CN1912230A - Fibric finishing agent with shape memory function and preparation method thereof - Google Patents
Fibric finishing agent with shape memory function and preparation method thereof Download PDFInfo
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- CN1912230A CN1912230A CN 200510085768 CN200510085768A CN1912230A CN 1912230 A CN1912230 A CN 1912230A CN 200510085768 CN200510085768 CN 200510085768 CN 200510085768 A CN200510085768 A CN 200510085768A CN 1912230 A CN1912230 A CN 1912230A
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- shape memory
- memory function
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- 230000006386 memory function Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 239000004814 polyurethane Substances 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000000675 fabric finishing Substances 0.000 claims description 37
- 238000009962 finishing (textile) Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 26
- -1 dihydroxymethyl dihydroxy ethylene-urea Chemical compound 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002708 enhancing effect Effects 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
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 34
- 239000004753 textile Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000009988 textile finishing Methods 0.000 abstract description 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 229920002050 silicone resin Polymers 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 42
- 235000019256 formaldehyde Nutrition 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 235000011147 magnesium chloride Nutrition 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000004672 propanoic acids Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004855 creaseproofing Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005525 durable press finishing Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a textile finishing agent with shape memory function and the preparing method. It is formed by the reacting of organosilicon modification polyurethane reinforcing resin emulsion, cross linking agent, de-ionized water under catalyst. The first one is formed by the reacting of 50-300 mess parts de-ionized water and pre-polymer which is formed by the reacting of 0.01-0.2 initiator, 30-100 poly-diatomic alcohol, 5-30 aliphatic series diisocyanate, 5-10 short chain aliphatic series diatomic alcohol contains carboxyl, 5-25 silicone resin with hydroxyl end capping, 1-15 tri-hydroxyl polyhydric alcohol, 2-10 salt forming agent, 50-100 organic solvent as mass parts. The textile after using the finishing agent has the advantages of obvious shape memory function, high breaking tearing strength, good flatness and form retention, almost same whiteness, low formaldehyde releasing quantity.
Description
Technical field
The present invention relates to a kind of fabric finishing agent, particularly a kind of fabric finishing agent and preparation method thereof with shape memory function.
Background technology
Utilize chemical method that cellulose fibre and BLENDED FABRIC thereof are carried out " wash and wear " arrangement, non-ironing press arrangement or wrinkle proofing and give the certain shape memory function of fabric for many years history has been arranged.The topmost application of textile finishing with shape memory function is in the wrinkle proofing and noniron finish of cellulosic fabric, this class finishing agent that uses in the prior art mainly contains two big classes: a class such as document " COTTON FABRIC durable press finish " (John D.Turner IBT Dyeing/Printing and Finishing, 1994,2:52～58, " RESIN FINISH application technology ". Beijing: textile industry publishing house, the N-methylol class finishing agent of report such as 1993), the apparent flatness and the pleat trace of this class finishing agent arrangement back fabric keep grade higher, but, have high and powerful the decline seriously and the problem of yellowing of burst size of methanal; Another kind of is polybasic carboxylic acid class finishing agent, as United States Patent (USP) 4820307,4936865,4975209 and document " Determination of Polycarboxylic Acids on Cotton Fabric by FT-IRSpectroscopy " (N.M.Morris, B.A.R.Andres and A.Catalano, Textile Chem.Color.1994), " Effect of pH on No formaldehyde Durable Press Finishing of CottonFabric:FT-IR Spectroscopy Study; Part 1:Ester Cross linking " (Yang, C.Q., Textile Res.J.1993,), " Effect of pH on No formaldehyde Durable Press Finishingof Cotton Fabric:FT-IR Spectroscopy Study; Part 2:Formation of the AnhydrideIntermediate " (Yang, C.Q., Textile Res.J.1993) report such as, though the problem that the fabric after the arrangement does not have formaldehyde to discharge, but, baking temperature height in the arrangement process, the fabric after the arrangement exists yellowing serious, the problem that strength loss is big and look becomes.
Up to the present, majority is used for the crease-proofing textiles containing finishing agent that industrialization uses and all exists fabric strength to reduce or the too high problem of burst size of methanal, does not also have a kind ofly not only to have given the fabric form memory function but also can keep putting in order back fabric strength height, appearance af hand wash flatness and pleat trace conformality is good and fabric finishing agent that whiteness fabric after putting in order is constant substantially, burst size of methanal is low is applied industrial.
Summary of the invention
The purpose of this invention is to provide a kind of fabric finishing agent with shape memory function, adopt this finishing agent to fabric dyeing and finishing processing method commonly used " pad-preliminary drying-bake " put in order in the process after, fabric has good shape memory function, its strength retention height, burst size of methanal is low, whiteness is constant substantially, the look of colored fabric characteristics such as diminish.
The present invention also aims to provide described preparation method with fabric finishing agent of shape memory function.
Fabric finishing agent with shape memory function provided by the present invention strengthens resin emulsion, crosslinking agent and deionized water by organic silicon modified polyurethane and reacts under catalyst action and prepare.It is following component to be carried out after the reaction prepolymer deionized water with 50～300 parts by mass again continue reaction and obtain that described organic silicon modified polyurethane strengthens resin emulsion:
Initator 0.01～0.2 parts by mass
Poly-dihydric alcohol 30～100 parts by mass
Aliphatic diisocyanate 5～30 parts by mass
Carboxylic short-chain fat family dihydroxylic alcohols 5～10 parts by mass
Hydroxy-end capped organic siliconresin 5～25 parts by mass
Trihydroxy polyalcohol 5～15 parts by mass
Salt forming agent 2～10 parts by mass
Solvent 50～100 parts by mass
Prepared fabric finishing agent is colourless to faint yellow viscous liquid, and its mass percent concentration is 25%～45%.
Described crosslinking agent is preferably the hexamethylol melamine of dihydroxymethyl ethylene-urea, dihydroxymethyl dihydroxy ethylene-urea or part etherificate.
Described catalyst is preferably a kind of in magnesium chloride and citric acid composition or magnesium chloride and the glacial acetic acid composition.
Described initator can be any material that can promote the reaction between isocyanate group and the alcoholic extract hydroxyl group, preferred organotin, organic germanium, organic zinc compound or polynary tertiary amine especially preferably use dibutyl tin laurate, stannous octoate or triethylenediamine.
Described poly-dihydric alcohol is preferably at least a in polyethylene glycol (PEG), polytetrahydrofuran diol (PTMG), the polypropylene glycol (PPG), and special preferred number average molecular weight is that 2000～6000 polyethylene glycol (PEG), number-average molecular weight are that 1000～4000 polytetrahydrofuran diol (PTMG) or number-average molecular weight are 2000～4000 polypropylene glycol (PPG) and combination thereof.
Described aliphatic diisocyanate is preferably hexamethylene diisocyanate (HDI), dicyclohexyl methylene diisocyanate (H
12MDI) or isophorone diisocyanate (IPDI).
Described carboxylic short-chain fat family dihydroxylic alcohols is preferably dihydromethyl propionic acid, dimethylolpropionic acid or tartaric acid.
Described hydroxy-end capped organic siliconresin is preferably the organosilicon polymer that number-average molecular weight is 3000～110000 hydroxyl end-blocking, and particularly preferred is 6000～110000 poly dimethyl dimethoxy silane or poly dimethyl diethoxy silane for number-average molecular weight.
Described trihydroxy polyalcohol is preferably glycerol, castor oil, trimethylolpropane or polypropylene glycol (PPG-303, PPG-330, its number average relative molecular mass is respectively 300 and 3000).
Described salt forming agent is preferably triethylamine, triethylenediamine or N, N-dimethyl cyclohexyl amine.
Described organic solvent is preferably dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone or MEK.
Preparation method with fabric finishing agent of shape memory function provided by the present invention comprises the following steps:
(1) preparation of prepolymer: be equipped with agitator, in the reactor of reflux condenser, add 30 ~ 50 parts by mass solvents, 0.01～0.2 parts by mass promoter, 30～100. parts by mass polyether Glycols, 5～30 parts by mass aliphatic diisocyanates, the organic siliconresin that 5～25 parts by mass are hydroxy-end capped, 5～15 parts by mass trihydroxy polyalcohols, 80～85 ℃ of temperature controls, reacted 2～3 hours, the carboxylic short-chain fat family dihydroxylic alcohols that adds 5～10 parts by mass then, 75～80 ℃ of temperature controls, continue reaction after 2～2.5 hours, be cooled to 40～50 ℃, add 2～10 parts by mass salt forming agents, react after 30～60 minutes, the solvent that adds 20～50 parts by mass is regulated viscosity, obtains the organic silicon modified polyurethane prepolymer.
(2) preparation of emulsion: add 50～300 parts by mass deionized waters in containing the reactor of above-mentioned prepolymer, under the high-speed stirred, reacted 1～2 hour, obtaining mass percent concentration is that 15%～40% organic silicon modified polyurethane strengthens resin emulsion.
(3) preparation of finishing agent: the crosslinking agent (strengthening resin quality in pure organic-silicon-modified polyurethane) of 1～1.5 times of organic silicon modified polyurethane enhancing resin quality part, the catalyst of 0.15～0.3 times of crosslinking agent parts by mass, the deionized water of 1.1～3.5 times of crosslinking agent parts by mass are joined in the reactor, continue to stir 1～2 hour, mix, the acquisition solid content is 25%～45% fabric finishing agent.
Adopt the fabric after fabric finishing agent of the present invention is put in order, have good shape memory function and have following characteristic:
1. described fabric finishing agent can react with fabric in the arrangement process, produces chemical bond;
2. adopt the fabric after described fabric finishing agent is put in order to have good apparent flatness and pleat trace maintenance grade;
3. adopt the fabric after described fabric finishing agent is put in order to have good hand feeling, water-wash resistance is good;
4. adopt the burst size of methanal of the fabric after described fabric finishing agent is put in order very low;
5. the light resistance of described fabric finishing agent is good.
The specific embodiment
Below by specific embodiment the present invention is carried out more detailed description.Polyurethane involved in the present invention is synthetic to be industrialization raw material with raw material, needs through processed before part material uses; Employed synthesis device is also for using the synthesis device of industrial polyurethane always.Described raw material umber is mass fraction except that specifying.
Embodiment 1:
With 0.02 kilogram of dibutyl tin laurate, 30 kilograms of polypropylene glycols (PPG) (number average relative molecular mass 3000), 5 kilograms of organic hydroxy silicates (number average relative molecular mass 6000), 20 kilograms of isophorone diisocyanate (IPDI), dimethyl formamide adds 500 liters for 50 kilograms and has agitator, in the reactor of thermometer and reflux condenser, reacted 2 hours down for 80～85 ℃ in temperature, add 5 kilograms of dihydromethyl propionic acids, 5 kilograms of glycerol, 80 ℃ of temperature controls, continue reaction after 2 hours, be cooled to 40～50 ℃, add 3.7 kilograms of triethylamines, continue reaction 30 minutes, add acetone and regulate viscosity for 50 kilograms, obtain colourless to faint yellow, thick polyurethane, in reactor, continue to add 290 kilograms of deionized waters, under the high-speed stirred, emulsion reaction 1 hour makes mass percent concentration and is 15% organic silicon modified polyurethane and strengthens resin emulsion.
Get the above-mentioned emulsion double centner and put into another reactor of 300 liters, add 22.5 kilograms of dihydroxymethyl dihydroxy ethylene-ureas, add 4 kilograms of magnesium chlorides and 0.75 kilogram of citric acid gradually, the deionized water that adds 33 kilograms at last, continue to stir 1 hour, mix, obtain stable fabric finishing agent, its solid content is 25%.
Get the above-mentioned fabrics finishing agent and be made into dressing liquid by mass ratio adding in 1: 1 deionized water, employing two is soaked two and is rolled finishing technique, pick-up is 80%, 80 ℃ of preliminary dryings 2 minutes, 150 ℃ baked 3 minutes, after sample cools off naturally, cloth specimen is placed in the thermostatic constant wet chamber balance more than 48 hours, adopts U.S. AATCC-88C and AATCC-124 standard to estimate respectively that the wrinkle of fabric keep grade and apparent flatness before and after the arrangement then.The mechanical property of fabric is utilized INSTRON 4411 types (Instron company) universal testing machine, according to the ASTM-D5034-2003 method of testing, fabric is carried out the test of mechanical property.The whiteness test instrument of fabric is the 7000A type of Data Color company, and examination criteria is: D65/10, CIE whiteness.Content of formaldehyde is measured according to the AATCC112-2003 standard.After the light resistance of fabric is carried out the Exposure to Sunlight processing with reference to the AATCC139-2000 standard, measure the whiteness of fabric then.Measurement result sees attached list 1.
Embodiment 2:
With stannous octoate 0.2 gram, polypropylene glycol (number average relative molecular mass 2000) 100 grams, organic hydroxy silicate (the number average relative molecular weight is 30000) 25 grams, hexamethylene diisocyanate 30 grams, dimethylacetylamide 30 grams add 1000mL and have in the reaction bulb of agitator, thermometer and reflux condenser, react 2 hours down for 80～85 ℃ in temperature.Be cooled to 75～80 ℃ then, castor oil 12 grams, dihydroxymethyl fourth carboxylic 10 grams, 75 ℃ of temperature controls, react after 3 hours, be cooled to 45 ℃, add salt forming agent triethylenediamine 5.2 grams, continue reaction and add MEK 25 gram adjusting viscosity after 50 minutes, obtain faint yellow, the thick base polyurethane prepolymer for use as that contains the organosilicon component, in above-mentioned reaction bulb, add 200 gram deionized waters then, under the high-speed stirred condition, emulsion reaction 2 hours, make organic-silicon-modified polyurethane and strengthen resin emulsion, its mass percent concentration is 40%.
The crosslinking agent dihydroxymethyl ethylene-urea that adds 200 grams in above-mentioned reaction bulb adds 40 gram magnesium chlorides and 6 gram glacial acetic acid gradually, adds the deionized water of 235 grams then, continues to stir 2 hours, obtains stable fabric finishing agent, and its solid content is 45%.
Get above-mentioned fabrics finishing agent adding deionized water (its mass ratio is 1: 3) and be made into dressing liquid, employing two is soaked two and is rolled finishing technique, the control pick-up is 80%, 80 ℃ of preliminary dryings 2 minutes, 150 ℃ baked 3 minutes, and cloth specimen was placed after 48 hours, washed according to the AATCC-124 standard, after washing 50 times, the wrinkle of estimating arrangement front and back fabric according to AATCC-88C and AATCC-124 respectively keep grade and apparent flatness.The mechanical property of this fabric is utilized INSTRON 4411 types (Instron company) universal testing machine, according to the ASTM-D5034-2003 method of testing, fabric is carried out the test of mechanical property.The whiteness test instrument of fabric is the 7000A type of Data Color company, and examination criteria is: D65/10, and the CIE whiteness, content of formaldehyde is measured according to the AATCC112-2003 standard.After the light resistance of fabric is carried out the Exposure to Sunlight processing with reference to the AATCC139-2000 standard, measure the whiteness of fabric then.Measurement result sees attached list 2.
Embodiment 3:
With 0.03 kilogram of stannous octoate, 40 kilograms of polyethylene glycol (number average relative molecular mass 4000), 10 kilograms of organic hydroxy silicates (the number average relative molecular mass is 110000), 5 kilograms of glycerol, dicyclohexyl methylene diisocyanate (H
12MDI) 30 kilograms, dimethyl sulfoxide (DMSO) adds 500L for 40 kilograms and has in the reactor of agitator, thermometer and reflux condenser, reacts 2 hours down for 80～85 ℃ in temperature.Be cooled to 75～80 ℃ then, 7 kilograms of dihydromethyl propionic acids, 75～80 ℃ of control reaction temperature, react after 3 hours, be cooled to 50 ℃, add salt forming agent N, 9.4 kilograms of N-dimethyl cyclohexyl amines, continue reaction 45 minutes, add dimethylacetylamide and regulate viscosity for 50 kilograms, obtain colourless, thick base polyurethane prepolymer for use as.Add 148 kilograms of deionized waters in aforesaid reaction vessel, emulsion reaction is 1 hour under high-speed stirred, obtains organic-silicon-modified polyurethane and strengthens resin emulsion, and its mass percent concentration is 30%.
With 80 kilograms of reactors of putting into 300 liters of above-mentioned emulsion, the hexamethylol melamine that adds 25 kilograms of part etherificates then, add 5 kilograms of magnesium chlorides, 0.5 kilogram of citric acid gradually, add 50 kilograms of deionized waters at last, continue to stir 2 hours, make stable fabric finishing agent, its solid content is 30%.(red part is not in protection domain)
Embodiment 4:
With 0.02 kilogram of dibutyl tin laurate, 20 kilograms of polyethylene glycol, 12 kilograms of PTMG 18 kilograms of (number average relative molecular mass 1000), organic hydroxy silicates (the number average relative molecular mass is 30000), polypropylene glycol (PPG303, number average relative molecular mass 300) 8 kilograms, 15 kilograms of isophorone diisocyanate (IPDI), dimethyl formamide add 500L for 50 kilograms and have in the reactor of agitator, thermometer and reflux condenser, in the reaction 2 hours down of 80～85 ℃ of temperature.Be cooled to 75～80 ℃ then, add 4 kilograms of dihydroxymethyl third carboxylics, 75～80 ℃ of temperature controls react after 2.5 hours, be cooled to 45 ℃, add 3.1 kilograms of triethylamines, add MEK and regulate viscosity for 50 kilograms, continue reaction 60 minutes, add 140 kilograms of deionized waters, reaction is 1.5 hours under the high-speed stirred, makes organic-silicon-modified polyurethane and strengthens resin emulsion, and its mass percent concentration is 20%.
Get in the reactor that the above-mentioned emulsion double centner joins another 300 liter, the crosslinking agent dihydroxymethyl dihydroxy ethylene-urea that adds 25 kilograms respectively, add 5 kilograms of magnesium chlorides and 0.6 kilogram of citric acid gradually, 60 kilograms of deionized waters, continuous stirring 1.5 hours, make stable fabric finishing agent, its solid content is 27%.
Embodiment 5:
With 0.1 kilogram of stannous octoate, 20 kilograms of polytetrahydrofuran diols (number average relative molecular mass 4000), 15 kilograms of polypropylene glycols (number average relative molecular mass 4000), 15 kilograms of organic hydroxy silicates (the number average relative molecular mass is 6000), 10 kilograms of polypropylene glycol PPG330 (number average relative molecular mass 3000), 25 kilograms of hexamethylene diisocyanates, dimethylacetylamide adds 500L for 50 kilograms and has in the reaction bulb of agitator, thermometer and reflux condenser, reacts 2.5 hours down for 83～85 ℃ in temperature.Be cooled to 78 ℃ then, add 8 kilograms of dihydroxymethyl third carboxylics, 78 ℃ of temperature controls, react after 2.5 hours, be cooled to 40 ℃, add 3.3 kilograms of salt forming agent triethylenediamines, continue reaction 50 minutes, and the adding MEK is regulated viscosity for 30 kilograms, obtain colourless, the thick polyurethane that contains the organosilicon component and strengthen resin prepolymer, add 200 kilograms of deionized waters, reaction is 1.5 hours under the high-speed stirred, make organic-silicon-modified polyurethane and strengthen resin emulsion, its mass percent concentration is 27.8%.
The above-mentioned polyurethane that contains the organosilicon component is strengthened resin emulsion to join in another 500 liter reactor for 200 kilograms, the crosslinking agent dihydroxymethyl dihydroxy ethylene-urea that adds 60 kilograms, add 14 kilograms of magnesium chlorides and 2 kg of ice acetic acid gradually, add 180 kilograms of deionized waters at last, continue to stir 2 hours, obtain stable fabric finishing agent, its solid content is 25%.
It is to be noted at this; above embodiment only is used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; those skilled in the art can be according to content of the present invention; do not exceeding in protection scope of the present invention, content of the present invention is being made some nonessential and improvement and adjustment others.
The correlated performance index of the fabric of subordinate list 1. after the fabric finishing agent arrangement that embodiment 1 makes
| Test event | Cotton (plain weave) | Cotton (twill) | ||
| Not arrangement | After the arrangement | Not arrangement | After the arrangement | |
| Whiteness (CIE) | 79.0 | 78.5 | 67.2 | 66.8 |
| Folding line keeps grade | 1.0 | 2.5 | 1.0 | 3.0 |
| The apparent flatness of fabric | 1.5 | 3.7 | 1.0 | 3.9 |
| Creasy recovery angle | 142 | 246 | 182 | 263 |
| Ultimate strength conservation rate (%) | 100 | 87 | 100 | 86 |
| Tearing brute force conservation rate (%) | 100 | 86 | 100 | 88 |
| Content of formaldehyde (ppm) | 0 | 52 | 0 | 60 |
| The whiteness of Exposure to Sunlight fabric after 40 hours | 76.2 | 76.0 | 65.8 | 65.3 |
The correlated performance index of the fabric of subordinate list 2. after the fabric finishing agent arrangement that embodiment 2 makes
| Test event | Cotton (plain weave) | Cotton (twill) | ||
| Not arrangement | After the arrangement | Not arrangement | After the arrangement | |
| Whiteness (CIE) | 79.0 | 78.3 | 67.0 | 66.2 |
| Fold keeps grade (washing 50 times for 60 ℃) | 1.0 | 2.6 | 1.0 | 3.0 |
| Apparent flatness (washing 50 times for 60 ℃) | 2.5 | 3.6 | 1.0 | 3.8 |
| Creasy recovery angle | 142 | 248 | 182 | 270 |
| Ultimate strength conservation rate (%) | 100 | 88 | 100 | 86 |
| Tearing brute force conservation rate (%) | 100 | 85 | 100 | 87 |
| Content of formaldehyde (ppm) | 0 | 42 | 0 | 50 |
| The whiteness of Exposure to Sunlight fabric after 40 hours | 76.4 | 76.1 | 66.0 | 65.4 |
Claims (13)
1. the fabric finishing agent with shape memory function is characterized in that, this fabric finishing agent is organic silicon modified polyurethane to be strengthened resin emulsion, crosslinking agent, deionized water react under the effect of catalyst and make.
2. the fabric finishing agent with shape memory function according to claim 1, it is characterized in that described organic silicon modified polyurethane enhancing resin emulsion is the initator with 0.01～0.2 parts by mass, the poly-dihydric alcohol of 30～100 parts by mass, the aliphatic diisocyanate of 5～30 parts by mass, the carboxylic short-chain fat family dihydroxylic alcohols of 5～10 parts by mass, the hydroxy-end capped organic siliconresin of 5～25 parts by mass, the trihydroxy polyalcohol of 5～15 parts by mass, the salt forming agent of 2～10 parts by mass, the prepolymer that the organic solvent of 50～100 parts by mass obtains after reaction and the deionized water of 50～300 parts by mass continue reaction and make.
3. the fabric finishing agent with shape memory function according to claim 1 is characterized in that, described crosslinking agent is to be selected from a kind of in the hexamethylol melamine of dihydroxymethyl dihydroxy ethylene-urea, dihydroxymethyl ethylene-urea and part etherificate.
4. the fabric finishing agent with shape memory function according to claim 1 is characterized in that, described catalyst is to be selected from a kind of in the composition of the composition of magnesium chloride and citric acid and magnesium chloride and glacial acetic acid.
5. the fabric finishing agent with shape memory function according to claim 2 is characterized in that, described initator is to be selected from a kind of in dibutyl tin laurate, stannous octoate and the triethylenediamine.
6. the fabric finishing agent with shape memory function according to claim 2, it is characterized in that described poly-dihydric alcohol is that to be selected from number-average molecular weight be that 2000～6000 polyethylene glycol, number-average molecular weight are that 1000～4000 polytetrahydrofuran diol and number-average molecular weight are a kind of in 1000～4000 the polypropylene glycol.
7. the fabric finishing agent with shape memory function according to claim 2, it is characterized in that described aliphatic diisocyanate is to be selected from a kind of in hexamethylene diisocyanate, dicyclohexyl methylene diisocyanate and the isophorone diisocyanate.
8. the fabric finishing agent with shape memory function according to claim 2, it is characterized in that described trihydroxy polyalcohol is that to be selected from glycerol, castor oil, trimethylolpropane, number-average molecular weight be that 300 polypropylene glycol and number-average molecular weight are a kind of in 3000 the polypropylene glycol.
9. the fabric finishing agent with shape memory function according to claim 2 is characterized in that, described carboxylic short-chain fat family dihydroxylic alcohols is to be selected from a kind of in dihydromethyl propionic acid, dimethylolpropionic acid and the tartaric acid.
10. the fabric finishing agent with shape memory function according to claim 2, it is characterized in that described hydroxy-end capped organic siliconresin is that to be selected from number-average molecular weight be a kind of in 6000～110000 poly dimethyl dimethoxy silane and the poly dimethyl diethoxy silane.
11. the fabric finishing agent with shape memory function according to claim 2 is characterized in that, described salt forming agent is to be selected from triethylamine amine, triethylenediamine and N, a kind of in the N-dimethyl cyclohexyl amine.
12. the fabric finishing agent with shape memory function according to claim 2 is characterized in that, described organic solvent is to be selected from a kind of in dimethyl formamide, dimethylacetylamide, acetone and the MEK.
13. one kind prepares, and any one has the method for the fabric finishing agent of shape memory function among the claim 1-12, it is characterized in that, comprises following steps:
(1) preparation organic silicon modified polyurethane prepolymer: be equipped with agitator, in the reactor of reflux condenser, with organic solvent, initator, poly-dihydric alcohol, aliphatic diisocyanate, hydroxy-end capped organic siliconresin and trihydroxy polyalcohol, reacted 2～3 hours down at 80～85 ℃, adding the continuation under 75～80 ℃ of carboxylic short-chain fat family's dihydroxylic alcohols then reacted 2～2.5 hours, after treating that temperature is reduced to 40～50 ℃, add salt forming agent, continue reaction 30～60 minutes, add organic solvent at last again, regulate viscosity, obtain the organic silicon modified polyurethane prepolymer; The mass fraction of above-mentioned each component is as follows:
Initator 0.01～0.2 parts by mass
Poly-dihydric alcohol 30～100 parts by mass
Aliphatic diisocyanate 5～30 parts by mass
Carboxylic short-chain fat family dihydroxylic alcohols 5～10 parts by mass
Hydroxy-end capped organic siliconresin 5～25 parts by mass
Trihydroxy polyalcohol 5～15 parts by mass
Salt forming agent 2～10 parts by mass
Solvent 50～100 parts by mass
(2) preparation emulsion: in the reactor that contains above-mentioned organic silicon modified polyurethane prepolymer, add 50～300 parts by mass deionized waters, reacted under high-speed stirred 1～2 hour, obtaining mass percent concentration is that 15%～40% organic silicon modified polyurethane strengthens resin emulsion;
(3) preparation of finishing agent: above-mentioned organic silicon modified polyurethane is strengthened resin emulsion, crosslinking agent and deionized water under the effect of catalyst, in reactor, stirred 1～2 hour, mix, obtain solid content after reaction is finished and be 25%～45% finishing agent; The mass ratio of above-mentioned each component is as follows:
Organic silicon modified polyurethane strengthens resin (net content) 1.0
Crosslinking agent 1.0～1.5
Catalyst 0.15～0.45
Deionized water 1.1～5.25.
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| CN101298490B (en) * | 2008-06-13 | 2010-09-01 | 陈春潮 | Memory foam and production method thereof |
| CN102786648A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院化学研究所 | Cross-linking type shape memory polyurethane |
| CN103059797A (en) * | 2012-12-31 | 2013-04-24 | 东莞市粤泰高分子材料有限公司 | Two-component waterborne binding agent with low-surface energy material and preparation method thereof |
| CN103132330A (en) * | 2011-11-25 | 2013-06-05 | 香港纺织及成衣研发中心有限公司 | Textile having shape memory interpenetrating polymer network |
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| CN101298490B (en) * | 2008-06-13 | 2010-09-01 | 陈春潮 | Memory foam and production method thereof |
| CN102786648A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院化学研究所 | Cross-linking type shape memory polyurethane |
| CN102786648B (en) * | 2011-05-20 | 2014-04-23 | 中国科学院化学研究所 | Cross-linking type shape memory polyurethane |
| CN103132330A (en) * | 2011-11-25 | 2013-06-05 | 香港纺织及成衣研发中心有限公司 | Textile having shape memory interpenetrating polymer network |
| CN103132330B (en) * | 2011-11-25 | 2015-04-01 | 香港纺织及成衣研发中心有限公司 | Textile having shape memory interpenetrating polymer network |
| CN103524702A (en) * | 2012-07-04 | 2014-01-22 | 福懋兴业股份有限公司 | Polyurethane, fabric structure with shape memory function and fabrication method of fabric structure |
| CN103059797A (en) * | 2012-12-31 | 2013-04-24 | 东莞市粤泰高分子材料有限公司 | Two-component waterborne binding agent with low-surface energy material and preparation method thereof |
| CN103059797B (en) * | 2012-12-31 | 2014-10-22 | 东莞市粤泰高分子材料有限公司 | Two-component waterborne binding agent with low-surface energy material and preparation method thereof |
| CN103215810A (en) * | 2013-05-09 | 2013-07-24 | 安徽大学 | Finishing liquid for silk wrinkle finishing and silk wrinkle finishing method |
| CN103215810B (en) * | 2013-05-09 | 2015-06-24 | 安徽大学 | Finishing liquid for silk wrinkle finishing and silk wrinkle finishing method |
| CN109281196A (en) * | 2018-09-04 | 2019-01-29 | 嘉兴市嘉盛印染有限公司 | The dyeing and finishing processing method for precious jade imitation memory fabric of partly fluffing cotton |
| CN110685161A (en) * | 2019-11-18 | 2020-01-14 | 江南大学 | Preparation method and use method of fabric after-finishing liquid |
| CN116180452A (en) * | 2023-05-04 | 2023-05-30 | 张家港市德宝化工有限公司 | Multifunctional finishing agent, preparation method thereof and application of multifunctional finishing agent in polyester-cotton tooling fabric |
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