CN107083684A

CN107083684A - The technique and equipment without chlorine anti-shrinking for raw wool and product

Info

Publication number: CN107083684A
Application number: CN201610086083.XA
Authority: CN
Inventors: 姚金波; 刘建勇; 万忠发; 张伟民; 杨万君
Original assignee: Tianjin Lvyuan Tianmei Science And Technology Co Ltd
Current assignee: Tianjin Lvyuan Tianmei Science And Technology Co Ltd
Priority date: 2016-02-15
Filing date: 2016-02-15
Publication date: 2017-08-22

Abstract

The present invention relates to the technique and equipment without chlorine anti-shrinking for raw wool and product.Specifically, present invention process is included without steps such as chlorine anti-shrinking, washing, albumen enzyme-deactivating, soft treatment, dehydration, drying, wherein from by protease and specific organic phosphine compound etc. constitute without chlorine catalyst system and catalyzing, so as to cooperate with the scale layer for efficiently removing wool surface, it is modified scale layer, so that reaching improves the shrinkproof performance of wool product.Present invention process can replace the shrinkproof method of chlorination of the prior art completely, not only environment-friendly and low for equipment requirements, can continuous operation, suitable large-scale industrialized production.

Description

The technique and equipment without chlorine anti-shrinking for raw wool and product

Technical field

The present invention relates to wool product manufacture field, more particularly to for the shrinkproof without chlorine of raw wool and product The technique and equipment of processing, particularly a kind of continuous processing technology without chlorine wool tops and wool product anti-shrinking And equipment.

Background technology

Wool is the important source material of textile industry, and it has many good characteristics, such as elasticity is good, hygroscopicity is strong, It is difficult to stain, warmth retention property is good, gloss is soft.Wool has one as a kind of natural protein fibre on surface The main scale layer overlapped such as fish scale being made up of keratin protein of layer, due to the friction along forbidden lamella piece direction Coefficient is different, under external force repeated action, wool fiber will mutually intert, tangles, hand over volume, felting and produce Fulling milling.Though fulling milling makes wool fabric with the good effect of attractive appearance, the abundant soft, thermal property of feel, Also wool fabric is made easily to produce dimensional contraction and deformation in washing process.Therefore, it is raising wool textile Shrinkproof, to improve the dimensional stability of woolen product, makes the product can reach " machine washable " effect, Need to carry out surface scale modification to wool fiber from source.

At present, the main method of wool surfaces scale modification anti-shrinking has：Chloridising, cladding process, protease Method etc..It is most widely organohalogen compounds AOX (its produced by chloridising anti-shrinking chloridising processing procedure For absorbable organohalogen compounds) can severe contamination environment.

Chinese patent CN201010605809.9 report by by potassium permanganate and DCCA in the form of catalyst It is added in clear water, then is passed through chlorine, shrinkproof stripping squama technique is carried out to wool top, this method makes chlorine usage amount 30% is reduced on the original basis.Although this method is improved traditional chlorinated method, but still uses chlorine Gas, can still cause serious environmental pollution.Cladding process in wool surfaces by depositing one layer of resin film so that sheep Hair surface scale space is tamped so that wool surfaces are smoothened, and then reach the low-fiber mantle friction of drop Effect.Although this processing method can improve the felting performance of fiber to a certain extent, it can have a strong impact on The feel of wool fabric, and the deficiency of generally existing poor durability.Protease method is to utilize proteases on wool The hydrolysis of fiber surface macromolecular peptide bond is so that the generation such as scale and cell membrane complexes of wool part is molten Solution, so as to reach the purpose for partly or entirely removing scale.This processing method has that treatment conditions are gentle, section The advantages of about energy and reduction pollute, is a kind of environmentally friendly wool anti-felting finishing method.But, individually adopt The shrinkproof result handled with proteases on wool can not also meet be actually needed at present, therefore much use egg When white enzyme carries out bio-modification processing to wool, all need first to carry out pre-treatment (as used strong oxidizer high to the wool Potassium manganate etc. is pre-oxidized or pre-processed with chlorinated solvent).At above-mentioned pre-treating method is present Reason overlong time, enzyme easy in inactivation, treatment conditions are difficult to the deficiencies such as control.

In addition, although there is researcher to attempt exploitation for raw wool without chlorine anti-shrinking technique, but deposit In following shortcoming：(a) processing time length (can not be foreshortened in the case where ensureing processing quality within 30 minutes)； (b) treating capacity is limited, is not suitable for industry application；(c) processing quality fluctuation is big, it is difficult to obtain treatment effect equal One wool converted products.Therefore, in China etc., main raw wool processes state, at present still not in reality The situation that raw wool is processed without chlorine anti-shrinking technique is used in production.

In summary, this area is badly in need of that a kind of environment-friendly, technique of exploitation is simple and easy to control, anti-felting effect is held Long, treatment effeciency high (or quick) and the wool shrinkproof handling process of suitable large-scale production.

The content of the invention

It is an object of the invention to provide a kind of environment-friendly, technique is simple and easy to control, anti-felting effect is lasting, Treatment effeciency high (or quick) and the wool shrinkproof handling process for being adapted to large-scale production.

The first aspect of the present invention there is provided it is a kind of be used for the anti-shrinking agent without chlorine anti-shrinking, it is described shrinkproof Inorganic agent is included：(a) optional solvent；(b) protease；Organic phosphine compound shown in formula A (c) and Optional inorganic salts；

P-(X)₃ A

In formula, each X is independently selected from the following group：Substituted or unsubstituted C1-C10 alkyl, wherein described takes Acute pyogenic infection of finger tip has one or more substituents being selected from the group：- OH ,-COOH (carboxyl), C2-C8 ester groups ,-SH, - CN, C1-C3 alkyl, C1-C3 alkoxies；

And at least one X is the substituted C1-C10 alkyl with-OH or COOH substituents；

The weight ratio of described protease and the organic phosphine compound is 0.2-10：0.5-20；

And protease is selected from the group in the anti-shrinking agent：Neutral proteinase, alkali protease or its group Close.

In another preference, it is described without chlorine processing include carrying out raw wool and/or wool product desquamation/ Anti-shrinking.

In another preference, described raw wool includes wool tops.

In another preference, described protease and the weight ratio of the organic phosphine compound are 0.5-5： 1-10；More preferably it is 1-5：1-10.

In another preference, described anti-shrinking agent also contains alkali compounds.

It is preferred that described alkali compounds is selected from the group：Alkali metal hydroxide, alkaline earth metal hydroxide, The carbonate of alkali metal, the carbonate of alkaline-earth metal, the bicarbonate of alkali metal, the bicarbonate of alkaline-earth metal, Or its combination.

In another preference, described alkali compounds is selected from the group：NaOH、KOH、Ca(OH)₂、Na₂CO₃、 K₂CO₃Or its combination.

In another preference, described " no chlorine " refer to the anti-shrinking agent not comprising organochlorine compound, Also the hypochlorous acid class compound being selected from the group is not included：Containing ClO^-The compound of ion (root), ClO can be produced^-From The compound (such as chlorine) of son.

In another preference, in the anti-shrinking agent, the content of the hypochlorous acid class compound≤ 0.05wt%, preferably≤0.01wt%, more preferably≤0.001wt%, are most preferably about 0.

In another preference, described anti-shrinking agent is liquid (i.e. treatment fluid).

In another preference, described solvent is selected from the group：Water or aqueous solvent.

In another preference, described anti-shrinking agent is solid, semisolid, and can passed through when applying Addition solvent (such as water) is reconstructed into treatment fluid.

In another preference, in described treatment fluid (or treatment fluid of reconstruct), the organic phosphine compound Concentration is 1-10g/L, preferably 1.5-10g/L, more preferably 5-10g/L.

In another preference, in described treatment fluid (or treatment fluid of reconstruct), the concentration of the protease is 0.1-25g/L, preferably 0.2-10g/L, more preferably 0.5-5g/L.

In another preference, in described treatment fluid (or treatment fluid of reconstruct), the concentration of inorganic salts is 0.01-10g/L, preferably 0.05-5g/L, more preferably 0.1-2g/L

In another preference, 2 X are identicals.

In another preference, 3 X are identicals.

In another preference, 3 X are different.

In another preference, each X is independently selected from the following group：Substituted or unsubstituted C1-C6 alkyl.

In another preference, described C1-C10 alkyl includes C1-C10 alkyl, C2-C10 alkenyls, C2-C10 Alkynyl and C3-C8 cycloalkyl.

In another preference, described C1-C10 alkyl includes C1-C10 alkyl and C3-C8 cycloalkyl.

In another preference, when described anti-shrinking agent contains selected from protease, organic phosphine compound, nothing When machine salt, one or more components of surfactant, its content is as follows：

In another preference, the consumption (wt) of protease described in the anti-shrinking agent is less than or equal to (≤) institute State the consumption (wt) of organic phosphine compound.

In another preference, when the anti-shrinking agent is the aqueous solution or is reconstructed into the aqueous solution, its pH is 6.5-12, preferably 7-11.5, are more preferably 7.5-10.5.

In another preference, the protease is alkali protease.

In another preference, described organic phosphine compound is water-soluble aliphatic organic phosphine compound.

In another preference, it is molten in 25 DEG C of 100g water that described water solubility refers to the organic phosphine compound Xie Du >=0.1g, preferably >=0.5g, such as more preferably >=2g, 0.1-10g or 0.5-5g.

In another preference, the organic phosphine compound has formula：

P-(R₁-R₂)₃ I

Wherein,

R₁For substituted or unsubstituted C2-C8 alkylidenes (preferably C1-C6 alkylidenes)；And/or

R₂It is selected from the group：- OH ,-COOH or C2-C8 ester groups, alkali metal or alkaline-earth metal.

In another preference, in compound shown in Formulas I,

R₁For unsubstituted C1-C6 alkylidenes；And/or

R₂It is selected from the group：- OH and-COOH.

In another preference, R₁It is selected from the group：Methylene, ethylidene, propylidene, butylidene, pentylidene, Hexylidene or its combination.

In another preference, the aliphatic organic phosphine compound is selected from the group：Three (3- hydroxypropyls) phosphines, three (3- carboxylics propyl group) phosphine, three (2- ethoxys) phosphines, three (4- carboxylics butyl) phosphines or its combination.

In another preference, described inorganic salts are selected from the group：Ca salt, Mg salt, Na salt, Zn salt, Al Salt, Ba salt or its combination.

In another preference, described inorganic salts are selected from the group：Hydrochloride, sulfate, carbonate, carbonic acid Hydrogen salt, nitrate, nitrite, phosphate, dibasic alkaliine, dihydric phosphate or its combination.

In another preference, the inorganic salts are selected from the group：Mg(NO₃)₂, sodium phosphate, calcium monohydrogen phosphate, CaCl₂、 Or its combination.

In another preference, the surfactant is selected from the group：Nonionic surfactant, anion table Face activating agent, cationic surfactant, amphoteric surfactant or its combination.

In another preference, described anti-shrinking agent also contains pH buffer.

In another preference, the content of the pH buffer is 0.1-10g/, preferably 0.2-5g/L.

In another preference, the pH buffer is selected from the group：Disodium hydrogen phosphate-sodium dihydrogen phosphate buffer (PBS)、NaHCO₃-Na₂CO₃Buffer or its combination.

In another preference, the anti-shrinking agent is liquid at 25-80 DEG C.

In another preference, the anti-shrinking agent is liquid at temperature used below：30-70 DEG C, compared with It is goodly 40-60 DEG C, is more preferably 45-55 DEG C.

In another preference, in the processing without chlorine, processed wool top specification is 10-30g/ meters/root hair Bar, preferably 20-25g/ meters/root wool top.

In another preference, in the processing without chlorine, parallel to handle n root wool tops simultaneously, wherein n is 10-100 roots, 20-70 roots, preferably 30-60 roots.

In the second aspect of the present invention there is provided a kind of anti-shrinking equipment without chlorine wool tops or wool product, The equipment includes：

Multiple squeeze device, the multiple squeeze device includes that n is independent, continuously arranged to pad device, institute State and respectively pad device including soaking compartment and rolling roller, wherein, described soaking compartment is used to place without chlorine anti-shrinking Anti-shrinking liquid so that pending wool tops or wool product is soaked in described treatment fluid；And it is described Rolling roller is used for the soaking wool tops or wool product of rolling, and the wool after the progress rolling of upstream rolling roller Bar or wool product, are sequentially entered downstream and are padded the soaking compartment and rolling roller of device, thus repeat the immersion and Rolling is handled, and wherein n is 2-20 positive integer；

Water washing device, for washing the wool top or wool product through padding, forms the wool top through washing or sheep Woolen；

Enzyme-deactivating device, goes out for the protease alkalescence to the residual in the wool top through washing or wool product Processing living, forms wool top or wool product through enzyme-deactivating；

Optional soft treatment device, for the wool top or wool product handled described in soft treatment through enzyme-deactivating, Form wool top or wool product through soft treatment；With

Optional drier, for wool top or wool product through soft treatment obtained by previous step to be dried Processing.

In the third aspect of the present invention there is provided a kind of Antishrinking method without chlorine wool tops or wool product, Comprise the following steps：

(a) provide it is pending without chlorine wool tops or wool product, and described in first aspect present invention without chlorine sheep The anti-shrinking agent of wool top or wool product；

(b) pending carried out n to described with described anti-shrinking agent without chlorine wool tops or wool product and padded again Processing, so as to obtain the wool product through padding, wherein n is 2-20 positive integer；

(c) nothing through washing is obtained through padding without chlorine wool tops or wool product progress washing process to described Chlorine wool tops or wool product；

(d) through washing enzyme-deactivating processing is carried out without chlorine wool tops or wool product to described, so as to obtain through anti- Contracting processing without chlorine wool tops or wool product.

In another preference, n is 3-10 positive integer.

, can be extraly with only among described n pads processing again and/or afterwards in another preference Treatment fluid containing protease but without the organic phosphine compound is handled.

In another preference, total time T≤15 minute for padding processing of the step (b), preferably≤ 10 minutes, more preferably≤5 minute, most preferably≤3 minute.

In another preference, pending described in step (a) is flattened without chlorine wool tops or wool product Change processing.

In another preference, the composition of the wool tops is selected from the group：Wool, cashmere or its combination.

In another preference, the specification of the wool tops is 40-150 branch, preferably 40-120 branch, more It is 56-100 branch goodly.

In another preference, in step (b), the temperature of described infiltration/roll compacting operation is 5-80 DEG C, compared with 10-60 DEG C of good ground, most preferably more preferably 25-50 DEG C, 40-50 DEG C.

In another preference, in step (b), what described infiltration/roll compacting was operated does not limit especially total time System, usually 1-20 minutes, preferably 1-10 minutes, be more preferably 1-5 minutes.

In another preference, in step (c), washing temperature is not particularly limited, usually 5-60 DEG C, Preferably 10-50 DEG C, more preferably 20-40 DEG C, be most preferably 20-30 DEG C.

In another preference, in step (c), washing time is not particularly limited, usually 30 seconds -120 Minute, preferably -60 minutes 1 minute, be more preferably 2-30 minutes.

In another preference, described enzyme-deactivating operation can be using conventional inactivation condition, as long as by residual Albumen enzyme-deactivating or basic inactivation.

In another preference, in the process, without using hypochlorous acid class compound.

In another preference, in step 2) in, the volume of the anti-shrinking liquid and the pending wool system The weight ratio of product is not particularly limited, as long as pending wool top or wool product can be infiltrated.

In another preference, in step 2) in, the number of times padded may be the same or different, preferably identical.

In another preference, in step 2) in, the number of times padded is respectively 3-15 times, preferably 4-12 times, be more preferably 5-10 times.

In another preference, step 2) processing time padded is 3-1000s, preferably 5-800s, It is more preferably 8-600s, is most preferably 10-300s.

In another preference, step 2) liquid carrying rate of wool product of the gained through padding is 50-160wt%, compared with It is goodly 60-150wt%, is more preferably 80-140wt%.

In another preference, in step 3) before, repeat step 2), number of repetition is 3-15 times, Preferably 4-12 times, be more preferably 5-10 times.

In another preference, repeat step 2 every time) before, in addition to step：Change the shrinkproof place Manage liquid.

In another preference, in step 3) in, the temperature of water used in the washing is 10-40 DEG C, preferably For 20-30 DEG C.

In another preference, the pH of water used in the washing is 6.5-7.5, preferably 7.

In another preference, in step 3) in, step 2) wool product of the gained through padding be with a certain amount of Water is washed.

In another preference, step 3) number of times of the washing is 1-6 times, preferably 2-4 times.

In another preference, step 3) time of the washing is 1-60 minutes, preferably 1-30 minutes, More preferably it is 1-10 minutes.

In another preference, in step 4) before, repeat step 3), number of repetition is 1-6 times, Preferably 2-4 times.

In another preference, in step 4) in, the inactivation treatment is by the way of being selected from the group：Hot water goes out Living, hydrogen peroxide (H₂O₂) inactivate or its combination.

In another preference, the temperature that hot water inactivates used hot water is 85-100 DEG C, preferably 90-98 DEG C, it is more preferably 92-96 DEG C.

In another preference, hot water inactivation processing time be 5-300s, preferably 8-200s, more preferably Ground is 10-100s.

In another preference, in step 4) in, the processing time of the hydrogen peroxide inactivation treatment is 5-300s, Preferably 8-200s, is more preferably 10-100s.

In another preference, in step 4) also optionally comprise the following steps afterwards：

5) soft treatment step 4) products therefrom, wool product needed for being made；With

6) optionally it is dehydrated and/or drying and processing previous step products therefrom, wool product needed for obtaining.

In another preference, step 5) soft treatment is using softening treating agent immersion treatment step 4) Products therefrom.

In another preference, in step 5) in, step 4) products therefrom and the softening treating agent consumption Than the amount ratio for routine.

In another preference, step 5) soak time of the soft treatment in the inorganic agent be 5-200s, preferably 8-100s, are more preferably 10-50s.

In another preference, step 5) number of times of the soft treatment is 1-10 times, preferably 2-5 times, More preferably it is 3-4 times.

In another preference, step 5) temperature of inorganic agent that is used of the soft treatment for 25-65 DEG C, Preferably 30-50 DEG C.

In another preference, step 5) pH of inorganic agent that is used of the soft treatment is 5-8, preferably Ground is 5.5-7.5.

In another preference, step 5) concentration of inorganic agent that is used of the soft treatment for 5-100g/L, Preferably 10-50g/L, is more preferably 15-30g/L.

In another preference, step 5) inorganic agent that is used of the soft treatment is selected from the group：Wool is smooth Agent, wool softening agent or its combination.

In another preference, step 6) treatment temperature of the drying and processing is 60-100 DEG C, preferably 70-90℃。

In another preference, step 6) in, the drying and processing time under the treatment temperature is 1-30 points Clock, preferably 3-15 minute.

In the fourth aspect of the present invention there is provided a kind of shrinkproof without chlorine wool product, in described wool product There is no the residual of organochlorine.

In another preference, described wool product is carried out with anti-shrinking technique (method) of the present invention Anti-shrinking.

In another preference, described wool product be with described in first aspect present invention without chlorine wool tops Or the anti-shrinking agent of wool product carries out anti-shrinking.

In another preference, the wool product is using anti-shrinking equipment described in second aspect of the present invention Carry out without chlorine processing.

In another preference, after being handled through the Antishrinking method, compared to pending wool product, The scale layer clearance without wool top layer in chlorine wool product through processing is 80-100%, preferably 90-100%, is more preferably 95-100%, such as 99-100%.

In another preference, after being handled through the Antishrinking method, compared to pending wool product, Absolute value≤10% of the shrinkage factor without chlorine wool product through processing, preferably≤8%, preferably≤6%, more Goodly≤5%, most preferably≤3%, wherein, assay method be International Wool Secretariat's TWC.TM31 method of testings,

In another preference, after being handled through the Antishrinking method, compared to pending wool product, The strength without chlorine wool product through processing keeps >=80%, preferably >=82%, more preferably >=84%.

In another preference, after being handled through the Antishrinking method, compared to pending wool product, The elongation without chlorine wool product through processing keeps >=70%, preferably >=75%, more preferably >=80%.

In another preference ,≤the 30s that drips diffusion time without chlorine wool product through processing, preferably Ground≤15s, more preferably≤10s.

In the fifth aspect of the present invention there is provided a kind of product, the product is comprising described in fourth aspect present invention Wool product or be made up of described wool product.

In another preference, described product includes wool top, woollen blanket, clothing.

In the sixth aspect of the present invention, there is provided a kind of use of the anti-shrinking agent described in first aspect present invention On the way, it be used to carry out without chlorine anti-shrinking wool top or wool product.

In the seventh aspect of the present invention there is provided a kind of anti-shrinking liquid without chlorine wool tops and wool product, it Main composition be：Protease, the water-soluble substitution of aliphatic three organic phosphine compound, inorganic salts；Described water Insoluble aliphatic three substitution organic phosphine structure be：P-(R-S)₃, wherein R:For the alkyl containing 1~6 carbon, S is Hydroxyl or carboxyl and its derivative；Its mass concentration is 1~10g/L；Inorganic salts are calcium chloride, its concentration be 0~ 2g/L。

In another preference, three described substitution organic phosphines are：Three (3- hydroxypropyls) phosphines, three (3- carboxylics propyl group) At least one of phosphine, three (2- ethoxys) phosphines, three (4- carboxylics butyl) phosphines.

Add in the eighth aspect of the present invention there is provided a kind of without chlorine wool tops and the continuous of wool product anti-shrinking Work technique, comprises the following steps：

1) anti-shrinking：By wool tops and wool product row it is smooth at the uniform velocity delivered into by roll it is some equipped with anti- Alternately infiltrated in contracting processing liquid tank and be with roll compacting 3-10 times, process conditions：The pH of anti-shrinking liquid be 7~ 10.5, temperature is 40~50 DEG C；Roll compacting liquid carrying rate is 60%~150%；Technique conveys 3~15 ms/min of speed Clock, infiltration and 1~5 minute roll compacting total time；

2) wash：Wool tops after above-mentioned processing is entered to enter in 1~4 Rinsing Area by roll action transport Row repeatedly washing, to remove the biological enzyme activator and enzyme preparation of residual, prevents it from continuing to corrode wool；

3) inactivation of protease：Quickly through 85-95 DEG C of hot water storgae or it is uniformly by the wool tops after washing Containing 0~1 g/l of solution of hydrogen peroxide, by the albumen enzyme-deactivating not washed completely；

4) soft treatment：Wool tops after inactivation treatment is soaked in Conventional wool smooth agent or silicone softening agent Groove in, general soft treatment is carried out, to improve the feel of wool fabric；

5) it is dehydrated, dries；

Described anti-shrinking liquid is mainly contained：

Three substitution organic phosphines, concentration is 1~10g/L

Calcium chloride, concentration is 0.3~2g/L

Protease, concentration is 0.5~5g/L

Remaining is water

Described three substitutions organic phosphines are：Three (3- hydroxypropyls) phosphines, three (3- carboxylics propyl group) phosphines, three (2- ethoxys) At least one of phosphine, three (4- carboxylics butyl) phosphines.

In another preference, described immersion repeats 3-10 times with extruding or roll compacting；Described immersion The total time of processing is between 1~5 minute；Technique conveys 3-8 ms/min of speed.

In another preference, described wool tops is the wool or cashmere of 56~100.

It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and below (such as embodiment) It can be combined with each other between each technical characteristic of middle specific descriptions, so as to constitute new or preferred technical side Case.As space is limited, no longer tire out one by one herein and state.

Brief description of the drawings

Fig. 1 is that the wool fiber scale of the embodiment of the present invention 1 divests design sketch.

Fig. 2 is that the wool fiber scale of the embodiment of the present invention 2 divests design sketch.

Fig. 3 is that the wool fiber scale of the embodiment of the present invention 3 divests design sketch.

Fig. 4 is that the wool fiber scale of the embodiment of the present invention 4 divests design sketch.

Fig. 5 is that the wool fiber scale of the embodiment of the present invention 5 divests design sketch.

Fig. 6 is the FB(flow block) of the craft embodiment of the present invention.

Fig. 7 is a schematic diagram without chlorine processing equipment of the invention.

Embodiment

The present inventor's in-depth study by long-term, is unexpectedly prepared for a kind of free from chloride wool tops/wool system The de-scaling shrink-proof process of product and corresponding anti-shrinking agent and equipment.The technique and anti-shrinking liquid of the present invention can The scale layer of wool surface efficiently and is rapidly removed under the conditions of without chlorine, scale layer is modified, so as to reach To the felting performance of wool product is improved, product size stability is improved.On this basis, inventor completes The present invention.

Specifically, the invention provides a kind of Continuous maching work without chlorine wool tops and wool product anti-shrinking Skill.Including anti-shrinking, washing, the inactivation of protease, soft treatment, dehydration, baking step, according to sheep Wool fibre is the feature of protein fibre, replaces organic phosphine structure with water-soluble aliphatic three from by protease The efficient integrated catalytic system of activator, metal salt and nonionic surfactant composition, can be cooperateed with, efficiently The scale layer of wool surface is removed, scale layer is modified, so that reaching improves the felting performance of wool product, Product size stability is improved, makes fabric that there is anti-fluffing and anti-pilling characteristic and smooth feel.The present invention can be with complete Replace the shrinkproof method of chlorination of the prior art entirely, it is to avoid environmental pollution caused by chloridising, be one kind meets ring The clean type handling process that border is required, in the absence of chlorination pollution problem.This method reagent dosage is small, cost is low, Technique is simple, low for equipment requirements, can continuous operation, it is possible to achieve industrialization production.

Term

As used herein, term " raw wool " include without the shrinkproof wool of de-scaling, wool top or its half into Product.Although in addition, the term may also include by de-scaling anti-shrinking, the raw wool of incomplete de-scaling.

As used herein, term " wool tops/wool product ", " wool tops and/or wool product " are interchangeable Use, refer to wool tops or wool product, or both combination.The term can both include pending wool Bar/wool product, can also include in processing procedure or treated wool tops/wool product.

As used herein, term " present invention is without chlorine products ", " of the invention without chlorine wool tops/wool product " It is used interchangeably, refers to the wool tops/wool product obtained without chlorine de-scaling anti-shrinking technique through the present invention.By Without using organochlorine compound in the present invention is without chlorine de-scaling shrink-proof process, also without using hypochlorous acid class compound (i.e. the compound of the ion containing ClO- or the compound of ClO- ions can be produced), therefore be that a kind of security is excellent It is different without chlorine wool product (including wool tops/wool product).

As used herein, term " anti-piping compound (or liquid) of the invention ", " de-scaling anti-piping compound of the invention (or Liquid) " " no chlorine anti-shrinking agent (or liquid) ", " no chlorine de-scaling anti-shrinking agent (or liquid) " be used interchangeably, Refer to the anti-shrinking agent (or liquid) without chlorine wool tops/wool product of the present invention.

Anti-shrinking agent without chlorine wool tops/wool product

It is used for the de-scaling anti-shrinking agent of the invention without chlorine wool tops/wool product the invention provides a kind of.This The de-scaling anti-shrinking agent of invention can be solid-state or liquid., can when the present invention is solid-state without chlorine anti-piping compound To be reconstructed into the corresponding anti-shrinking without chlorine wool tops/wool product by adding water (or aqueous solvent) Liquid.

In addition, it is of the invention, wherein each combination can have been mixed and (existed in a mixed manner), can also Exist in non-mixed mode, and carry out extemporaneous preparation when in use.

In a preference, a kind of main composition of the anti-shrinking liquid without chlorine wool tops and wool product is： Protease, the water-soluble substitution of aliphatic three organic phosphine compound, inorganic salts；Described water-soluble aliphatic three takes It is for organic phosphine structure：P-(R-S)₃, wherein R:For the alkyl containing 1~6 carbon, S be hydroxyl or carboxyl and its Derivative；Its mass concentration is 1~10g/L；Inorganic salts are calcium chloride, and its concentration is 0~2g/L.

In the present invention, it is preferred to three substitution organic phosphines include (but being not limited to)：Three (3- hydroxypropyls) phosphines, three (3- carboxylics propyl group) phosphine, three (2- ethoxys) phosphines, three (4- carboxylics butyl) phosphines or its combination.

In another preference, described protease includes neutral proteinase, alkali protease or its combination.

In another preference, the neutral proteinase refers to the egg that optimal pH is neutral (such as from about 6.8~7.0) White enzyme, its molecular weight is generally 35~40kD.Suitable for the present invention neutral proteinase include it is commercially available or The neutral proteinase prepared with conventional method, such as neutral proteinase from microorganism, Neutrase or its Combination.

In another preference, the alkali protease refers to the protease that optimal pH is alkaline (such as from about 9~11), Its molecular weight is generally 26~34kD.Suitable for the present invention alkali protease include it is commercially available or with routine side Method prepare alkali protease, such as from bacillus licheniformis alkali protease (molecular weight is about 27300, Belong to the endo protease of serine-type), the alkali protease from streptomycete, 2709 alkali proteases, Novo Protease, Carsberg protease etc..

In the shrinkproof liquid of the present invention, the concentration of protease is generally 0.1-25g/L, preferably 0.2-10g/L, The shrinkproof liquid of more preferably 0.5-5g/L.Based on international unit (IU), the consumption (or concentration) of protease is generally 1 ×10⁴-1×10⁸The shrinkproof liquid of U/L, preferably 5 × 10⁴-5×10⁷U/L, is more preferably 1 × 10⁵-1×10⁷U/L。

In another preference, anti-shrinking liquid of the present invention also contains nonionic surfactant (such as JFC) or the moon Ionic surface active agent.Representational nonionic surfactant includes (but being not limited to)：Polyoxyethylene-type table Face activating agent (such as APES (APEO), polyoxyethylene carboxylate (AE), fatty acid methyl ester second Epoxide compound (FMEE)) and EPE polyol EPE (such as sorbitan ester, including Tween and Span), Or its combination.Representational example includes：Tween, Span, JFC or its combination.Representational anion Surfactant includes (but being not limited to)：Neopelex, lauryl sodium sulfate (SDS), ten Six alkylsulfonates or its combination.

Generally, the concentration of surfactant is 0.001-1.0wt% or 0.01-10g/L, preferably 0.1~2g/L.

Preferably, the pH of anti-shrinking liquid of the present invention is 7~10.5.

In another preference, the invention provides a kind of anti-shrinking liquid without chlorine wool tops and wool product, Its prevailing quality is constituted：

Three substitution organic phosphines, concentration is 1~10g/L

Calcium chloride, concentration is 0~2g/L

Protease, concentration is 0.5~5g/L

Remaining is water.

The anti-shrinking agent (liquid) of the present invention can directly handle wool tops/wool product, so that it is shrinkproof to obtain de-scaling Wool tops/wool product.

With the chloride anti-shrinking liquid phase ratio of prior art, anti-shrinking liquid of the invention is closed without organic chloride Thing, also (the compound of the ion containing ClO- or can produce the change of ClO- ions without using hypochlorous acid class compound Compound such as Cl₂).Described organochlorine compound includes DCCA, chloroform, carbon tetrachloride, TCCA etc..

In another preference, main group of the anti-shrinking liquid of the invention without chlorine wool tops and wool product Into：Protease, the water-soluble substitution organic phosphine compound of aliphatic three and inorganic salts.

Wherein, described water-soluble aliphatic three substitution organic phosphine structure is：P-(R-S)₃,

R:For the alkyl containing 1~6 carbon (C), S is hydroxyl (- OH) or carboxyl (- COOH) and its derivative.Its Usage amount is 1g~10g/L；Inorganic salts are calcium chloride etc., and its consumption is 0g/L~2g/L.

Described protease is neutral proteinase, alkali protease etc., and the concentration of protease is 0.5g/L~5g/L.

The pH of described anti-shrinking liquid is 7~10.5.

In another preference, the prevailing quality composition of described anti-shrinking liquid is：

Three substitution organic phosphines, concentration is 1~10g/L

Calcium chloride, concentration is 0~2g/L

Protease, concentration is 0.5~5g/L

Remaining is water.

Antishrinking method (technique) without chlorine wool tops or wool product

Present invention also offers a kind of Antishrinking method without chlorine wool tops or wool product, wherein using this hair Bright is handled wool tops/wool product without chlorine de-scaling anti-shrinking liquid, so as to obtain with excellent shrinkproof Wool tops/wool product of performance.Although it should be understood that the anti-shrinking liquid and method of the present invention can be very abundant De-scaling is realized on ground, so that the wool product of complete de-scaling is obtained, but as required, the inventive method also can use In the wool product for producing non-fully de-scaling (i.e. part de-scaling).

As shown in fig. 6, in a preference, it is shrinkproof without chlorine wool tops and wool product the invention provides one kind The continuous processing technology of processing, comprises the following steps：

1) de-scaling anti-shrinking：By wool tops/wool product row it is smooth at the uniform velocity delivered into by roll one or It is multiple to be equipped with anti-shrinking liquid bath, alternately infiltrate and roll compacting (such as 3-10 times), process conditions are：It is anti- The pH of contracting treatment fluid is 7~10.5, and temperature is 40~50 DEG C；Wherein, 1~5 point of infiltration and roll compacting total time Clock；

It is preferred that by wool tops side by side it is smooth at the uniform velocity delivered into by roll it is some be equipped with anti-shrinking liquid bath in Alternately infiltrate and roll (crowded) pressure 3-10 times, process conditions are：The pH of anti-shrinking liquid is 7~10.5, Temperature is 40~50 DEG C；Roll compacting liquid carrying rate is 60%~150%；Technique 3~15 ms/min of speed of conveying (can be excellent Select 3-8 ms/min), infiltration and 1~5 minute roll compacting total time；

3) inactivation of protease：Wool tops after will be scrubbed quickly through 85-95 DEG C of hot water storgae or for containing The solution that 0.1~1 g/l of hydrogen peroxide, by the albumen enzyme-deactivating not washed completely；

5) it is dehydrated, dries；

Described anti-shrinking liquid is mainly contained：

Three substitution organic phosphines, concentration is 1~10g/L

Calcium chloride, concentration is 0.3~2g/L

Protease, concentration is 0.5~5g/L

Remaining is water

In another preference, described immersion can be repeated several times with roll compacting operation, for example, carry out 3-10 times.

In the present invention, what described immersion was handled with roll compacting is not particularly limited total time, usually 0.5-20 Minute, preferably 1-10 minutes, be more preferably 1-5 minutes.

Present invention only requires the total time of very short infiltration/roll compacting operation, because the present invention's removes without chlorine The agent of squama anti-shrinking efficiently and almost can nondestructively carry out de-scaling very much.

In another preference, of the invention is continous way without chlorine anti-shrinking technique, wherein, continuous processing In conveying speed can be 0.5-20 ms/min, preferably 1-10 ms/min.

In the preference of the present invention, the handling process includes：

1) anti-shrinking：Wool tops is carried out to the stripping squama processing of protease integrated catalytic system effect.In every sheep In the case of wool top is tension-free, at the uniform velocity delivered into wool tops is smooth side by side by roll by protease, water-soluble Property the substitution of aliphatic three organic phosphine biological enzyme activator, the efficient catalytic system of inorganic salt catalyst composition, also may be used To add conventional nonionic surfactant as assist infiltration agent, pH is 7~10.5, and catalyst system and catalyzing temperature is 40~50 DEG C, wool tops be impregnated with completely after (can by the equipment such as suction roll accelerate be impregnated with and wool fiber with The exchange velocity of surrounding treatment fluid), wool tops is extruded by roll effect, liquid carrying rate is 60%~150%. Transmit again afterwards in the catalyst system and catalyzing that temperature is 40~50 DEG C, again by roll effect to wool tops after being impregnated with Extruded, so padded repeatedly, technique speed is controlled at 3~15 ms/min (optional 3-8 ms/min), It is in the treatment fluid of same integrated catalytic system and identical according to wool number and the difference of product quality requirement Under treatment conditions, experience 1~5 minute is simultaneously padded by 3~10 times, is finally sent to follow-up relevant treatment groove, Reach continuous and automatic effect.

2) wash.Wool tops after above-mentioned processing is entered to enter in 1~4 Rinsing Area by roll action transport Row repeatedly washing, to remove the biological enzyme activator and enzyme preparation of residual, prevents it from continuing to corrode wool.

3) inactivation of protease.Wool tops after second step is cleaned it is uniform quickly through boiling water groove or for containing The solution that 0~1 g/l of hydrogen peroxide.With the albumen enzyme-deactivating that will do not washed completely.

4) soft treatment.Wool tops after inactivation treatment is soaked in Conventional wool smooth agent or silicone softening agent (i.e. in slot type soft treatment, carry out general soft treatment, softening agent be containing hydrogen silicone oil, amido silicon oil with And modified silicon oil or their emulsion), to improve the feel of wool fabric.

5) it is dehydrated, dries (conventional method can be used).

Without chlorine processing equipment

Present invention also offers it is a kind of for the inventive method without chlorine processing equipment.

A kind of typical processing equipment is as shown in Figure 7.The equipment includes：

Multiple squeeze device 10, the multiple squeeze device includes that n is independent, continuously arranged to pad device (not Show), the device that respectively pads includes soaking compartment and rolling roller, wherein, described soaking compartment is used to place without chlorine The anti-shrinking liquid of anti-shrinking so that pending wool tops or wool product is soaked in described treatment fluid In；And described rolling roller is used for the soaking wool tops or wool product of rolling, and enter through upstream rolling roller Wool tops or wool product after row rolling, being sequentially entered downstream pads the soaking compartment and rolling roller of device, so as to weigh The multiple immersion and rolling processing, wherein n is 2-20 positive integer；

Water washing device 20, for washing the wool top or wool product through padding, formed wool top through washing or Wool product；

Enzyme-deactivating device 30, for the protease alkalescence to the residual in the wool top through washing or wool product Inactivation treatment, forms wool top or wool product through enzyme-deactivating；

Optional soft treatment device 40, for the wool top or wool system handled described in soft treatment through enzyme-deactivating Product, form wool top or wool product through soft treatment；With

Optional drier 50, for being done to wool top or wool product through soft treatment obtained by previous step Dry processing.

In another preference, the multiple squeeze device, water washing device, enzyme-deactivating device, optional softness Processing unit and optional drier sequential.

In another preference, respectively padding between device or afterwards, be additionally provided with one in described multiple squeeze device Individual or multiple auxiliary pad device, and described each auxiliary, which pads device, independently includes auxiliary soaking compartment and auxiliary rolling Roller, wherein, the Protease Treatment liquid without organic phosphine compound is placed in described auxiliary soaking compartment, and/or Organic phosphine compound treatment fluid without protease.

In another preference, described auxiliary soaking compartment is ferment treatment groove.

In another preference, described ferment treatment groove is located at the 2nd, 3,4 or 5 pad device after.

In another preference, wherein n be 2,3,4,5,6,7,8,9,10,11,12,13,14, 15th, 16,17,18,19 or 20, preferably 3-15, are more preferably 4-10.

In another preference, the shape and size for respectively padding device may be the same or different.

It is described respectively to pad device sequential in another preference.

In another preference, the soaking compartment built with described in first aspect present invention anti-shrinking agent (or Liquid).

In another preference, the soaking compartment is suction cylinder washing trough.

In another preference, the soaking compartment is independently provided with or without heater or temperature regulating device.

In another preference, each heater or temperature regulating device control temperature range at 25-80 DEG C, Preferably 30-70 DEG C, be more preferably 40-60 DEG C, is most preferably 45-55 DEG C.

In another preference, the water washing device includes m water scrubber, and wherein m is 1-10 positive integer, Preferably 1-6, preferably 2-4.

In another preference, each built-in aqueous solvent of water scrubber.

In another preference, the temperature of aqueous solvent described in each water scrubber is 10-40 DEG C, preferably 20-30℃。

In another preference, the pH of aqueous solvent described in each water scrubber is 6.5-7.5, preferably pH7±0.2。

In another preference, the enzyme-deactivating device is high-temperature inactivation groove and/or hydrogen peroxide inactivation groove.

In another preference, the temperature of aqueous solvent described in the enzyme-deactivating device is 85-100 DEG C, preferably It it is more preferably 92-96 DEG C for 90-98 DEG C.

In another preference, the enzyme-deactivating device is built-in to contain H₂O₂Solution.

In another preference, the enzyme-deactivating device fills H described in solution₂O₂Concentration be 0.01-50g/L, preferably 0.05-30g/L, more preferably 0.1-10g/L.

In another preference, the soft treatment device is built-in containing the softening treating agent being selected from the group：Wool is put down Lubrication prescription, wool softening agent or its combination.

In another preference, in the soft treatment device, the concentration of the softening treating agent is about 1-50g/L, preferably 2-40g/L, are more preferably 5-25g/L.

In another preference, the wool softening agent includes：Organic silicon softening agent.

In another preference, the organic silicon softening agent is selected from the group：Silicone oil, hydrogen silicone oil, amido silicon oil, Modified silicon oil or its combination.

Without chlorine wool tops/wool product

Present invention also offers have with of the present invention without the acquisition of chlorine anti-shrinking technique, little or no It is shrinkproof without chlorine wool tops/wool product that machine chlorine is remained.

As used herein, term " Eve is glad (ecoshine) " or " glad (ecoshine) product of Eve " refer to use Of the invention is being obtained without chlorine anti-shrinking technique, little or no organochlorine residue shrinkproof without chlorine sheep Wool top/wool product.

The wool top through being handled without chlorine or wool product (i.e. the glad product of Eve) of the present invention with excellent performance, its Include and (being not limited to)：

(a) high scale layer clearance：Compared to pending wool product, wool in the wool product through processing The scale layer clearance on top layer is 80-100%, preferably 90-100%, is more preferably 95-100%, such as 99-100%.

(b) low-shrinkage：Compared to pending wool product, the shrinkage factor of the wool product through processing it is exhausted To being worth≤10%, preferably≤8%, preferably≤6%, more preferably≤5%, most preferably≤3%, wherein, determine Method is International Wool Secretariat's TWC.TM31 method of testings.

(c) high-tenacity conservation rate：After being handled through the Antishrinking method, compared to pending wool product, The strength of wool product through processing keeps >=80%, preferably >=82%, more preferably >=84%.

(d) high elongation rate is kept：After being handled through the Antishrinking method, compared to pending wool product, The elongation of wool product through processing keeps >=70%, preferably >=75%, more preferably >=80%.

(e) excellent wetting, permeance property：Drip diffusion time (by GB/T21655.1-2008) by without Before reason >=10 minutes, bring up to≤10 seconds.

Treatment mechanism and advantage

For the ease of understanding the present invention, the present inventor provides following mechanism.It should be understood, however, that the present invention not by The limitation of the mechanism.

The inventors discovered that, there is some special constructions and material in the scale layer of wool surfaces, for example, contain two Cystine and lipides of sulfide linkage etc., so that protease, which is difficult to effectively digestion, decomposes epicuticula and therein High-sulphur protein.However, in the presence of the formula A organic phosphine compounds of the present invention, using of the present invention multiple Padding process, on the one hand can effectively change the structure of the scale layer of wool surfaces so that the albumen such as High-sulphur protein Matter is more easy to proteases for decomposing, on the other hand can maintain or improve the vigor of protease, so that extremely efficiently and rapidly Realize that the desquamation to wool is shrinkproof.

For currently preferred inorganic agent, the effect of protease is mainly fine by hydrolysis degraded wool The scale in dimension table face；On the one hand water-soluble aliphatic three substitution organic phosphine passes through its uniqueness to disulfide bond in wool Effect, it is quick to reduce the disulfide bond largely existed in scale and activate reaction substrate, be conducive to protease and sheep Hair macromolecular reaction, still further aspect, its vigor to protease has good stabilization, can effectively subtracted The decline of prolease activity in few integrated catalytic system, while being capable of the catalysis work of further activator protein enzyme again With so as to produce quick reaction effect.In addition, the main function of inorganic salt catalyst is can be further to egg White enzyme enters line activating；And surfactant main function is aid in treatment liquid soaks and ooze as early as possible in wool surface Thoroughly.

In the technique of the present invention, multiple to pad or pad repeatedly be also that the present invention realizes the necessary bar of shock processing Part.During padding repeatedly, pressure realizes the Rapid contact of protease and activator and wool surface And effect, while being also beneficial to clean out reactant and hydrolysate, be conducive to the further progress of reaction.

Compared with prior art, the present invention has following major advantage：

(1) it is environment-friendly, chloride organic matter or chlorine is not used.This present invention has with protease, water solubility Efficient catalytic system based on the activator of machine phosphine structure is arranged as treatment fluid to wool, utilizes both Synergy, which is reached in no shrinkproof Continuous maching of chlorine wool tops mercerising, processing procedure, will not produce venomous injurant Matter, fundamentally solves pollution of the chlorination mercerising to environment, meets " ecological spinning " concept, will not cause Environmental pollution

(2) technique is simple and easy to control.

(3) treatment effeciency height, processing speed are fast.Compared with known protease method shrink-proof process, this method speed Degree is fast, can complete the anti-shrinking of wool in 1~5min, and ensure its mechanical characteristic in tolerance interval It is interior.

(4) anti-felting effect is lasting.

(5) it is adapted to large-scale production.Present invention process is low for equipment requirements, can continuous operation, be conducive to reality Existing industrialization production.

With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate The present invention rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, Generally according to normal condition or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and Number is calculated by weight.

Involved reagent, without specified otherwise, is commercially available in embodiment.

Treatment fluid of the present invention weighs protease, the water-soluble substitution of aliphatic three according to the amount of main formula to be had Machine phosphine compound, inorganic salts and surfactant, are prepared by general mass concentration (g/L) compound method. Organic phosphine compound used is purchased from the production of Tianjin Binhai east Science and Technology Ltd..

Embodiment 1

In the present embodiment, the continuous processing padded again using five, is carried out without chlorine anti-shrinking to wool tops.

Pending full wool wool tops, specification is 70.The technique comprises the following steps：

First groove：Pad treatment fluid.The groove is wide 1 meter, 360 liters of volume and the suction with one meter of girth is rolled There is automatic heating device (fexible unit) in cylinder (formula) washing trough (fexible unit), the suction cylinder groove, equipped with main Constitute and (add nonionic table for alkali protease (alkali protease) 3g/L, three (3- hydroxypropyls) phosphine 3g/L Face activating agent JFC 1g/L) efficient catalytic solution, pH is 9 (using disodium hydrogen phosphate and sodium dihydrogen phosphate as pH Conditioning agent), it is 50 DEG C to control temperature.

Wool wool tops is uniformly laid in side by side on roller and treatment fluid is at the uniform velocity entered with 8 ms/min of speed, Make wool tops complete wetting, it is ensured that every fiber appearance in wool tops all obtains uniform and complete processing；Again to add Pressure roller ensures that wool tops pick-up rate is about 135% to wool tops pressurization；Make the wool tops with enzyme liquid afterwards with 8 meters The speed of/minute enters second treatment trough.To entering second since wool tops enters the first groove treatment fluid Untill groove treatment fluid, 15 seconds are taken.

Second groove：Pad treatment fluid.With the first groove.

3rd groove：Pad treatment fluid.With the first groove.

4th groove：Pad treatment fluid.With the first groove.

5th groove：Pad treatment fluid.With the first groove.To the 5th trough end since the first groove, take as 15 Second × 5=75 seconds.

6th groove：Washing.Wool tops is rolled by roll and washed, make wool surface adhere to reagent, enzyme and The product cleaning of degraded is clean, and water temperature is that normal temperature, pH are 7.0.

7th groove：Secondary washing.With the 6th groove.

8th groove：High temperature is washed, and plays enzyme-deactivating effect, prevents follow-up continuation from corroding wool fiber, temperature 95 DEG C, 15 seconds time.

9th groove：Conventional soft treatment, makes wool fiber softening reach soft effect, improves feel.It is right afterwards Wool tops carries out conventional dehydration, dried (for example：Stoving process condition：70-90 DEG C of drying temperature, drying time 3-10 minutes).

The technique speed is 8 ms/min, and total immersion rolls treatment fluid 5 times.The wool fiber after this PROCESS FOR TREATMENT Scale divests effect and sees Fig. 1.

Wool after this PROCESS FOR TREATMENT is compared with before processing, and strength keeps 85%, and elongation keeps 83%.

Wool after this PROCESS FOR TREATMENT, according to International Wool Secretariat's TWC.TM31 method of testings, 5 × 5A test results are： - 4.86%.

Chlorinity detection is carried out to the wool after the processing, the chlorine-containing component (organic matter) of residual is not as a result detected.

Embodiment 2

In the present embodiment, the continuous processing padded using sixfold, is carried out without chlorine anti-shrinking to wool tops.

Pending full wool wool tops, specification is 56.The technique comprises the following steps：

First groove：Pad treatment fluid.The groove is wide 1 meter, 360 liters of volume and the suction with one meter of girth is rolled Cylinder groove, has automatic heating device in the suction cylinder groove, equipped with containing alkali protease 3g/L, three (3- hydroxypropyls Base) phosphine 3g/L efficient catalytic solution, pH is 10.5, control temperature be 50 DEG C.

Wool top is uniformly laid in side by side on roller and treatment fluid is at the uniform velocity entered with 3.8 ms/min of speed, Make wool tops complete wetting, it is ensured that every fiber appearance in wool tops all obtains uniform and complete processing；Again to add Pressure roller ensures that wool tops pick-up rate is 130% to wool tops pressurization；Make the wool tops with enzyme liquid afterwards with 3.8 meters The speed of/minute enters second treatment trough.To entering second since wool tops enters the first groove treatment fluid Untill groove treatment fluid, 31.5 seconds are taken.

Second groove：Pad treatment fluid.With the first groove.

3rd groove：Pad treatment fluid.With the first groove.

4th groove：Pad treatment fluid.With the first groove.

5th groove：Pad treatment fluid.With the first groove.

6th groove：Pad treatment fluid.With the first groove.To the 6th trough end since the first groove, take as 31.5 Second × 6=189 seconds.

7th groove：Washing.Wool tops is rolled by roll and washed, make wool surface adhere to reagent, enzyme and The product cleaning of degraded is clean, and water temperature is that normal temperature, PH are 7.0.

8th groove：Secondary washing.With the 7th groove.

9th groove：High temperature is washed, and plays enzyme-deactivating effect, prevents follow-up continuation from corroding wool fiber, temperature 95 DEG C, 15 seconds time.

Tenth groove：Wool top pads the 20g/L soft agent solution of wool, wool fiber softening is reached soft effect, Improve feel.It is 15 seconds 7.0, time that 40 DEG C of softening agent solution temperature, pH value, which are,.Wool tops is entered afterwards Row dewatered drying.

The technique speed is 3.8 ms/min, and total immersion rolls treatment fluid 6 times.The wool fiber after this PROCESS FOR TREATMENT Scale divest effect and see Fig. 2.

Wool after this PROCESS FOR TREATMENT is compared with before processing, and strength keeps 83%, and elongation keeps 72%.

Wool after this PROCESS FOR TREATMENT, according to International Wool Secretariat's TWC.TM31 method of testings, 5 × 5A test results are： - 3.82%.

Embodiment 3

Pending full wool wool tops, specification is 90.The technique comprises the following steps：

First groove：Pad treatment fluid.The groove is wide 1 meter, 360 liters of volume and the suction with one meter of girth is rolled There is automatic heating device in cylinder groove, the suction cylinder groove, equipped with alkali protease 3g/L, three (3- carboxylics propyl group) Phosphine 3g/L, anhydrous calcium chloride 0.3g/L (adding nonionic surfactant JFC 1g/L) efficient catalytic it is molten Liquid, pH is 8.5 (with proper amount of sodium carbonate or sodium hydroxide solution regulation pH), and it is 50 DEG C to control temperature.

Second groove：Pad treatment fluid.With the first groove.

3rd groove：Pad treatment fluid.With the first groove.

4th groove：Pad treatment fluid.With the first groove.

5th groove：Pad treatment fluid.With the first groove.To the 5th trough end since the first groove, take as 31.5 Second × 5=about 158 seconds.

7th groove：Secondary washing.With the 6th groove.

9th groove：Wool top pads the 20g/L soft agent solution of wool, wool fiber softening is reached soft effect, Improve feel.It is 15 seconds 6.0, time that 40 DEG C of softening agent solution temperature, pH value, which are,.Wool tops is entered afterwards Row dewatered drying.

The technique speed is 3.8 ms/min, and total immersion rolls treatment fluid 5 times.The wool fiber after this PROCESS FOR TREATMENT Scale divest effect and see Fig. 3.

Wool after this PROCESS FOR TREATMENT is compared with before processing, and strength keeps 81%, and elongation keeps 80%.

Wool after this PROCESS FOR TREATMENT, according to International Wool Secretariat's TWC.TM31 method of testings, 5 × 5A test results are： - 2.98%.

Embodiment 4

Pending full wool wool tops, specification is 80.The technique comprises the following steps：

First groove：Pad treatment fluid.The groove is wide 1 meter, 360 liters of volume and the suction with one meter of girth is rolled There is automatic heating device in cylinder groove, the suction cylinder groove, loading mainly contains alkali protease 3g/L, three (2- Ethoxy) phosphine 3g/L, anhydrous calcium chloride 0.3g/L (adding nonionic surfactant JFC 1g/L) it is efficient Catalytic solution, pH is 7.5, and it is 50 DEG C to control temperature.

Wool top is uniformly laid in side by side on roller and treatment fluid is at the uniform velocity entered with 4.5 ms/min of speed, Make wool tops complete wetting, it is ensured that every fiber appearance in wool tops all obtains uniform and complete processing；Again to add Pressure roller ensures that wool tops pick-up rate is 130% to wool tops pressurization；Make the wool tops with enzyme liquid afterwards with 4.5 meters The speed of/minute enters second treatment trough.To entering second since wool tops enters the first groove treatment fluid Untill groove treatment fluid, 26.7 seconds are taken.

Second groove：Pad treatment fluid.With the first groove.

3rd groove：Pad treatment fluid.With the first groove.

4th groove：Pad treatment fluid.With the first groove.

5th groove：Pad treatment fluid.With the first groove.To the 5th trough end since the first groove, take as 26.7 Second × 5=about 134 seconds.

7th groove：Secondary washing.With the 6th groove.

The technique speed is 4.5 ms/min, and total immersion rolls treatment fluid 5 times.The wool fiber after this PROCESS FOR TREATMENT Scale divest effect and see Fig. 4.

Wool after this PROCESS FOR TREATMENT is compared with before processing, and strength keeps 82%, and elongation keeps 81%.

Wool after this PROCESS FOR TREATMENT, according to International Wool Secretariat's TWC.TM31 method of testings, 5 × 5A test results are： - 3.56%.

Embodiment 5

In the present embodiment, the continuous processing padded using septuple, is carried out without chlorine anti-shrinking to wool tops.

First groove：Pad treatment fluid.The groove is wide 1 meter, 360 liters of volume and the suction with one meter of girth is rolled There is automatic heating device in cylinder groove, the suction cylinder groove, loading mainly contains alkali protease 2g/L, three (4- Carboxylic butyl) phosphine 3g/L, anhydrous calcium chloride 0.3g/L be (optional:Add nonionic surfactant JFC 1g/L Or anion surfactant) efficient catalytic solution, pH is 8, control temperature be 50 DEG C.

Wool top is uniformly laid in side by side on roller and treatment fluid is at the uniform velocity entered with 6 ms/min of speed, Make wool tops complete wetting, it is ensured that every fiber appearance in wool tops all obtains uniform and complete processing；Again to add Pressure roller ensures that wool tops pick-up rate is 130% to wool tops pressurization；Make afterwards the wool tops with enzyme liquid with 6 meters/ The speed of minute enters second treatment trough.To the second groove of entrance since wool tops enters the first groove treatment fluid Untill treatment fluid, 20 seconds are taken.

Second groove：Pad treatment fluid.With the first groove.

3rd groove：Pad treatment fluid.With the first groove.

4th groove：Pad treatment fluid.With the first groove.

5th groove：Pad treatment fluid.With the first groove.

6th groove：Pad treatment fluid.With the first groove.

7th groove：Pad treatment fluid.With the first groove.To the 7th trough end since the first groove, take as 20 Second × 7=140 seconds.

8th groove：Washing.Wool tops is rolled by roll and washed, make wool surface adhere to reagent, enzyme and The product cleaning of degraded is clean, and water temperature is that normal temperature, pH are 7.0.

9th groove：Secondary washing.With the 8th groove.

Tenth groove：High temperature is washed, and plays enzyme-deactivating effect, prevents follow-up continuation from corroding wool fiber, temperature 95 DEG C, 15 seconds time.

11st groove：Wool top pads the 20g/L soft agent solution of wool, wool fiber softening is reached soft effect Really, feel is improved.It is 15 seconds 6.0, time that 40 DEG C of softening agent solution temperature, pH value, which are,.Afterwards to wool Bar carries out dewatered drying.

The technique speed is 6 ms/min, and total immersion rolls treatment fluid 7 times.The wool fiber after this PROCESS FOR TREATMENT Scale divests effect and sees Fig. 5.

Wool after this PROCESS FOR TREATMENT is compared with before processing, and strength keeps 82%, and elongation keeps 80%.

Wool after this PROCESS FOR TREATMENT, according to International Wool Secretariat's TWC.TM31 method of testings, 5 × 5A test results are： - 3.01%.

Embodiment 6

In the present embodiment, the continuous processing padded using quadruple, is carried out without chlorine anti-shrinking to wool product.

Pending product is wool product (serge).Method is as follows：

Using four groups of Kroy deepim reaction chambers (every group of 1.5 meters of depth, 1.8 meters of breadth, 0.4 meter of thickness), Protease integrated catalytic treatment fluid is padded, its treatment fluid, which is mainly constituted, is：Alkali protease 1.8g/L, three (4- Carboxylic butyl) phosphine biological enzyme activator 3.0g/L, anhydrous calcium chloride 0.3g/L be (also optional to add non-ionic surface Activating agent JFC1g/L) efficient catalytic solution, pH is 7.5, control temperature be 50 DEG C.By pending serge Sound of a bird chirping open width sequentially enters four groups of Kroy deepim reaction chambers, and quadruple is at the uniform velocity carried out with 6 ms/min of speed Liquid carrying rate control is 100% between padding processing 2 minutes, every group, is washed, inactivated afterwards, soft, baking Dry-cure.

After above-mentioned processing, wool product not only has good shrinkproof performance, particularly wetting, permeance property Be greatly enhanced, its drip diffusion time (by GB/T21655.1-2008) by before processing >=carry within 10 minutes Height arrives≤10 seconds.

Comparative example 1

Infusion method processing

Desquamation anti-shrinking is carried out using conventional infusion method, method is as follows：

Wool tops (70,20g) is fully soaked 20 minutes or 60 minutes (50 DEG C) with immersion treatment liquid.Through After immersion treatment, post-processed with conventional method and (be similar to embodiment 1), including 3 washings, so Enzyme-deactivating processing and soft treatment are carried out afterwards, are finally dehydrated and are dried.

Wherein, immersion treatment formula of liquid is as follows：Alkali protease (alkali protease) 3g/L, nonionic Surfactant JFC 1g/L (pH=8.5), solvent is water.

As a result show, when soak time is 20 minutes, the desquamation of part wool is insufficient.Work as soak time For 60 minutes when, the desquamation effect of wool is substantially uniform, but still with the presence of the insufficient feelings of a small amount of wool desquamation Condition.This shows that the infusion method technique is unfavorable for large-scale production because time-consuming, treatment effect heterogeneity.

Comparative example 2

Immersion-steam method processing

This comparative example carries out desquamation anti-shrinking using conventional batch (-type) by immersion-steam method.Method is such as Under：

Wool tops (70,20g) is fully soaked with immersion treatment liquid (50 DEG C, pick-up rate 120%), carried out pre- Leaching is handled about 1 minute, decatize (50 DEG C) is then carried out in steaming box 25 minutes, during which the 5th, 10,15 With 20 minutes supplement individual composition liquid (composition and immersion treatment liquid phase are same).Immersion-individual composition takes 26 altogether Minute.

After soaking-steam method processing, post-processed with conventional method and (be similar to embodiment 1), including 3 washings and then progress enzyme-deactivating processing and soft treatment, are finally dehydrated and are dried.

Wherein, immersion treatment liquid with embodiment 1 to pad prescription for the treatment of liquid close, but without three (3- hydroxypropyls Base) phosphine.It is formulated as follows：Alkali protease (alkali protease) 3g/L, nonionic surfactant JFC 1g/L。

As a result：

Wool is carried out after above-mentioned anti-shrinking, wool surfaces scale wedge angle is substantially all to be eliminated.But it is homogeneous Property is poor, wherein thinner wool surfaces scale is very fuzzy, thicker wool scale layer is cut very thin, table This bright handling process to fine wool scale to divest effect better than common and braid wool.

Fiber strength is 10.34cN after processing, and strength retention is 83.25%；Elongation is 32.30%, is stretched Long rate retention rate is 64.77%.This shows that the wool after this PROCESS FOR TREATMENT can reach shrinkproof requirement, and fracture is strong Power loss is in tolerance interval, but elongation loss is than larger.

In addition, time-consuming up to 26 minutes for whole immersion-individual composition, and treatment effect is but far inferior to embodiment 1-5.In contrast, in 1-5 of the embodiment of the present invention multiple total time padded it is very low (≤5 minutes, more preferably ≤ 3 minutes), and desquamation effect is more homogeneous, and shrinkproof performance is more excellent.

The outstanding feature of the present invention is no chlorine, quick Continuous maching, to reach the substitution anti-compression method of chlorination completely, Improve the deficiency that protease biological handling process is used alone, improve protease biological processing method, be finally reached Optimization processing effect, improves the purpose of all woolen product quality.

All documents referred in the present invention are all incorporated as reference in this application, just as each document quilt It is individually recited as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, this Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application institute Attached claims limited range.

Claims

1. a kind of be used for the anti-shrinking agent without chlorine anti-shrinking, it is characterised in that the anti-shrinking agent bag Contain：(a) optional solvent；(b) protease；Organic phosphine compound formula A shown in and optional nothing (c) Machine salt；

P-(X)₃ A

2. anti-shrinking agent as claimed in claim 1, it is characterised in that when the anti-shrinking agent is water Solution or when being reconstructed into the aqueous solution, its pH is 6.5-12, preferably 7-11.5, is more preferably 7.5-10.5.

3. anti-shrinking agent as claimed in claim 1, it is characterised in that described organic phosphine compound is Water-soluble aliphatic organic phosphine compound.

4. anti-shrinking agent as claimed in claim 1, it is characterised in that the organic phosphine compound has Formula：

P-(R₁-R₂)₃ I

Wherein,

5. anti-shrinking agent as claimed in claim 1, it is characterised in that the organic phosphine compound is selected from The following group：Three (3- hydroxypropyls) phosphines, three (3- carboxylics propyl group) phosphines, three (2- ethoxys) phosphines, three (4- carboxylics butyl) phosphines, Or its combination.

6. a kind of anti-shrinking equipment without chlorine wool tops or wool product, it is characterised in that the equipment bag Include：

7. anti-shrinking equipment as claimed in claim 6, it is characterised in that in described multiple squeeze device Respectively pad between device or afterwards, be additionally provided with one or more auxiliary and pad device, it is only that described each auxiliary pads device On the spot include auxiliary soaking compartment and auxiliary rolling roller, wherein, placed in described auxiliary soaking compartment and be free of organic phosphine The Protease Treatment liquid of compound, and/or the organic phosphine compound treatment fluid without protease.

8. a kind of Antishrinking method without chlorine wool tops or wool product, it is characterised in that including following step Suddenly：

(a) provide it is pending without chlorine wool tops or wool product, and described in claim 1 without chlorine wool tops Or the anti-shrinking agent of wool product；

(b) pending carried out n to described with described anti-shrinking agent without chlorine wool tops or wool product and padded again Processing, so as to obtain the wool product through padding, wherein n is 2-10 positive integer；

9. method as claimed in claim 8, it is characterised in that the step (b) pad processing it is total when Between T≤15 minute, preferably≤10 minute, more preferably≤5 minute, most preferably≤3 minute.

10. it is a kind of shrinkproof without chlorine wool product, it is characterised in that there is no organochlorine in described wool product Residual, and described without chlorine wool product is to be carried out with the anti-shrinking equipment described in claim 6 at no chlorine Reason, or carry out what no chlorine was handled with the method described in claim 8.