CN1704523A - Reactive aqueous polyurethane fabric finishing agent, its preparation method and application - Google Patents
Reactive aqueous polyurethane fabric finishing agent, its preparation method and application Download PDFInfo
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- CN1704523A CN1704523A CN 200410047647 CN200410047647A CN1704523A CN 1704523 A CN1704523 A CN 1704523A CN 200410047647 CN200410047647 CN 200410047647 CN 200410047647 A CN200410047647 A CN 200410047647A CN 1704523 A CN1704523 A CN 1704523A
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Abstract
This invention relates to an aquosity polyurethane with end-closed or polyurethane structure preparing process and finishing method for preventing the fabric from winkle and distortion, which has a new application being used as finishing agent. The agent adopts prepolymer aggregating and end terminating technology to make out stable aquosity polyurethane with response type end group, whose emulsion particle diameter ranges from 50 to 500 nm and can be adjusted. The invention has functions of high adhesive strength, good impact resistance, hydrolytic resistance and shape memorization.
Description
Technical field
The present invention relates to a kind of novel fabric finishing agent, relate in particular to a kind of fabric finishing agent that constitutes by aqueous polyurethane with end-blocking or unsaturated bond structure.The method that the invention still further relates to the preparation method of this fabric finishing agent and adopt described finishing agent that fabric is put in order.
Background technology
At present traditional crease-proofing textiles containing finishing agent adopts formaldehyde resin mostly, as DMEHU, 2D etc., after with this class after-finishing of textile products agent fabric being put in order, can to a certain degree improve the wrinkle resistant shrinkproof performance of fabric; But there is a very big defective in such finishing agent, promptly can discharge the formaldehyde of grievous injury health in arrangement and wearing process.With epoxy resin, double hydroxyethyl sulfone, silicone based, vinyl monomer grafting agent etc. fabric is put in order, though can solve the release problem of formaldehyde, but because the degree of cross linking that these finishing agents and fabric fibre form is not enough even just simple the coating, make the wrinkle resistant shrinkproof poor durability of fabric, particularly non-refractory washing.Under the catalyst condition, fabric is carried out crosslink finishing, can reach good wrinkle resistant effect with polybasic carboxylic acid.But crosslinked polybasic carboxylic acid has reduced the tearing strength of fabric, produces the yellowing effect simultaneously.
Aqueous polyurethane is a decentralized medium with water, has environmentally safe, does not fire, cost is low etc. a bit, be widely used at coating and adhesive field, but the application facet of textile finishing is less.Adopt plain edition aqueous polyurethane finish fabric, can effectively improve fabric softening and wrinkle resistant shrink resistance, but the effect of this improvement can not be lasting, particularly not water-fast washing, thus limited its application aspect textile finishing.
Have not yet to see the report of relevant shape memory fabrics, the fine wrinkle that fabric produces in dress or washing process needs just can return to original formation state through processes such as flatirons, adopt the response type aqueous polyurethane fabric finishing agent finish fabric of the present invention's preparation, can make fabric obtain functions such as wrinkle resistant and folding line reservation, keep good flexibility, feel degree and preferable whiteness simultaneously, have splendid water-wash resistance, do not have tangible strength loss.After particularly adopting the aqueous polyurethane fabric finishing agent finish fabric with shape memory function that the present invention prepares, fabric can recover the wrinkle that produce in everyday general purpose or the washing in hot water or hot-air, have tangible shape memory function.
As from the foregoing, if can be that a kind of new fabric finishing agent is prepared on the basis with the aqueous polyurethane, overcome present aqueous polyurethane effect not lastingly, not laundry-resistant shortcoming, the above-mentioned advantage that has aqueous polyurethane simultaneously, can make fabric produce shape memory function, then this fabric finishing agent will have broad application prospects.
Summary of the invention
The objective of the invention is to overcome the defective of the wrinkle resistant shrink-resistant agent of above-mentioned these textiless, provide a kind of nontoxic, have good sucting wet air permeability, soft, wrinkle resistant good endurance, fire resistant water-based, a fabric finishing agent with shape memory function.
Therefore, the present invention at first desires to provide a kind of low yellowing, stable, easy to use response type aqueous polyurethane fabric finishing agent;
The present invention also desires to provide above-mentioned response type Synthesis of Waterborne Polyurethane method;
The present invention desires to provide the method for utilizing above-mentioned response type aqueous polyurethane that fabric is put in order simultaneously.
Above-mentioned purpose of the present invention is achieved in that
A kind of fabric finishing agent is characterized in that, it is:
(1) mixture of response type aqueous polyurethane and deionized water, wherein the volume ratio of response type aqueous polyurethane and deionized water is 1: 1～5;
(2) response type aqueous polyurethane, crosslinking agent and mixture of catalysts, wherein response type aqueous polyurethane: crosslinking agent: the weight ratio of catalyst is 1: 0.05～0.2: 0.005～0.01;
Wherein said response type aqueous polyurethane is the aqueous polyurethane with end-blocking or unsaturated bond structure.
Described crosslinking agent can be selected from triethanolamine, diethanol amine, glycerine and trimethylolpropane; Described catalyst can be for being stannous octoate.
Described aqueous polyurethane with end-blocking or unsaturated bond structure prepares by following method: (1) preparation contains the polyurethane prepolymer of hydrophilic group; (2) add end-capping reagent or unsaturated monomer preparation feedback type polyurethane; (3) add ionization reagent and deionized water preparation feedback type aqueous polyurethane;
The response type aqueous polyurethane of gained is a kind of emulsion, and it is interior and adjustable that latex particle size is distributed in the 50-500nm scope, and this regulation and control are to come selectivity to prepare the different emulsions of particle size between 50-500nm by control hydrophilic group content to realize.
In above-mentioned preparation method, described polyurethane prepolymer can be made by polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction, its weight ratio is respectively 1: 0.2～0.5: 0.03～0.06: 0.1～0.5, reaction condition can for: reaction temperature is 50～90 ℃, reaction time is 1～5 hour, makes the polyurethane prepolymer of band carboxyl.
Wherein, described polyisocyanates can be selected from toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); The optional own polyester polyol of described polyalcohol, polyether polyol, Merlon, polycaprolactone, castor oil and epoxy resin; Described hydrophilic monomer chain extender can be dihydromethyl propionic acid; Described retarder thinner can be selected from dimethyl formamide, acetone, butanone, ethyl acetate, dimethyl sulfoxide (DMSO).
End-capping reagent or unsaturated monomer are joined in the above-mentioned polyurethane prepolymer, the isocyanate end of prepolymer is carried out end-blocking, make reaction type polyurethane.Described end-capping reagent can be the compound of the active hydrogen atom that contains simple function group, described unsaturated monomer can be maleic anhydride and the methacrylate or the acrylate that have hydroxyl, the condition of preparation feedback type polyurethane can for: reaction temperature is 50～90 ℃, and the reaction time is 1～5 hour.
Wherein, described end-capping reagent can be selected from diacetylmonoxime, sodium hydrogensulfite, gaultherolin, phenmethylol, septichen, ethyl acetoacetate, caprolactone; Described unsaturated monomer can be selected from maleic anhydride, hydroxyethyl methylacrylate, hydroxy-ethyl acrylate.
Add in the ionization reagent and above-mentioned reaction type polyurethane, reaction temperature is 40～50 ℃, and the reaction time is 1～2 hour, and the ratio of carboxyl is 1 in ionization reagent and the polyurethane: (0.5～1.1); Make ionic polyurethanes, in ionic polyurethanes, add deionized water then, under stirring, in water, disperses high-tenacity, distillation removes solvent, make self-emulsifying and contain end-blocking or the response type aqueous polyurethane of two keys, it is a kind of anionic emulsion, and it is adjustable that its latex particle size is distributed in 50-500nm, and the polyurethane solid content is 10～40%.
Above-mentioned used ionization reagent can be tertiary amine.
The present invention also provides a kind of method that fabric is put in order, and it is to utilize above-mentioned response type aqueous polyurethane to finish as fabric finishing agent, and fabric wherein can be selected from cotton fiber, flax fibre, synthetic fiber, reach BLENDED FABRIC.
When aqueous polyurethane of the present invention is applied in textile finishing, can use separately, also can use with blendings such as crosslinking agent, catalyst, described crosslinking agent can be triethanolamine, diethanol amine, glycerine and trimethylolpropane; Described catalyst is a stannous octoate.Do not contain or only contain the solvent of minute quantity in the aqueous polyurethane, environmentally safe is to human body nonhazardous effect; The existence of carbamate makes it have strong polarity and adhesive strength in the polyurethane molecular chain, shows good compatibility and adhesion with fabric fibre.
Aqueous polyurethane of the present invention can activate under certain condition crosslinked or graft reaction takes place, thereby be a kind of response type aqueous polyurethane owing to contain closed-end structure or unsaturated bond.Described aqueous polyurethane can possess or not possess the function of shape memory.
The above-mentioned method that fabric is put in order can comprise the steps: that the above-mentioned finishing agent two of (1) employing soaks two and rolls the method finish fabric; (2) use flocculating agent that fabric is carried out the back crosslinking Treatment, or finish fabric behind the employing plasma technology, thereby fabric is carried out post processing.
With above-mentioned end-sealed type polyurethane finishing agent with after a certain amount of water (volume ratio of aqueous polyurethane and deionized water is 1: 1～5) dilution, soak two with two and roll the method finish fabric, pick-up rate 70%～120%, (80～110 ℃ of dryings, 1～3 minute), bake and bank up with earth (140～170 ℃, 2～5 minutes) back and obtain product.Particularly bake and bank up with earth the stage in oven dry, polyurethane is separated end-blocking and is discharged isocyanate group, isocyanate group can self or with crosslinking agent take place crosslinked or under certain catalytic condition with fabric fibre on activity hydroxy react, this polyurethane finishing agent also might infiltrate the fabric fibre inside deposition and solidify, thereby pay fabric good wrinkle resistant durability, water-wash resistance, DIMENSIONAL STABILITY, fabric has good hand feeling, there is not obvious strength loss, 160 ℃ of flatirons did not have obvious flavescence in 3 minutes, showed good finishing effect.
Fabric to above-mentioned arrangement carries out post processing with flocculating agent, can further improve do, wet pincher elasticity, washability and the durability of fabric, and described flocculating agent can be an aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, various slaines such as sylvite; Or hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, various organic or inorganic acid such as acetate; Or the mixture that is constituted in the above-mentioned flocculating agent.The flocculating agent of configuration 1～5% soaks one with one and rolls method post processing fabric, and temperature is at 100～120 ℃, and fabric has good wrinkle durability, resistance to water and chemical-resistant.
Also can adopt the further post processing fabric of plasma technology, chamber pressure is 0.3～1.5*133.32Pa, power 300W, irradiation time 30～300S, under the effect of oxygen gas plasma, two keys of polyurethane are opened polymerization, form to a certain degree crosslinked, the spike that simultaneously two keys are opened back formation may combine with fabric face, form grafting to a certain degree, the raising of this crosslinked and very big degree of grafting the adhesive strength between fabric and the polyurethane, show good wettability, ABRASION RESISTANCE, water-wash resistance and wrinkle durability.
With the above-mentioned aqueous polyurethane finish fabric that possesses shape memory function, fabric when water temperature during at 10 ℃～90 ℃, can return to original formation state in washing process, can wear without flatiron.
Innovation part of the present invention is first end-sealed type and unsaturated type polyurethane to be applied to textile finishing, and adopt and to add thermal deblocking end or plasma post technology and make and take place to produce chemistry by graft reaction between internal crosslinking and polyurethane and fabric between polyurethane molecular and connect, significantly improve the adhesive strength of polyurethane and fabric, make fabric obtain good wrinkle resistant durability, water-wash resistance and DIMENSIONAL STABILITY.Fabric can recover the wrinkle of generation in everyday general purpose or the washing in hot water or hot-air, have tangible shape memory function.
Response type aqueous polyurethane fabric finishing agent of the present invention can give fabric good functions such as wrinkle resistant and folding line reservation, in 10～90 ℃ of water, has good especially recovery function, has high water-wash resistance simultaneously, the washing of hot water and washing machine below 60 ℃ still keeps good spreading and folding line to keep more than 50 times, be a kind of good fabric finishing agent therefore.
Below, in conjunction with specific embodiments the present invention is described in further detail.Yet following embodiment only is not to be for the present invention being made restriction, also should not limiting the present invention to the disclosed particular content of embodiment for a better understanding of the present invention.
The specific embodiment
Embodiment 1
With 100g polypropylene glycol (molecular weight 2000; dry), 40g isophorone diisocyanate and 6.7g dihydromethyl propionic acid drop into flask at the bottom of the four-hole garden that reflux condensing tube, thermometer, mixer are housed successively; feed nitrogen protection; stir; add solvent dimethylformamide 30ml;, 75 ℃ of reactions of constant temperature 2-3 hour make the PU performed polymer.Be warming up to 85 ℃ and add the 6g methyl ethyl ketoxime, add two dibutyl tin laurate catalyst, reacted 2 hours.Reduce the temperature to 50 ℃ of reactant, add the triethylamine neutralization of 4.5g, and add water and stir phase inversion, obtain solid content and be 25% end-sealed type aqueous polyurethane.
Embodiment 2
With 50g PolyTHF (molecular weight 2000; dry), 22g methyl diphenylene diisocyanate and 6g dihydromethyl propionic acid drop into flask at the bottom of the four-hole garden that reflux condensing tube, thermometer, mixer are housed successively; feed nitrogen protection; stir; add butanone solvent 50ml;, 80 ℃ of reactions of constant temperature 2-3 hour make the PU performed polymer.Be warming up to 85 ℃ and add the 2g hydroxyethyl methylacrylates, react and levy absworption peak (2270cm-1) to the NCO Gent and disappear.Reduce the temperature to 50 ℃ of reactant, add the triethylamine neutralization of 4.5g, and add water and stir phase inversion, butanone is extracted in decompression at last out, obtains solid content and be 30% double bond containing aqueous polyurethane.
Embodiment 3
With 95g polycaprolactone (molecular weight 4000; dry); 21g methyl diphenylene diisocyanate, 5.5g dihydromethyl propionic acid and 100ml solvent dimethylformamide; drop into flask at the bottom of the four-hole garden that reflux condensing tube, thermometer, mixer are housed successively; feed nitrogen protection; stir, 80 ℃ of reactions of constant temperature 2-3 hour make the PU performed polymer.Be warming up to 90 ℃ and add the 4g phenmethylols, react and levy absworption peak (2270cm-1) to the NCO Gent and disappear.Reduce the temperature to 50 ℃ of reactant, add small amount of acetone or do not need solubilizer.Add the triethylamine neutralization of 4g, and add water stirring phase inversion, the acquisition solid content is 15% end-sealed type aqueous polyurethane.
Embodiment 4
The solid content of getting embodiment 1 is 25% aqueous polyurethane, (its weight ratio is 1: 0.07: 0.005: 3) be made into dressing liquid to add triethanolamine curing agent, stannous octoate catalyst and deionized water, to treat that finish fabric is immersed in the dressing liquid, soaking two roll process with two puts in order, pick-up is 80%, 100 ℃ of oven dry, finalized the design 2 minutes for 150 ℃, cloth specimen was placed after 30 days, keep grade and spreading with U.S. AATCC evaluation criterion test wrinkle, carry out the Mechanics Performance Testing of fabric with fabric strength machine.
| Cotton | Gauze | |||
| Former state | After the arrangement | Former state | After the arrangement | |
| Whiteness | ??85 | ??85 | ??78 | ??78 |
| Folding line keeps grade (50 ℃ of hot water) | ??1.0 | ??3.5 | ??1.0 | ??2.0 |
| Fabric spreading (50 ℃ of hot water) | ??2.5 | ??4.0 | ??1.0 | ??1.5 |
| Creasy recovery angle (doing) | ??188 | ??236 | ??140 | ??150 |
| Tearing brute force retention rate (%) | ??100 | ??104 | ??100 | ??99 |
Embodiment 5
The solid content of getting embodiment 1 is 25% aqueous polyurethane, water with 3 times of weight is made into dressing liquid, to treat that finish fabric is immersed in the dressing liquid, soak two roll process with two and put in order, pick-up is 80%, 100 ℃ of oven dry, finalized the design 2 minutes for 150 ℃, cloth specimen was placed after 30 days, kept grade and spreading with U.S. AATCC evaluation criterion test wrinkle, carried out the Mechanics Performance Testing of fabric with fabric strength machine.
| Cotton | Gauze | |||
| Former state | After the arrangement | Former state | After the arrangement | |
| Whiteness | ??85 | ??85 | ??78 | ??78 |
| Folding line keeps grade (50 ℃ of hot water) | ??1.0 | ??3.2 | ??1.0 | ??1.8 |
| Fabric spreading (50 ℃ of hot water) | ??2.5 | ??4.3 | ??1.0 | ??2.0 |
| Creasy recovery angle (doing) | ??188 | ??241 | ??140 | ??170 |
| Tearing brute force retention rate (%) | ??100 | ??98 | ??100 | ??98 |
Embodiment 6
The solid content of getting embodiment 2 is 30% aqueous polyurethane, adds the water dilution of 3 times of weight, will treat that finish fabric is immersed in the dressing liquid, soaking two roll process with two puts in order, pick-up is 80%, 100 ℃ of oven dry, finalizes the design 2 minutes for 150 ℃, adopt the further post processing fabric of plasma technology, chamber pressure is 1.0*133.32Pa, power 300W, irradiation time 60S, cloth specimen was placed after 30 days, kept grade and spreading with U.S. AATCC evaluation criterion test wrinkle.
| Cotton | Gauze | |||
| Former state | After the arrangement | Former state | After the arrangement | |
| Creasy recovery angle (doing) | ??188 | ??244 | ??140 | ??160 |
| 20 creasy recovery angles (doing) of soaping | ??153 | ??220 | ??130 | ??147 |
| Fabric spreading (50 ℃ of hot water) | ??2.5 | ??4.0 | ??1.0 | ??2.5 |
| 20 the fabric spreadings (50 ℃ of hot water) of soaping | ??2.4 | ??3.8 | ??1.0 | ??2.3 |
Embodiment 7
The solid content of getting embodiment 2 is 30% aqueous polyurethane, add the water dilution of 3 times of weight, will treat that finish fabric is immersed in the dressing liquid, soak two roll process with two and put in order, pick-up is 80%, the magnesium chloride brine flocculating agent of configuration 2% was finalized the design 2 minutes in 100 ℃ of oven dry for 150 ℃, soak one with one and roll method post processing fabric, finalized the design 3 minutes for 120 ℃, place after 30 days, keep grade and spreading with U.S. AATCC evaluation criterion test wrinkle.
| Cotton | Gauze | |||
| Former state | After the arrangement | Former state | After the arrangement | |
| Creasy recovery angle (doing) | ??188 | ??250 | ??140 | ??180 |
| 20 creasy recovery angles (doing) of soaping | ??153 | ??170 | ??130 | ??135 |
| Fabric spreading (50 ℃ of hot water) | ??2.5 | ??4.0 | ??1.0 | ??2.7 |
| 20 the fabric spreadings (50 ℃ of hot water) of soaping | ??2.4 | ??2.8 | ??1.0 | ??1.5 |
Embodiment 8
The solid content of getting embodiment 3 is 15% aqueous polyurethane, the deionized water that adds 1 times of weight is made into dressing liquid, to treat that finish fabric is immersed in the dressing liquid, soaking two roll process with two puts in order, pick-up is 75%, 100 ℃ of oven dry, finalizes the design 2 minutes for 150 ℃, cloth specimen was placed after 30 days, with the spreading of U.S. AATCC evaluation criterion test fabric.
| Cotton | Gauze | |||
| Former state | After the arrangement | Former state | After the arrangement | |
| Fabric spreading (15 ℃ in cold water) | ??2.5 | ??3.0 | ??1.0 | ??1.5 |
| Fabric spreading (25 ℃ in cold water) | ??2.4 | ??3.0 | ??1.0 | ??1.5 |
| Fabric spreading (40 ℃ of hot water) | ??2.4 | ??3.8 | ??1.0 | ??2.2 |
| Fabric spreading (60 ℃ of hot water) | ??2.5 | ??4.3 | ??1.0 | ??2.7 |
Above result shows, adopt response type aqueous polyurethane fabric finishing agent finish fabric of the present invention, plasma technology post processing fabric particularly, the application of its finishing technique and whole finishing effect all are brand-new breakthroughs, it has following characteristics:
● described response type aqueous polyurethane uses pre-polymerization method and end blocking method preparation, has unsaturated or closed-end structure, and can react with fabric at certain condition produces the chemistry connection;
● adopt above-mentioned waterborne blocked polyurethane to cooperate crosslinking agent and catalyst finish fabric, or adopt above-mentioned unsaturated type polyurethane to cooperate plasma technology post processing technique, make between polyurethane and the fabric to produce the grafting reaction, also there be to a certain degree chemical crosslinked in polyurethane itself simultaneously;
● fabric has wrinkle resistant, shrinkproof good endurance after the described arrangement, comfortable feel, good moisture-penetrable ventilated property, the characteristics that water-wash resistance is good;
● described arrangement agent is environmentally friendly, formaldehydeless release in production and the wearing process.
● use shape memory aqueous polyurethane arrangement agent, can also make fabric in hot water or hot-air, can recover the wrinkle that produce in daily dress or the washing, have obvious shape memory function.
Claims (16)
1. a fabric finishing agent is characterized in that, it is:
(1) mixture of response type aqueous polyurethane and deionized water, wherein the volume ratio of response type aqueous polyurethane and deionized water is: 1: 1～5, or
(2) response type aqueous polyurethane, crosslinking agent and mixture of catalysts, wherein response type aqueous polyurethane: crosslinking agent: the weight ratio of catalyst is 1: 0.05～0.2: 0.005～0.01;
Wherein said response type aqueous polyurethane is the aqueous polyurethane with end-blocking or unsaturated bond structure.
2. the described fabric finishing agent of claim 1, wherein:
Described crosslinking agent is selected from triethanolamine, diethanol amine, glycerine and trimethylolpropane;
Described catalyst is a stannous octoate.
3. the preparation method of a fabric finishing agent, it comprises following step:
(1) prepare aqueous polyurethane with end-blocking or unsaturated bond structure:
(1a) preparation contains the polyurethane prepolymer of hydrophilic group;
(1b) add end-capping reagent or unsaturated monomer preparation feedback type polyurethane;
(1c) add ionization reagent and deionized water preparation feedback type aqueous polyurethane;
The response type aqueous polyurethane of gained is a kind of emulsion, and it is interior and adjustable that latex particle size is distributed in the 50-500nm scope;
(2) utilize the aqueous polyurethane with end-blocking or unsaturated bond structure of the method preparation of above-mentioned (1) to prepare fabric finishing agent, it passes through:
(2a) response type aqueous polyurethane and deionized water are that 1: 1～5 ratio is mixed and made with volume ratio, perhaps
(2b) response type aqueous polyurethane: crosslinking agent: the weight ratio of catalyst is that 1: 0.05～0.2: 0.005～0.01 ratio is mixed and made.
4. the described preparation method of claim 3, wherein in (2b) step:
Described polyurethane prepolymer is that 1: 0.2～0.5: 0.03～0.06: 0.1～0.5 polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction make by weight ratio, reaction condition is: reaction temperature is 50～90 ℃, and the reaction time is 1～5 hour.
5. the described preparation method of claim 4, wherein:
(1) described polyisocyanates is selected from TDI, MDI, HDI, IPDI, TMXDI;
(2) described polyalcohol has been selected from polyester polyol, polyether polyol, Merlon, polycaprolactone, castor oil and epoxy resin;
(3) described hydrophilic monomer chain extender is a dihydromethyl propionic acid;
(4) described retarder thinner is selected from dimethyl formamide, acetone, butanone, ethyl acetate, dimethyl sulfoxide (DMSO).
6. the described preparation method of claim 3, wherein in step (1b):
Described end-capping reagent is the compound that contains the active hydrogen atom of simple function group;
Described unsaturated monomer is maleic anhydride and methacrylate or the acrylate that has hydroxyl;
The condition of preparation feedback type polyurethane is: reaction temperature is 50～90 ℃, and the reaction time is 1～5 hour.
7. the described preparation method of claim 6, wherein:
Described end-capping reagent is selected from diacetylmonoxime, sodium hydrogensulfite, gaultherolin, phenmethylol, septichen, ethyl acetoacetate, caprolactone;
Described unsaturated monomer is selected from maleic anhydride, hydroxyethyl methylacrylate, hydroxy-ethyl acrylate.
8. the described preparation method of claim 3, wherein in step (1c):
(1) add ionization reagent earlier in reaction type polyurethane solution and prepare ionic polyurethanes, reaction temperature is 40～50 ℃, and the reaction time is 1～2 hour, and the ratio of carboxyl is 1 in ionization reagent and the polyurethane: (0.5～1.1);
(2) add deionized water preparation feedback type aqueous polyurethane then in ionic polyurethanes, it is a kind of emulsion, and it is adjustable that latex particle size is distributed in 50-500nm, and the polyurethane solid content is 10～40% in the gained response type aqueous polyurethane.
9. the described preparation method of claim 8, wherein used ionization reagent is a tertiary amine.
10. method that fabric is put in order, it comprises and adopts any described fabric finishing agent of claim 1-2 or adopt fabric finishing agent of any described method preparation of claim 3-9 by two two methods of rolling of soaking fabric to be put in order.
11. the described method that fabric is put in order of claim 10, it also comprises the step of fabric being carried out post processing, and wherein said post-processing step is:
(i) use flocculating agent that fabric is carried out the back crosslinking Treatment, or
(ii) adopt finish fabric behind the plasma technology.
12. the described method of claim 11, wherein:
In the step of back crosslinking Treatment, described flocculating agent is selected from slaine, organic or inorganic acid and composition thereof.
13. the described method of claim 12, wherein:
Described slaine is an aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, or sylvite;
Described inorganic acid is a hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid;
Described organic acid is an acetate.
14. the described method of claim 11, wherein the condition of finish fabric is behind the plasma technology:
Oxygen atmosphere, chamber pressure are 0.3～1.5
*133.32Pa, power 300W, irradiation time 30～300S.
15. the described method of claim 10, wherein two two conditions of rolling the method finish fabric of soaking are:
Fabric two soaks two and rolls padding finishing liquid, pick-up rate 70%～120%;
80～110 ℃ of oven dry were baked and banked up with earth 2～5 minutes for 1～3 minute, 140～170 ℃.
16. any described method of claim 10-15, wherein said fabric are selected from cotton fiber, flax fibre, synthetic fiber, reach BLENDED FABRIC.
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