CN101687888B - A zinc complex, process for preparing thereof and a method for treating fabric therewith - Google Patents
A zinc complex, process for preparing thereof and a method for treating fabric therewith Download PDFInfo
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- CN101687888B CN101687888B CN2008800186709A CN200880018670A CN101687888B CN 101687888 B CN101687888 B CN 101687888B CN 2008800186709 A CN2008800186709 A CN 2008800186709A CN 200880018670 A CN200880018670 A CN 200880018670A CN 101687888 B CN101687888 B CN 101687888B
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- fabric
- zinc
- complex compound
- acid
- alkanolamine
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- 239000004744 fabric Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 230000001476 alcoholic effect Effects 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 229960004418 trolamine Drugs 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 230000005595 deprotonation Effects 0.000 claims description 4
- 238000010537 deprotonation reaction Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002632 lipids Chemical class 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- -1 Carboxyl Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 27
- 229920000742 Cotton Polymers 0.000 description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 229960000314 zinc acetate Drugs 0.000 description 10
- 239000004246 zinc acetate Substances 0.000 description 10
- 239000004753 textile Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 6
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000002953 phosphate buffered saline Substances 0.000 description 4
- 241000191963 Staphylococcus epidermidis Species 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229960003604 testosterone Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 241000186031 Corynebacteriaceae Species 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PROXTKDYKVVKOT-UHFFFAOYSA-L C(CC)(=O)[O-].C(O)CN.[Zn+2].C(CC)(=O)[O-] Chemical compound C(CC)(=O)[O-].C(O)CN.[Zn+2].C(CC)(=O)[O-] PROXTKDYKVVKOT-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/62—Complexes of metal oxides or complexes of metal salts with ammonia or with organic amines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to a Zinc complex, a process for making the Zinc complex and to method of fabric treatment, particularly to a method of increasing the stain repellence by increasing the hydrophobicity of fabrics using complexes of Zinc.
Description
Invention field
The present invention relates to method of fabric treatment, particularly relate to the method that increases pollution resistance through the hydrophobicity of using zinc complex to increase fabric.
The present invention mainly is used for fabric treating by exploitation, will describe this application hereinafter.Yet, be to be understood that the present invention is not limited in this specific use field.
Background and correlation technique
Whole specification sheets should be considered to never to admit that to any discussion of prior art these prior aries are cognitive or form the part of the common practise in this field by extensively.
Fabric or textile fibres are easy to stain when touching moisture spot (stain).These spots comprise ink, dyestuff, tea, coffee and Other Drinks.Repellency (repellenc) is meant that textiles repels the ability of moisture or oily liquid.
Therefore, the material that repellency is good is not easy to absorb liquid, and opposite liquid will tend to " balling-up (roll-up) " perhaps by the exclusion from such textiles.Usually hope to obtain the repellency of higher degree.Be so particularly for causing the situation of contamination by the product that contains persistence dyestuff or pigment (such as the persistence dyestuff or the pigment that are present in coffee, tea, wine, fruit juice and the ink).An approach is that coating or impregnate fabric become relatively easy so that follow-up spot is removed.Therefore the fabric through hydrophobic treatment can repel spot.
For this reason, the report of existing anti-staining agent (stain repellant) in the document.There is report to claim compound, can makes this purpose like zinc oxide and silicone based on zinc.
Zinc-amine complex is reported in the art.
GB119806 (British Petroleum) has described the zinc complex with following structure: (RCOO) ZnO (R1NH2) n; Wherein the R representative contains alkyl, naphthenic base, aryl, aralkyl or the alkaryl group that is no more than 24 carbon atoms; The R1 representative contains the alkyl of 1 to 30 carbon atom; It can be saturated or undersaturated, and side chain or straight chain, n are from 1 to 8 integers.In this complex compound, zinc atom is arranged in around the central Sauerstoffatom with tetrahedral form.
Zinc complex also is used to give antibiotic and/or the bacteriostatic performance to textiles.
US4172841 (US Commerce, 1981) has described preparation bacteriostatic, water-fast, the zinc acetate complex compound that contains superoxide, discloses in the presence of acetate to prepare through zinc acetate and hydroperoxidation.Having described these complex compounds original position on cellulosic and polyester-containing textiles forms and sedimentary method.The textiles aftertreatment (finishes) that so produces can suppress to produce growth and the diffusion of peculiar smell and infectious Gram-positive and gram negative bacterium on treated textiles.The anti-microbial activity of finished product textiles is persistent in laundering repeatedly.Jitaru, people Complex compounds with positively charged ligands such as I.
Biological applications, Roum.Biotechnol.Lett. the 4th volume, the 3rd phase, 213-220 (1999) disclose the 2-monoethanolamine the coordination ability of quaternary ammonium salt, Jitaru further discloses Zn
2+((CH
3)
3N
+-C
2H
4-O
-) (CH3COO
-)
2
Report that hydrophobic polymer, particularly fluorocarbon and silicone can make fabric face have pollution resistance.
Yet, need renewal, better product always.
Goal of the invention
The purpose of this invention is to provide to increase the hydrophobic method of fabric.
The inventor has found one type of new zn cpds, unexpectedly demonstrates excellent benefit when this type zn cpds is applied in fabric treating.Observe according to the inventor, these compounds can be the surface, and particularly fabric is given the hydrophobicity of height.
Summary of the invention
According to an aspect, formula Zn the present invention relates to see service
x(AA)
y(BB)
zZinc complex, wherein " AA " represent neutral or deprotonation single, two or three-alkanolamine; " BB " represents formula H (CH
2)
pCO
2 -Carboxyl (carboxylate group), p=1-5 wherein, its Sauerstoffatom through terminal or bridging is connected with zinc; X, y and z are the integers that satisfies the divalence of zinc.
Preferably, complex compound has following structure:
Wherein, p=1-5
According to another aspect, the present invention relates to prepare the complex compound method, it may further comprise the steps
(i) under the situation that the alcoholic solvent that has basically no moisture exists, with formula H (CH
2)
pCO
2The zinc salt of the carboxylic acid that H representes contacts with alkanolamine, wherein p=1-5; With,
(ii) separate solvent, to obtain said complex compound.
According to another aspect, the present invention relates to handle the method for fabric, it may further comprise the steps:
(i) fabric is contacted with alcoholic solution according to complex compound of the present invention;
Fiber is contacted with the water-bearing media of pH value between 5 to 9; With,
(iii) dry fabric.
Preferably, this method comprises the additional step that fabric is contacted with adipic acid solution.
According to another aspect, the present invention relates to the purposes that complex compound according to the present invention is used for fabric treating.To be elaborated to the present invention.
Specify
Formula Zn the present invention relates to see service
x(AA)
y(BB)
zZinc complex, wherein " AA " represent neutral or deprotonation single, two or three-alkanolamine; " BB " represents formula H (CH
2)
pCO
2 -Carboxyl, p=1-5 wherein, its Sauerstoffatom through terminal or bridging is connected with zinc; X, y and z are the integers that satisfies the divalence of zinc.
Preferably, alkanolamine is selected from carbinolamine, monoethanolamine, diethylolamine or trolamine, more preferably trolamine.
In a preferred form, carboxyl is by formula H (CH
2)
pCO
2 -Expression, wherein p=1-5.This comprises acetate, propionic acid, butyric acid, valeric acid and caproic acid.Preferably this acid is acetate.
Preferred especially complex compound has following structure:
P=1-5 wherein.
Can prepare by a kind of method that may further comprise the steps according to complex compound of the present invention:
(i) under the situation that the alcoholic solvent that has basically no moisture exists, with formula H (CH
2)
pCO
2The zinc salt of the carboxylic acid that H representes contacts with alkanolamine, wherein p=1-5; With,
(ii) separate solvent, to obtain complex compound.
Show that according to observations the existence of moisture causes forming some particles, rather than complex compound, this possibly be because the hydrolysis of complex compound causes.Have basically no moisture and refer to the moisture that can contain 5wt% in the alcoholic solvent at most.
Can adopt any known method of from liquid, separating complex compound, be preferred although evaporating solvent obtains complex compound.Selectively, with solution together be dissolved in wherein complex compound be cooled to about 0 ℃ obtaining complex compound, and slowly pour out (decant off) solvent.
In being suitable for zinc salt of the present invention, zinc acetate is most preferred salt.
Preferred solvent is the alcoholic solvent that is selected from methyl alcohol, ethanol or Virahol.Ethanol is because of low with respect to methyl alcohol toxicity, and is low and have low relatively boiling point but most preferred solvent with respect to Virahol viscosity.
The mol ratio of preferred zinc salt and alkanolamine is 3: 1 to 1: 3, is more preferably 2: 1 to 1: 2, most preferably is 1: 1.
The present invention also provides the method for handling fabric, and it may further comprise the steps:
(i), make fabric and contact with the water-bearing media of pH value between 5 to 12 according to the alcoholic solution of complex compound of the present invention with random order; With
(ii) dry fabric.
Preferred especially pH value is between 6 to 8.
The preferred concentration of alcoholic solution is 0.05% to 2.0%, and more preferably between 0.1% to 0.5%, wherein % is by weight.
In this method, fabric takes out from solution after contacting with alcoholic solution, contacts with water-bearing media afterwards.On the other hand, can from alcoholic solution, remove alcohol, afterwards fabric contacted with aqs soln.Aqs soln can be water or contain washing composition or electrolytical aqs soln.The order of contact can be put upside down, and promptly fabric can be at first and water-bearing media, like the detergent solution contact, contacts with alcoholic solution according to complex compound of the present invention more subsequently.Drying is preferably through dry air, although also can carry out drying through forced air drying and blowing hot-air.Treated fiber can press, and helps fixedly to be considered to the particle that is formed by the complex compound hydrolysis like this.
Preferably, this method comprises the additional step that fabric is contacted with adipic acid solution, and lipid acid is selected from C
10To C
18Straight chain or branched carboxylic acids.Preferred lipid acid is LAURIC ACID 99 MIN and Triple Pressed Stearic Acid.
Adipic acid solution prepares in non-aqueous solvent, and these non-aqueous solvents are selected from primary alconol, alkane or ketone, preferred primary alconol, more preferably ethanol.
Strength of solution is preferred between 0.25%wt to 2%wt, more preferably between 0.5%wt to 1.0%wt.
Do not hope to be retrained by theory; The hydrophobic increase of fabric treated is attributable to the particulate deposition according to the present invention; The common scope of these particulate sizes at 100-1000nm; Be more in particular between the 200nm to 500nm, these particulates can be the semispheres (dimpled hemispherical shaped) of annular (dough-nut shaped) or nick.
Can select any suitable fabric to be used for the present invention, but be preferably cotton fabric, polyester-cotton fabric (polycotton), polyester textile, silk fabrics, wool fabric or be used for other syntheticss such as the application of clothes, footwear, upholstery, curtain, carpet and coating manufacturing.
Hydrophobicity is to measure through the contact angle of water droplet in the Measurement of Air.Preferred contact angle is 90 ° to 140 ° scope.When using fatty acid treatment, the contact angle that water in air is dripped can reach 145 ° to 170 ° scope.The contact angle that increases means higher hydrophobicity, and hydrophobicity is equal to the repellency to the water-based spot.
Contact angle is to be positioned at the join angle of part of liquid (perhaps two kinds of immiscible liquid) interface and solid surface.Contact angle is specific for any given system, is determined by the interaction at three interfaces.The most frequently, this notion describes through the little water droplet that is still on the smooth horizontal solid surface.The shape of this water droplet is determined by Young-Laplace equation.One of method of measuring contact angle is to adopt the contact angle protractor to be measured by the liquid sessile drop method.This method is used for judging the wettability of the regional area of solid surface.Angle between the tangent line on the baseline of drop and drop border is exactly a contact angle, shown in figure-1.
Here, angle θ (=∠ ABC) is the contact angle of spherical drop on the base plane.It shows angle θ=2tan
-1(h/r), h=AD wherein, r=AB.
On extremely hydrophilic surface, water droplet can be sprawled (effectively contact angle is 0 °) fully.
This betides the surface big to water avidity (comprising water-absorbing material, like cotton fabric).On hydrophobic surface, can observe big contact angle (70 ° to 90 °).Hydrophobicity is high more, and contact angle is big more.Some surfaces can reach 140 ° or bigger with the contact angle of water.
On these surfaces, water droplet is from the teeth outwards static, and in fact can be not wetting to any significant degree.These surfaces are called as super-hydrophobicity.In the present invention, can obtain high hydrophobicity to super-hydrophobicity effect through handling hydrophilic fabrics (contact angle is 0 to 20 °).
Except that increasing pollution resistance, according to observations, treated fabric also demonstrates antimicrobial and presses down smelly benefit.
Now will present invention is described by following non-restrictive example.
Trolamine zinc complex (synthetic (ratio 1: 1) of compound-1A)
With 11g (0.05M) zinc acetate 2H
2O AR (Ex Merck) puts into round-bottomed flask, to wherein adding 500ml ethanol (other absolute ethyl alcohol of HPLC level).Ethanol evaporation on Rotary Evaporators is evaporated up to about 250ml ethanol.Then flask is cooled to 0 ℃ in ice bath.
In the beaker of a 250ml, 7.45g trolamine AR (ex.SD Fine Chem) is dissolved in the absolute ethyl alcohol of 100ml.Under continuously stirring, dropwise splashing into of this solution contained in the round-bottomed flask of zinc acetate alcoholic solution.Obtain vitreosol.Then, ethanol evaporation is obtained the compound-1A of white powder.
The sign of above-mentioned white powder
Above-mentioned powder (complex compound) characterizes through powder X-ray RD analysis, NMR spectrum, IR spectrum and monocrystalline XRD.
IR spectrum
The mixture of preparation and KBR is by Perkin Elmer appearance spectra re-recorded.
Spectrum is at 3500cm
-1Near demonstrate broadband corresponding to hydroxyl (OH), at 1580cm
-1The place shows the peak corresponding to the carbonyl moiety of acetoxyl.This spectrum is included among the figure-2.
NMR spectrum
With sample dissolution in deuterated methyl alcohol, by Perkin Elmer appearance spectra re-recorded.Spectrum demonstrates 4 peaks, shown in figure-3 (peak of getting rid of solvent).
In order more to clearly illustrate the peak, part spectrum is amplified, this is included among the figure-4.Because the existence of methyl in the aceticoceptor, the unimodal of point appears in the 1.95ppm place.Triplet at the 2.88ppm place can be owing to the N-in the complex structure
CH2-group.Near 3.76ppm another triplet is attributable to N-CH2-
CH2The existence of-OH group.Near 3.3ppm and 4.87ppm other 2 peaks can be left in the basket, because they come from the impurity (being respectively the first alcohol and water) in the solvent.To display as next, this molecule comprises the complex construction that has two different acetate environment, they in a part as terminal part and bridge ligand.As if in solution, both can change fast each other, like unimodal sign the among the NMR.
Powder X-ray RD
Analysis is carried out on Siemens D-500 appearance, uses copper K α 1.54A wavelength unit, 2-θ ratio.Spectrum demonstrates other peaks beyond the corresponding spectrum of zinc acetate, therefore can confirm that this complex compound is not a zinc acetate.
Monoclinic crystal structure is resolved
The vitreosol that obtains among the embodiment 1 is put in the vial about 30 days of evaporating solvent.Collect one crystal then and observation under opticmicroscope.The single crystal of selecting to be fit to (size is 0.40mmx0.15mmx0.10mm) carries out structure elucidation.Use Enraf-Nonius CAD-4 (MACH-3) monocrystalline x-ray diffractometer to collect diffraction data at ambient temperature; Adopt SHELX-97 and SHELXTL software package to adopt the complete matrix method of least squares to carry out structure elucidation and correction [G.M.Sheldrick, SHELX-97, Program for crystal structuresolution and refinement; University of Gottingen; Gottingen, Germany, 1997].Analytic structure is shown in figure-5.
Crystalline structure confirms that this molecule is four nuclear zinc complexes, and for having the centrosymmetric structure of two different zinc environment, a zinc is four-coordination, and another zinc is pentacoordinate.Two hydroxyls of trolamine part are deprotonation (their symmetrical equivalents among the O2, O3 and figure), between two zinc atoms as bridge linkage group.The 3rd OH (O1 and its symmetrical equivalents) keeps protonated (for the purpose of clear, not showing in the drawings), only with a zinc atom coordination.
In complex molecules, existing bridging (through 04,05 with their symmetrical equivalents) aceticoceptor, also have terminal aceticoceptor (through 06 with its symmetrical equivalents).Also has water molecules (being expressed as O111) with two Wasserstoffatomss.
Embodiment 2
Synthetic (the compound-1B) of pulverous trolamine zinc acetate complex compound
With pestle and mortar the dehydration crystal of 11g zinc acetate is ground the pure trickle powder that becomes, to the slow about 6g trolamine of adding wherein.Under agitation the thorough mixing mixture obtains compound-1B, pulverizes with kitchen mixer.
Synthetic diethylolamine zinc acetate complex compound in alcoholic solution (compound-1C)
Anhydrous zinc acetate (0.05M) and diethylolamine (0.1M) are joined in the ethanol of round-bottomed flask, stirred 30 minutes, obtain compound-1C.
Synthetic monoethanolamine zinc propionate complex compound in alcoholic solution (complex compound-1D)
Zinc propionate (0.1M) and monoethanolamine (0.05M) are joined in the Virahol in round-bottomed flask, refluxed 30 minutes.Use Rotary Evaporators, from system, remove lentamente and desolvate, stay gumminess (gummy) thing.Then with the substance dissolves that obtains in methyl alcohol, obtain the methanol solution of compound-1D.
The measurement of fabric treating and treated fabric contact angle
The cotton (100% cotton is purchased acquisition) of a 50cmX50cm was soaked 30 minutes in compound-1A solution of 500ml 0.5wt%.
Then cloth specimen is immersed in the zero(ppm) water, soaked 15 minutes, from water, take out, dry under the sun.After this press cloth specimen.
Cut a treated fabric of 10cmX10cm, coated with adhesive on the fabric angle pastes on the slick slide glass.
Then slide glass is placed on the platform of the protractor that is equipped with camera.On fabric, drip water and take pictures with syringe.Through the water droplet shape analysis of standard, confirm that water in air drops in the contact angle of fabric face.In this case, the contact angle of water on undressed and treated fabric cloth specimen is respectively 0 ° and 145 °.
In washing process through the research of compound 1-A fabric treated contact angle
A 10cmX10cm is purchased cotton (100%) fabric and the polyester-cotton blend of acquisition, and (67% polyester: 33% cotton) fabric (their initial water contact angle all is 0 ° (that is to say, be high-hydrophilic)) soaked 30 minutes in 3% water-detergent solution.After this cloth specimen was soaked 30 minutes in 1% compound 1-A solution immediately.
Then with cloth specimen with deionized water rinsing twice, place air drying.After this press cloth specimen.Polyester-cotton blend (67: 33) fabric to be purchased acquisition repeats identical experiment.In another group experiment, cloth specimen is soaked in detergent solution, with deionized water rinsing twice, after this in compound 1-A solution, soaked 30 minutes.
Dry cloth specimen and flatiron.In another group of experiment, at first cloth specimen was soaked 30 minutes in compound-1A solution, next in 3% detergent solution, soak.Cloth specimen is used deionized water rinsing twice then, this after drying and flatiron.
At the contact angle that passes through on these method fabric treated, its measuring result is summarized in the following table-1 according to the commercial measurement water droplet of mentioning among the embodiment 5.
Table 1
Annotate: sample 1-5 is a cotton appearance, and 6-9 is the polyester-cotton blend cloth specimen
Det: refer to 3% detergent solution.
Will recognize that described compound-1A provides the benefit of good repulsion water, as contact angle confirmed.Also will recognize that aspect processing sequence, to have handiness, because handled before or after flushing with compd A-1, contact angle does not have significant difference.
Carry out additional processing to strengthen hydrophobicity with lipid acid
Handle polyester-cotton blend (67% terylene: 33% cotton) fabric cloth specimen with method mentioned among the embodiment 5.Show that the aerial contact angle of water is 142 °.Treated fabric was soaked 30 minutes in 0.5% Triple Pressed Stearic Acid ethanolic soln, take out, with washing 3 times and at air drying.After handling like this, the aerial contact angle of water is increased to 165 ° on the fabric, this equates uniform hydrophobic surface.
Antibioticly press down smelly benefit
On cotton sample that contrasts and treated cotton sample, carry out testosterone and different tributyrin (isobutyrin) and decompose experiment (as follows), next by the 0-5 classification stink on the fabric is assessed (the minimum smell of 0=by the professional; 5=is the most smelly).The stink scoring of control sample is 1.5 to 2, and the scoring of treated sample is 0 to 0.5.This proves that clearly treated fabric is in the benefit that presses down aspect smelly.
Testosterone and different tributyrin decompose experiment
In contrast or under the situation about existing of the cotton sample after handling, on the pancreas peptone soybean broth substratum, cultivated staphylococcus epidermidis (S.epidermidis) or coryneform bacteria (Corynebacterium sp) 24 hours in 37 ℃.Centrifugal, for staphylococcus epidermidis, suspend being deposited in the phosphate buffered saline (PBS) (PBS) that contains 0.1% tributyrin, for coryneform bacteria, will be deposited in 1X PBS and 0.05% testosterone and suspend.With the test tube sealing, under 37 ℃, hatched 6 hours.Next by specialized review person these are smelt examination, and mark by the 0-5 classification.
Therefore, said embodiment provides complex compound, and it can be used for giving excellent hydrophobicity to fabric, and increase fabric hydrophobicity is provided, and then increases the method for pollution resistance.
It is also recognized that said embodiment provides the method for handling fabric, this method is given fabric and is pressed down smelly benefit.
Although invention has been described according to concrete embodiment, those skilled in the art will recognize that the present invention can otherwise embody.
Claims (14)
1. the formula that sees service Zn
x(AA)
y(BB)
zZinc complex, wherein;
" AA " represent neutral or deprotonation single, two or three-alkanolamine;
" BB " represents formula H (CH
2)
pCO
2Carboxyl, p=1-5 wherein, its Sauerstoffatom through terminal or bridging is connected with zinc; With, x, y and z are the integers that satisfies the divalence of zinc; Wherein said alkanolamine is selected from carbinolamine, monoethanolamine, diethylolamine or trolamine.
2. complex compound as claimed in claim 1 has following structure:
P=1-5 wherein.
3. prepare the method for complex compound as claimed in claim 1, it may further comprise the steps:
(i) under the situation that the alcoholic solvent that has basically no moisture exists, with formula H (CH
2)
pCO
2The zinc salt of the carboxylic acid that H representes contacts with alkanolamine, wherein p=1-5; With,
(ii) separate said solvent, obtaining said complex compound,
Wherein said alkanolamine is selected from carbinolamine, monoethanolamine, diethylolamine or trolamine.
4. method as claimed in claim 3, wherein said carboxylic acid is selected from acetate, propionic acid, butyric acid, valeric acid or caproic acid.
5. like the method for claim 3 or 4, wherein said alcoholic solvent is selected from methyl alcohol, ethanol or Virahol.
6. like the method for claim 3 or 4, the mol ratio of wherein said zinc salt and said alkanolamine is 3: 1 to 1: 3.
7. method as claimed in claim 6, wherein said ratio are 2: 1 to 1: 2.
8. method as claimed in claim 7, wherein said ratio are 1: 1.
9. handle the method for fabric, it may further comprise the steps:
(i), said fabric is contacted with alcoholic solution and the water-bearing media of pH value between 5 to 12 like the complex compound of claim 1 or 2 with random order; With
(ii) dry said fabric.
10. method as claimed in claim 9, the concentration of wherein said alcoholic solution are 0.05%wt to 2.0%wt.
11. like the method for claim 9 or 10, it comprises the step that said fabric is contacted with adipic acid solution.
12. like the method for claim 11, wherein said lipid acid is C
10To C
18Straight chain or branched carboxylic acids.
13. like the method for claim 11, wherein said adipic acid solution is in the non-aqueous solvent that is selected from primary alconol, alkane or ketone, to prepare.
14. the complex compound of claim 1 or 2 is used for the purposes of fabric treating.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1047/MUM/2007 | 2007-06-04 | ||
| IN1047MU2007 | 2007-06-04 | ||
| PCT/EP2008/055143 WO2008148610A1 (en) | 2007-06-04 | 2008-04-28 | A zinc complex, process for preparing thereof and a method for treating fabric therewith |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101687888A CN101687888A (en) | 2010-03-31 |
| CN101687888B true CN101687888B (en) | 2012-11-14 |
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ID=39734933
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| CN2008800186709A Expired - Fee Related CN101687888B (en) | 2007-06-04 | 2008-04-28 | A zinc complex, process for preparing thereof and a method for treating fabric therewith |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2150555A1 (en) |
| CN (1) | CN101687888B (en) |
| BR (1) | BRPI0810352A2 (en) |
| WO (1) | WO2008148610A1 (en) |
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| WO2011134756A1 (en) | 2010-04-30 | 2011-11-03 | Unilever Nv | A stain repellence composition |
| DE102010043896A1 (en) | 2010-11-15 | 2012-05-16 | Henkel Ag & Co. Kgaa | Use of in situ prepared zinc soap as pearlescent donor agents in liquid, paste, gel-form to cut-resistant agent, preferably detergents or cleaning agents |
| WO2020030414A1 (en) | 2018-08-09 | 2020-02-13 | Unilever N.V. | An antiperspirant composition |
| EP4061317B1 (en) * | 2019-11-20 | 2023-06-07 | Unilever IP Holdings B.V. | An antiperspirant composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1198060A (en) * | 1966-11-10 | 1970-07-08 | British Petroleum Co | Zinc Complexes |
| US4172841A (en) * | 1978-08-17 | 1979-10-30 | The United States Of America As Represented By The Secretary Of Agriculture | Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE573273A (en) * | 1958-01-20 | |||
| US3480653A (en) * | 1966-07-05 | 1969-11-25 | Stauffer Chemical Co | Metal organic compounds containing metal - o - n linkage |
| US4199322A (en) * | 1978-08-17 | 1980-04-22 | The United States Of America As Represented By The Secretary Of Agriculture | Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide |
-
2008
- 2008-04-28 BR BRPI0810352-6A2A patent/BRPI0810352A2/en not_active IP Right Cessation
- 2008-04-28 WO PCT/EP2008/055143 patent/WO2008148610A1/en active Application Filing
- 2008-04-28 CN CN2008800186709A patent/CN101687888B/en not_active Expired - Fee Related
- 2008-04-28 EP EP08749775A patent/EP2150555A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1198060A (en) * | 1966-11-10 | 1970-07-08 | British Petroleum Co | Zinc Complexes |
| US4172841A (en) * | 1978-08-17 | 1979-10-30 | The United States Of America As Represented By The Secretary Of Agriculture | Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide |
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| Publication number | Publication date |
|---|---|
| WO2008148610A1 (en) | 2008-12-11 |
| CN101687888A (en) | 2010-03-31 |
| BRPI0810352A2 (en) | 2014-10-21 |
| EP2150555A1 (en) | 2010-02-10 |
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