multiple ionic bonds that render the complex molecule water-insoluble. The high density of these ionic bonds unites the chemistry and the textile substrate tenaciously, reducing the likelihood that detergent will attack and strip dyes from the textile. It is also believed that any dyestuffs, which ordinarily might be pulled away from the textile fibers during laundering, may be "captured" by the nano-sized core of the h-PEI derivative, in effect holding the dye against the substrate and preserving its dyed appearance. Finally, the long hydrocarbon chains of the h-PEI derivatives provide softness and wrinkle resistance to the textile substrate.
Preferably, when durability to laundering (e.g., for 10 or more washes) is desired, a cross-linking agent is incorporated into the aqueous solution or dispersion.
Suitable cross-linking agents for this purpose include epoxides, chlorotriazines and their derivatives, azetidines, blocked isocyanates, and melamine derivatives, which may further enhance the durability of the treatment chemistry. Other finishing agents may also be used, although softeners are unlikely to be needed due to the softening effects of the treatment chemistry.
In order to further illustrate the present derivative and advantages thereof, the following specific examples are given, it being understood that the same are intended only as illustrative and are in no way limiting.
To a round-bottom flask with a mechanical agitator were added 100 grams of hyperbranched polyethyleneimine (sold under the name EPOMIN SP012 by Summit Specialty Chemical, New Jersey) and 50 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mõ of 1200.
The mixture was heated under nitrogen, with agitation, at a temperature of about 150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained and that the reaction was complete. The resulting product was a waxy solid.
The same procedure, as described in Example 1, was followed, except that 100 grams of stearic acid were used. The resulting product was a waxy solid.
The same procedure, as described in Example 1, was followed, except that 250 grams of stearic acid were used. The resulting product was a waxy solid.
To a round-bottom flask with a mechanical agitator were added 100 grams of hyperbranched polyethyleneimine (sold under the name EPOMINO SP200 by Summit Specialty Chemical, New Jersey) and 120 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a M,, of 10,000.
The mixture was heated under nitrogen, with agitation, at a temperature of about 150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained and that the reaction was complete. The resulting product was a waxy solid.
EVALUATION OF EXAMPLES 1 and 2 Commercially available black denim jeans (LEEO brand) were washed once with TIDEO laundry detergent.
The h-PEI derivatives of Examples 1 and 2 were separately dispersed into hot water via high speed and high shear agitation. To solubilize the h-PEI
derivatives, acetic acid was added to the dispersions to achieve a pH level of about 5. The h-PEI derivatives comprised about 2.0% by weight of dispersions.
The black denim fabric samples were dipped into the treatment dispersions (one sample in the dispersion of Example 1 and one in the dispersion of Example 2), passed through two nip rolls at 40 p.s.i. to remove excess water, dried in a dispatch oven at 320 F for about 10 minutes (or until dry), and then steam-pressed and vacuumed. The treated fabric samples felt noticeably softer to the touch than the untreated fabric.
A comparative sample (Comparative Example A) was also prepared by dipping a sample of the same black denim fabric with a mixture containing 5% by weight of solution of HIPOSOFTO LDS, a supposedly quaternary ammonium softener, commercially available from Boehme-Filatex Corporation of North Carolina.
Comparative Example A was also passed through nip rolls, dried, steam-pressed, and vacuumed, as described above.
The edges of the fabric samples (Examples 1 and 2 and Comparative Example A) were then sewn, and the samples were washed at 140 F. The samples were washed and dried ten times to evaluate color retention.
The L*a*b* color values for the samples were evaluated, using a Labscan XE
from Hunter Labs after 0, 5, and 10 washes. The shade change (AE) was calculated by comparing the 5 and 10 wash readings with the initial measurement after zero washes. Such values are shown in TABLE 1. Smaller DE values are indicative of better color retention.
Sample Identification AE (after 5 washes) DE (after 10 washes) Example 1 0.39 0.81 Example 2 0.58 1.76 Comp. Example A 1.42 2.46 Thus, the h-PEI derivatives of Examples 1 and 2 were better at preserving color than Comparative Example A. The fabric of Comparative Example A became stiffer after laundering, as well as fading.
Next, the fabrics of Example 1, Example 2, and Comparative Example A were evaluated to determine the effect, if any, of the applied treatment on drying time.
The drying procedure is described as follows. Each fabric sample to be tested was die cut, using a 3.5-inch diameter die cutter. The cut samples were soaked with water after having been treated and cured with the hyperbranched polyethyleneimine derivative treatment described herein. The soaked samples were then removed from water and padded (with approximately 40 p.s.i. of pressure) to remove the excess liquid from the samples and to insure that all of the samples had approximately the same amount of initial moisture.
The drying of the samples was measured and recorded by an IR-200 Moisture Analyzer made by the Denver Instrument Company. The standby temperature of this machine was set at 60 C. The machine has an internal weight scale.
Each wet sample was placed individually into the machine, which measured an initial weight and moisture content.
The temperature inside the machine was set at a constant temperature of 60 C, the scale recorder recording the actual weight and measuring the weight loss as moisture left the fabric. Measurements were recorded until the actual weight had varied less than 0.100 grams for about 30 seconds (which indicated that the fabric was completely dry). The machine then generated a print-out containing the sample identification, time elapsed, initial weight, final weight, total weight loss, and % moisture lost during the drying.
The drying times (minutes:seconds) are shown in TABLE 2.
Sample Identification Drying Time Drying Time (after 0 washes) (after 5 washes) Example 1 10:10 25:19 Example 2 13:39 21:14 Comp. Example A 16:39 55:20 Thus, the data shows that the h-PEI derivatives of Examples 1 and 2 significantly reduce drying time, as compared to the treatment of Comparative Example A.
EVALUATION OF EXAMPLES 3 and 4 In an alternate evaluation, a different commercially available black denim jean fabric (WRANGLER brand) was used. In this evaluation, the fabric was washed first with acidic water at 140 F (where the pH of the water was about 4.5, having been adjusted to that level by the addition of acetic acid) for about 5 minutes and then dried.
The h-PEI derivatives of Examples 3 and 4 were separately dispersed into hot water via high speed and high shear agitation. To solubilize the h-PEI
derivatives, acetic acid was added to the dispersions to adjust the pH to about 4.
The h-PEI derivatives comprised about 0.7% by weight of the Example 3 dispersion and about 0.9% by weight of the Example 4 dispersion. Included with the h-PEI dispersions (for Examples 3 and 4) was a cross-linking agent (sold under the name POLYCUP 172LX, from Hercules Inc. of Delaware), present in an amount of about 2.5% by weight of the dispersion.
The black denim fabric samples were dipped into the treatment dispersions (one sample in the dispersion of Example 3 and one in the dispersion of Example 4), passed through two nip rolls at 40 p.s.i. to remove excess water, dried in a dispatch oven at 220 F for about 20 minutes (or until dry), and then steam-pressed and vacuumed. The treated fabric samples felt noticeably softer to the touch than the untreated fabric.
A comparative sample (Comparative Example B) was also prepared by dipping a sample of the same black denim fabric with a mixture containing 2.0% by weight of solution of HIPOSOFTO LDS, a quaternary ammonium softener, commercially available from Boehme-Filatex Corporation. Comparative Example B was also passed through nip rolls, dried, steam-pressed, and vacuumed, as described above.
The edges of the fabric samples (Examples 3 and 4 and Comparative Example B) were then sewn, and the samples were washed at 120 F. The samples were washed and dried ten times to evaluate color retention.
The L*a*b* color values for the samples were evaluated, using a Labscan XE
from Hunter Labs after 0, 5, and 10 washes. The shade change (AE) was calculated by comparing the 5 and 10 wash readings with the initial measurement. Such values are shown in TABLE 3.
Sample Identification AE (after 5 washes) AE (after 10 washes) Example 3 0.58 1.90 Example 4 0.67 2.03 Comp. Example B 2.27 5.06 Thus, the h-PEI derivatives of Examples 3 and 4 were better at preserving color than Comparative Example B. The fabric of Comparative Example B became stiffer after laundering, as well as fading.
A third comparative example (Comparative Example C) was prepared, using the same fabric as that of Example 1, except that a solution containing 1.5% by weight of solution of only h-PEI was used, instead of an h-PEI derivative.
Such h-PEI was sold under the name EPOMIN SP012 by Summit Specialty Chemical of New Jersey. The hydrophilic molecule was easily put into solution with water, without the addition of a solubilizing agent, such as acetic acid.
The fabric of Comparative Example C was prepared by dipping the fabric into the solution described above, passing it through nip rolls, drying, steam-pressing, and vacuuming, as described above. The resulting fabric was noticeably stiffer than the untreated fabric and the treated fabrics of Examples 1, 2, 3, and 4.
To determine the necessary degree of hydrophobicity necessary to achieve the intended properties (i.e., reduced drying time and wrinkling, improved color retention) in the treated textile fabrics, a series of experiments was used to create compounds with various levels of amidation. The experiments were conducted following the procedure outlined in Example 1. The hyperbranched polyethyleneimine compounds that were used had a Mõ of approximately 10,000.
TABLE 4 also shows the amount of stearic acid (by weight %) used to produce the h-PEI derivatives and the degree of hydrophobicity resulting from the synthesis of such derivatives. The phrase "degree of hydrophobicity" refers to a calculated theoretical ratio of the amount of reacted amine groups present in the h-PEI derivative versus the total available reactive amine provided during the synthesis.
Example ID Hydrophobic Wt. % Degree of Hydrophobicity of Final Compound Comparative Ex. D 6.23 0.0100 5 20.0 0.0372 6 30.0 0.0630 7 42.6 0.1075 8 65.7 0.2580 9 72.7 0.3440 10 75.3 0.3870 11 84.1 0.6000 The h-PEI derivatives of Comparative Example D and Examples 5-11 were separately dispersed into hot water via high speed and high shear agitation.
To solubilize the h-PEI derivatives, acetic acid was added to the dispersions to achieve a pH level of about 5. The h-PEI derivatives comprised about 0.25% by weight of dispersions. It should be noted that the product of Example 11 was incapable of being dispersed into water, even with the addition of a significant amount of solubilizing agent. Accordingly, the evaluation described below excludes fabric treated with the h-PEI derivative of Example 11.
The black denim fabric samples (LEE brand) were dipped into the treatment dispersions (one fabric sample for each Example and the Comparative Example), passed through two nip rolls at 40 p.s.i. to remove excess, dried in a dispatch oven at 220 F for about 8 minutes (or until dry), and then steam-pressed and vacuumed. The fabric samples of Examples 5-10 felt noticeably softer to the touch than the untreated fabric or the fabric of Comparative Example D.
The fabrics of Comparative Example D and Examples 5 - 10 were then wet with water. Drying time and moisture % were measured for each Example as initially produced and again after being washed once with TIDE detergent at 105 F
and then dried.
The results are shown in TABLE 5 below.
Initial After I Wash Drying Time Moisture % Drying Time Moisture %
Example ID (min : sec) (min : sec) Water 37:00 49.45 45:50 55.08 Comparative D 15:09 21.13 29:40 41.11 5 14:19 18.63 27:05 37.46 6 13:39 18.60 17:30 24.55 7 13:39 17.63 13:30 24.02 8 12:00 16.21 21:09 30.58 9 12:30 21.57 16:50 26.31 10 12:00 15.34 33:50 47.15 The results shown above indicate that the present chemical treatment improves drying time, particularly when the weight percentage of the hydrophobic components is between about 20% and about 75% and, more particularly, when the weight percentage of the hydrophobic components is between 30% and 73%.
The fiber, the yarn, the fabric, or the finished garment is dyed in the normal manner and is then exposed (by methods known in the art such as by soaking, spraying, dipping, padding, foaming, exhausting, and the like) to the aqueous dispersion of the treatment chemistry. In some instances, it may be possible to introduce the treatment chemistry onto a garment by replacing the softening chemistry (normally applied during the laundering process) with the treatment described herein.
The treated web is then removed from the solution and dried, preferably at temperatures between room temperature and 400 F; more preferably, at temperatures between about 100 F to about 380 F; and, most preferably, at temperatures between about 160 F and 220 F. The typical add-on weight of the h-PEI derivative is from about. 0.1 % of the weight of the fabric to about 10%
of the weight of the fabric and, preferably, is from about 0.2% of the weight of the fabric to about 5% of the weight of the fabric.
The treated substrates exhibit improved color retention after multiple launderings. Additionally, and surprisingly, the substrates also have durable softness, reduced wrinkling after laundering / drying, and reduced drying time in a conventional home dryer.
Without wishing to be bound by theory, it is hypothesized that the h-PEI
derivatives, because of their potentially high cationic charge density, are readily attracted to the anionic groups of the cellulose fibers or dyes, thereby forming multiple ionic bonds that render the complex molecule water-insoluble. The high density of these ionic bonds unites the chemistry and the textile substrate tenaciously, reducing the likelihood that detergent will attack and strip dyes from the textile. It is also believed that any dyestuffs, which ordinarily might be pulled away from the textile fibers during laundering, may be "captured" by the nano-sized core of the h-PEI derivative, in effect holding the dye against the substrate and preserving its dyed appearance. Finally, the long hydrocarbon chains of the h-PEI derivatives provide softness and wrinkle resistance to the textile substrate.
Preferably, when durability to laundering (e.g., for 10 or more washes) is desired, a cross-linking agent is incorporated into the aqueous solution or dispersion.
Suitable cross-linking agents for this purpose include epoxides, chlorotriazines and their derivatives, azetidines, blocked isocyanates, and melamine derivatives, which may further enhance the durability of the treatment chemistry. Other finishing agents may also be used, although softeners are unlikely to be needed due to the softening effects of the treatment chemistry.
In order to further illustrate the present derivative and advantages thereof, the following specific examples are given, it being understood that the same are intended only as illustrative and are in no way limiting.
To a round-bottom flask with a mechanical agitator were added 100 grams of hyperbranched polyethyleneimine (sold under the name EPOMIN SP012 by Summit Specialty Chemical, New Jersey) and 50 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mõ of 1200.
The mixture was heated under nitrogen, with agitation, at a temperature of about 150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained and that the reaction was complete. The resulting product was a waxy solid.
The same procedure, as described in Example 1, was followed, except that 100 grams of stearic acid were used. The resulting product was a waxy solid.
The same procedure, as described in Example 1, was followed, except that 250 grams of stearic acid were used. The resulting product was a waxy solid.
To a round-bottom flask with a mechanical agitator were added 100 grams of hyperbranched polyethyleneimine (sold under the name EPOMINO SP200 by Summit Specialty Chemical, New Jersey) and 120 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a M,, of 10,000.
The mixture was heated under nitrogen, with agitation, at a temperature of about 150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained and that the reaction was complete. The resulting product was a waxy solid.
EVALUATION OF EXAMPLES 1 and 2 Commercially available black denim jeans (LEEO brand) were washed once with TIDEO laundry detergent.
The h-PEI derivatives of Examples 1 and 2 were separately dispersed into hot water via high speed and high shear agitation. To solubilize the h-PEI
derivatives, acetic acid was added to the dispersions to achieve a pH level of about 5. The h-PEI derivatives comprised about 2.0% by weight of dispersions.
The black denim fabric samples were dipped into the treatment dispersions (one sample in the dispersion of Example 1 and one in the dispersion of Example 2), passed through two nip rolls at 40 p.s.i. to remove excess water, dried in a dispatch oven at 320 F for about 10 minutes (or until dry), and then steam-pressed and vacuumed. The treated fabric samples felt noticeably softer to the touch than the untreated fabric.
A comparative sample (Comparative Example A) was also prepared by dipping a sample of the same black denim fabric with a mixture containing 5% by weight of solution of HIPOSOFTO LDS, a supposedly quaternary ammonium softener, commercially available from Boehme-Filatex Corporation of North Carolina.
Comparative Example A was also passed through nip rolls, dried, steam-pressed, and vacuumed, as described above.
The edges of the fabric samples (Examples 1 and 2 and Comparative Example A) were then sewn, and the samples were washed at 140 F. The samples were washed and dried ten times to evaluate color retention.
The L*a*b* color values for the samples were evaluated, using a Labscan XE
from Hunter Labs after 0, 5, and 10 washes. The shade change (AE) was calculated by comparing the 5 and 10 wash readings with the initial measurement after zero washes. Such values are shown in TABLE 1. Smaller DE values are indicative of better color retention.
Sample Identification AE (after 5 washes) DE (after 10 washes) Example 1 0.39 0.81 Example 2 0.58 1.76 Comp. Example A 1.42 2.46 Thus, the h-PEI derivatives of Examples 1 and 2 were better at preserving color than Comparative Example A. The fabric of Comparative Example A became stiffer after laundering, as well as fading.
Next, the fabrics of Example 1, Example 2, and Comparative Example A were evaluated to determine the effect, if any, of the applied treatment on drying time.
The drying procedure is described as follows. Each fabric sample to be tested was die cut, using a 3.5-inch diameter die cutter. The cut samples were soaked with water after having been treated and cured with the hyperbranched polyethyleneimine derivative treatment described herein. The soaked samples were then removed from water and padded (with approximately 40 p.s.i. of pressure) to remove the excess liquid from the samples and to insure that all of the samples had approximately the same amount of initial moisture.
The drying of the samples was measured and recorded by an IR-200 Moisture Analyzer made by the Denver Instrument Company. The standby temperature of this machine was set at 60 C. The machine has an internal weight scale.
Each wet sample was placed individually into the machine, which measured an initial weight and moisture content.
The temperature inside the machine was set at a constant temperature of 60 C, the scale recorder recording the actual weight and measuring the weight loss as moisture left the fabric. Measurements were recorded until the actual weight had varied less than 0.100 grams for about 30 seconds (which indicated that the fabric was completely dry). The machine then generated a print-out containing the sample identification, time elapsed, initial weight, final weight, total weight loss, and % moisture lost during the drying.
The drying times (minutes:seconds) are shown in TABLE 2.
Sample Identification Drying Time Drying Time (after 0 washes) (after 5 washes) Example 1 10:10 25:19 Example 2 13:39 21:14 Comp. Example A 16:39 55:20 Thus, the data shows that the h-PEI derivatives of Examples 1 and 2 significantly reduce drying time, as compared to the treatment of Comparative Example A.
EVALUATION OF EXAMPLES 3 and 4 In an alternate evaluation, a different commercially available black denim jean fabric (WRANGLER brand) was used. In this evaluation, the fabric was washed first with acidic water at 140 F (where the pH of the water was about 4.5, having been adjusted to that level by the addition of acetic acid) for about 5 minutes and then dried.
The h-PEI derivatives of Examples 3 and 4 were separately dispersed into hot water via high speed and high shear agitation. To solubilize the h-PEI
derivatives, acetic acid was added to the dispersions to adjust the pH to about 4.
The h-PEI derivatives comprised about 0.7% by weight of the Example 3 dispersion and about 0.9% by weight of the Example 4 dispersion. Included with the h-PEI dispersions (for Examples 3 and 4) was a cross-linking agent (sold under the name POLYCUP 172LX, from Hercules Inc. of Delaware), present in an amount of about 2.5% by weight of the dispersion.
The black denim fabric samples were dipped into the treatment dispersions (one sample in the dispersion of Example 3 and one in the dispersion of Example 4), passed through two nip rolls at 40 p.s.i. to remove excess water, dried in a dispatch oven at 220 F for about 20 minutes (or until dry), and then steam-pressed and vacuumed. The treated fabric samples felt noticeably softer to the touch than the untreated fabric.
A comparative sample (Comparative Example B) was also prepared by dipping a sample of the same black denim fabric with a mixture containing 2.0% by weight of solution of HIPOSOFTO LDS, a quaternary ammonium softener, commercially available from Boehme-Filatex Corporation. Comparative Example B was also passed through nip rolls, dried, steam-pressed, and vacuumed, as described above.
The edges of the fabric samples (Examples 3 and 4 and Comparative Example B) were then sewn, and the samples were washed at 120 F. The samples were washed and dried ten times to evaluate color retention.
The L*a*b* color values for the samples were evaluated, using a Labscan XE
from Hunter Labs after 0, 5, and 10 washes. The shade change (AE) was calculated by comparing the 5 and 10 wash readings with the initial measurement. Such values are shown in TABLE 3.
Sample Identification AE (after 5 washes) AE (after 10 washes) Example 3 0.58 1.90 Example 4 0.67 2.03 Comp. Example B 2.27 5.06 Thus, the h-PEI derivatives of Examples 3 and 4 were better at preserving color than Comparative Example B. The fabric of Comparative Example B became stiffer after laundering, as well as fading.
A third comparative example (Comparative Example C) was prepared, using the same fabric as that of Example 1, except that a solution containing 1.5% by weight of solution of only h-PEI was used, instead of an h-PEI derivative.
Such h-PEI was sold under the name EPOMIN SP012 by Summit Specialty Chemical of New Jersey. The hydrophilic molecule was easily put into solution with water, without the addition of a solubilizing agent, such as acetic acid.
The fabric of Comparative Example C was prepared by dipping the fabric into the solution described above, passing it through nip rolls, drying, steam-pressing, and vacuuming, as described above. The resulting fabric was noticeably stiffer than the untreated fabric and the treated fabrics of Examples 1, 2, 3, and 4.
To determine the necessary degree of hydrophobicity necessary to achieve the intended properties (i.e., reduced drying time and wrinkling, improved color retention) in the treated textile fabrics, a series of experiments was used to create compounds with various levels of amidation. The experiments were conducted following the procedure outlined in Example 1. The hyperbranched polyethyleneimine compounds that were used had a Mõ of approximately 10,000.
TABLE 4 also shows the amount of stearic acid (by weight %) used to produce the h-PEI derivatives and the degree of hydrophobicity resulting from the synthesis of such derivatives. The phrase "degree of hydrophobicity" refers to a calculated theoretical ratio of the amount of reacted amine groups present in the h-PEI derivative versus the total available reactive amine provided during the synthesis.
Example ID Hydrophobic Wt. % Degree of Hydrophobicity of Final Compound Comparative Ex. D 6.23 0.0100 5 20.0 0.0372 6 30.0 0.0630 7 42.6 0.1075 8 65.7 0.2580 9 72.7 0.3440 10 75.3 0.3870 11 84.1 0.6000 The h-PEI derivatives of Comparative Example D and Examples 5-11 were separately dispersed into hot water via high speed and high shear agitation.
To solubilize the h-PEI derivatives, acetic acid was added to the dispersions to achieve a pH level of about 5. The h-PEI derivatives comprised about 0.25% by weight of dispersions. It should be noted that the product of Example 11 was incapable of being dispersed into water, even with the addition of a significant amount of solubilizing agent. Accordingly, the evaluation described below excludes fabric treated with the h-PEI derivative of Example 11.
The black denim fabric samples (LEE brand) were dipped into the treatment dispersions (one fabric sample for each Example and the Comparative Example), passed through two nip rolls at 40 p.s.i. to remove excess, dried in a dispatch oven at 220 F for about 8 minutes (or until dry), and then steam-pressed and vacuumed. The fabric samples of Examples 5-10 felt noticeably softer to the touch than the untreated fabric or the fabric of Comparative Example D.
The fabrics of Comparative Example D and Examples 5 - 10 were then wet with water. Drying time and moisture % were measured for each Example as initially produced and again after being washed once with TIDE detergent at 105 F
and then dried.
The results are shown in TABLE 5 below.
Initial After I Wash Drying Time Moisture % Drying Time Moisture %
Example ID (min : sec) (min : sec) Water 37:00 49.45 45:50 55.08 Comparative D 15:09 21.13 29:40 41.11 5 14:19 18.63 27:05 37.46 6 13:39 18.60 17:30 24.55 7 13:39 17.63 13:30 24.02 8 12:00 16.21 21:09 30.58 9 12:30 21.57 16:50 26.31 10 12:00 15.34 33:50 47.15 The results shown above indicate that the present chemical treatment improves drying time, particularly when the weight percentage of the hydrophobic components is between about 20% and about 75% and, more particularly, when the weight percentage of the hydrophobic components is between 30% and 73%.
Claims (12)
1 A treated textile substrate, said treated textile substrate comprises:
(a) a cellulosic textile substrate; and (b) a treatment applied to at least one side of said textile substrate, said treatment comprising:
a water-insoluble hyperbranched polyethyleneimine derivative of the formula:
(R)x- h-PEI- (A)y where R is a non-hyperbranched hydrocarbon group, said hydrocarbon group having at least one linear portion, said linear portion having between 5 and 30 carbon atoms; where x is a number from 1 to 10,000;
where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having from 1 to 4 carbon atoms; where y is a number from 0 to 10,000; and wherein R is present in an amount of between about 20% and about 75% by weight of said hyperbranched polyethyleneimine derivative.
(a) a cellulosic textile substrate; and (b) a treatment applied to at least one side of said textile substrate, said treatment comprising:
a water-insoluble hyperbranched polyethyleneimine derivative of the formula:
(R)x- h-PEI- (A)y where R is a non-hyperbranched hydrocarbon group, said hydrocarbon group having at least one linear portion, said linear portion having between 5 and 30 carbon atoms; where x is a number from 1 to 10,000;
where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having from 1 to 4 carbon atoms; where y is a number from 0 to 10,000; and wherein R is present in an amount of between about 20% and about 75% by weight of said hyperbranched polyethyleneimine derivative.
2. The treated textile substrate of Claim 1, wherein said treatment is applied to said substrate at an add-on level of between about 0.1% to about 10%, based on the weight of said substrate.
3. The treated textile substrate of Claim 1, wherein said h-PEI has a number average molecular weight (M n) in range of about 1,000 to about 75,000.
4. The treated textile substrate of Claim 1, wherein said linear portion of said R
group has between about 10 and about 24 carbon atoms.
group has between about 10 and about 24 carbon atoms.
5. The treated textile substrate of Claim 1, wherein said h-PEI and said R
group are present, in a weight ratio, of from about 5:1 to about 1:10.
group are present, in a weight ratio, of from about 5:1 to about 1:10.
6. The treated textile substrate of Claim 1, wherein said A group is at least one compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, methyl, acetate, vinyl sulfonate, trifluoroacetate, and trialkyl silyl.
7. The treated textile substrate of Claim 6, wherein said A group is ethylene oxide or propylene oxide.
8. The treated textile substrate of Claim 1, wherein said treatment further comprises a cross-linking agent.
9. A process of treating a textile substrate, said process comprising:
(a) providing a cellulosic textile substrate;
(b) providing a dispersion of hyperbranched polyethyleneimine derivative, said hyperbranched polyethyleneimine derivative being of the formula:
(R)x - h-PEI - N - (A)y where R is a non-hyperbranched hydrocarbon group, said hydrocarbon group having at least one linear portion, said linear portion having between 5 and 30 carbon atoms; where x is a number from 1 to 10,000;
where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having between 1 to 4 carbon atoms; where y is a number from 0 to 10,000; and wherein R is present in an amount of between about 20% and about 75% by weight of said hyperbranched polyethyleneimine derivative, said dispersion containing said hyperbranched polyethylene derivative being produced by:
(i) providing said hyperbranched polyethyleneimine derivative, a solubilizing agent, and water, said water having a temperature at least equal to the melting point of said hyperbranched polyethyleneimine derivative; and (ii) subjecting said hyperbranched polyethyleneimine derivative, said solubilizing agent, and said water to high speed and high shear agitation;
(c) applying said dispersion to said textile substrate; and (d) drying said textile substrate.
(a) providing a cellulosic textile substrate;
(b) providing a dispersion of hyperbranched polyethyleneimine derivative, said hyperbranched polyethyleneimine derivative being of the formula:
(R)x - h-PEI - N - (A)y where R is a non-hyperbranched hydrocarbon group, said hydrocarbon group having at least one linear portion, said linear portion having between 5 and 30 carbon atoms; where x is a number from 1 to 10,000;
where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having between 1 to 4 carbon atoms; where y is a number from 0 to 10,000; and wherein R is present in an amount of between about 20% and about 75% by weight of said hyperbranched polyethyleneimine derivative, said dispersion containing said hyperbranched polyethylene derivative being produced by:
(i) providing said hyperbranched polyethyleneimine derivative, a solubilizing agent, and water, said water having a temperature at least equal to the melting point of said hyperbranched polyethyleneimine derivative; and (ii) subjecting said hyperbranched polyethyleneimine derivative, said solubilizing agent, and said water to high speed and high shear agitation;
(c) applying said dispersion to said textile substrate; and (d) drying said textile substrate.
10. The process of Claim 9, wherein said solubilizing agent is acetic acid.
11. The process of Claim 9, wherein said dispersion further comprises a cross-linking agent.
12. The process of Claim 9, wherein heat is applied during step (i) or step (ii) to facilitate formation of said dispersion.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/651,688 | 2007-01-10 | ||
US11/651,688 US20080163437A1 (en) | 2007-01-10 | 2007-01-10 | Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives |
PCT/US2008/000136 WO2008085901A1 (en) | 2007-01-10 | 2008-01-04 | Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2665628A1 true CA2665628A1 (en) | 2008-07-17 |
Family
ID=39363815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002665628A Abandoned CA2665628A1 (en) | 2007-01-10 | 2008-01-04 | Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives |
Country Status (4)
Country | Link |
---|---|
US (1) | US20080163437A1 (en) |
CA (1) | CA2665628A1 (en) |
MX (1) | MX2009004487A (en) |
WO (1) | WO2008085901A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007095670A1 (en) * | 2006-02-20 | 2007-08-30 | Commonwealth Scientific And Industrial Research Organisation | Method and composition for priming wood and natural fibres |
CA2657108C (en) * | 2006-07-27 | 2014-03-18 | Basf Se | Use of timber materials comprising polyamine for lowering formaldehyde content in ambient air |
US20080164439A1 (en) * | 2007-01-10 | 2008-07-10 | Xinggao Fang | Textiles treated with hyperbranched polyethyleneimine derivatives for odor control properties |
WO2009045384A1 (en) * | 2007-10-01 | 2009-04-09 | Nano-Tex, Inc. | Modification of cellulosic substrates to control body odor |
US20090246258A1 (en) * | 2008-03-28 | 2009-10-01 | Piyush Shukla | Antimicrobial and odor adsorbing textile |
WO2011108929A2 (en) | 2010-03-05 | 2011-09-09 | Stichting Voor De Technische Wetenschappen | Hollow fibre membrane |
US9248209B2 (en) * | 2011-01-14 | 2016-02-02 | The Procter & Gamble Company | Compositions comprising hydrophobically modified malodor control polymers |
US8486427B2 (en) | 2011-02-11 | 2013-07-16 | Kimberly-Clark Worldwide, Inc. | Wipe for use with a germicidal solution |
TR201712761A2 (en) * | 2017-08-25 | 2019-03-21 | Orta Anadolu Ticaret Ve Sanayi Isletmesi Tuerk A S | LOW WATER CONSUMING, ENVIRONMENTALLY AND SUSTAINABLE INDIGO DYEING PROCESS |
US11466122B2 (en) | 2018-10-18 | 2022-10-11 | Milliken & Company | Polyethyleneimine compounds containing N-halamine and derivatives thereof |
US11518963B2 (en) | 2018-10-18 | 2022-12-06 | Milliken & Company | Polyethyleneimine compounds containing N-halamine and derivatives thereof |
US11732218B2 (en) | 2018-10-18 | 2023-08-22 | Milliken & Company | Polyethyleneimine compounds containing N-halamine and derivatives thereof |
US11299591B2 (en) | 2018-10-18 | 2022-04-12 | Milliken & Company | Polyethyleneimine compounds containing N-halamine and derivatives thereof |
CN109517169B (en) * | 2018-10-19 | 2020-03-31 | 浙江大学 | Amphiphilic hyperbranched polymer and preparation and application thereof |
CN113699786B (en) * | 2021-10-14 | 2023-06-23 | 普宁市爱念制衣有限公司 | Durable antibacterial fiber fabric based on cotton fibers and preparation method thereof |
CN115105973B (en) * | 2022-06-28 | 2023-04-21 | 哈尔滨工业大学(深圳) | Nanofiltration membrane preparation method for efficient magnesium-lithium separation and application |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2649354A (en) * | 1947-12-01 | 1953-08-18 | Sandoz Ltd | Process for improving fastiness properties of direct dyestuffs |
US3141728A (en) * | 1959-12-23 | 1964-07-21 | Bayer Ag | Process for the improvement of the fastness to washing of direct dyeings on cellulose-containing materials |
DE1154070B (en) * | 1961-12-07 | 1963-09-12 | Bayer Ag | Process for improving the wash fastness of prints with dyes containing water-solubilizing groups on cellulose-containing materials |
US3334138A (en) * | 1963-08-02 | 1967-08-01 | Crompton & Knowles Corp | Polymeric quaternary ammonium compound |
US3622528A (en) * | 1968-06-13 | 1971-11-23 | Dow Chemical Co | Polyethylenimine fatty acid epichlorohydrin product |
US3676341A (en) * | 1971-03-15 | 1972-07-11 | Colgate Palmolive Co | Textile softening compositions |
GB1356025A (en) * | 1971-03-30 | 1974-06-12 | Ici Ltd | Colouration process |
NL8104330A (en) * | 1980-09-24 | 1982-04-16 | Sandoz Ag | METHOD FOR LAUNCHING CELLULOSE-CONTAINING TEXTILE AND SUBSTANCES TO BE USED THEREIN. |
CH669081GA3 (en) * | 1981-05-14 | 1989-02-28 | ||
US4605418A (en) * | 1983-03-09 | 1986-08-12 | Diamond Shamrock Chemicals Company | Aftertreatment of dyed cellulosic materials |
US4531946A (en) * | 1983-03-09 | 1985-07-30 | Diamond Shamrock Chemicals Company | Aftertreatment of dyed cellulosic materials |
DE3329029A1 (en) * | 1983-08-11 | 1985-02-28 | Cassella Ag, 6000 Frankfurt | METHOD FOR PRODUCING COLORINGS WITH REACTIVE DYES |
US4718918A (en) * | 1984-01-03 | 1988-01-12 | Sandoz Ltd. | Treatment of textile materials to improve the fastness of dyeings made thereon and polymers useful therefor |
FR2560240B1 (en) * | 1984-02-24 | 1987-07-10 | Sandoz Sa | TEXTILE FIBER AFTER-TREATMENT PROCESS |
JPS6134292A (en) * | 1984-07-20 | 1986-02-18 | 株式会社日本触媒 | Treatment of dyed article |
US4619665A (en) * | 1985-03-11 | 1986-10-28 | Technographics Printworld, Inc. | Sheet containing heat transferable dye and selective blocking agent for heat transfer printing |
DE3709766A1 (en) * | 1987-03-25 | 1988-10-06 | Hoechst Ag | METHOD FOR ALKALI-FREE DYEING WITH REACTIVE DYES |
JP2670624B2 (en) * | 1988-10-12 | 1997-10-29 | ミヨシ油脂株式会社 | Synthetic fiber treatment agent |
DE4325783A1 (en) * | 1993-07-31 | 1995-02-02 | Hoechst Ag | Process for modifying and dyeing modified fiber materials |
US5460736A (en) * | 1994-10-07 | 1995-10-24 | The Procter & Gamble Company | Fabric softening composition containing chlorine scavengers |
US6020302A (en) * | 1997-09-18 | 2000-02-01 | The Procter & Gamble Company | Color care compositions |
US5904738A (en) * | 1998-01-28 | 1999-05-18 | Crompton & Knowles Corporation | Gas-fade inhibition |
US6830593B1 (en) * | 1998-08-03 | 2004-12-14 | The Procter & Gamble Company | Fabric care compositions |
US6497733B1 (en) * | 2000-04-03 | 2002-12-24 | Nano-Tex, Llc | Dye fixatives |
DE10124387A1 (en) * | 2001-05-18 | 2002-11-28 | Basf Ag | Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations |
US20040166753A1 (en) * | 2002-06-10 | 2004-08-26 | Millward Dan B. | Modification of fabric fibers |
US20080164439A1 (en) * | 2007-01-10 | 2008-07-10 | Xinggao Fang | Textiles treated with hyperbranched polyethyleneimine derivatives for odor control properties |
-
2007
- 2007-01-10 US US11/651,688 patent/US20080163437A1/en not_active Abandoned
-
2008
- 2008-01-04 WO PCT/US2008/000136 patent/WO2008085901A1/en active Application Filing
- 2008-01-04 CA CA002665628A patent/CA2665628A1/en not_active Abandoned
- 2008-01-04 MX MX2009004487A patent/MX2009004487A/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2008085901A1 (en) | 2008-07-17 |
US20080163437A1 (en) | 2008-07-10 |
MX2009004487A (en) | 2009-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20080163437A1 (en) | Cellulosic textiles treated with hyperbranched polyethyleneimine derivatives | |
US20080164439A1 (en) | Textiles treated with hyperbranched polyethyleneimine derivatives for odor control properties | |
JP2001508139A (en) | Crosslinking agent for cellulosic fibers | |
Yang et al. | Crease Resistant Finishing of Silk Fabric with BTCA. | |
CN111601923B (en) | Use of non-formaldehyde technology to improve the balance of durable set properties of cotton fabrics | |
AU747983B2 (en) | Method for treating fibrous cellulosic materials | |
US6149549A (en) | Anionically derivatised cotton for improved comfort and care-free laundering | |
Welch | Improved Strength and Flex Abrasion Resistance in Durable Press Finishing with BTCA. | |
US6336943B1 (en) | Anionically derivatised cotton for improved comfort and care-free laundering | |
AU593948B2 (en) | Fabric treatment | |
US5135541A (en) | Flame retardant treatment of cellulose fabric with crease recovery: tetra-kis-hydroxy-methyl phosphonium and methylolamide | |
Reid et al. | Durable Creasing of Wrinkle Resistant Cotton1 | |
US6464730B1 (en) | Process for applying softeners to fabrics | |
EP4100568A1 (en) | Pad-steam cationization of textiles | |
JP3915056B2 (en) | Cellulose fiber processing method | |
JP4264767B2 (en) | Cellulosic fiber-containing fiber structure for form-stable processing and method for producing form-stable cellulosic fiber-containing fiber structure | |
JP2010144277A (en) | Denim product and method for producing the same | |
GB2360795A (en) | Anionically dyeable, durable press, natural fibre products | |
JP3765345B2 (en) | Cellulosic fiber-containing fiber structure for form-stable processing and method for producing form-stable cellulosic fiber-containing fiber structure | |
Abeysinghe | Cotton fabric functionalization to impart wrinkle free properties | |
MXPA99006490A (en) | Cross-linking agents of cellulosic fabrics |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |