CN102965959B - Wool refining treating fluid and treating method - Google Patents
Wool refining treating fluid and treating method Download PDFInfo
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Abstract
The invention discloses a wool refining treating fluid and a treating method. The treating fluid comprises the following components by weight percent: 0.1-10% of protease, 0.1-10% of activating agent and 0.1-10% of water softener, wherein the pH value of the refining treating fluid is 4-10; the activating agent is at least one of the following components, i.e. urea, thiourea dioxide, glycerol, dithiothreitol, tricarboxylic ethyl phosphine, beta-mercaptoethanol, carboxymethyl phosphate, peregal-10, ABS (acrylonitrile butadiene styrene), tri-propionitrile base phosphate, tri-N-butylphosphine and tri-(2-carboxyl ethyl phosphate) hydrochloride; and the water softener is sodium tripolyphosphate or sodium hexametaphosphate. The treating method uses the wool refining treating fluid provided by the invention, and adopts a bath one-step method treatment technology; and the treatment technology has the following technological process: cleaning wool-wetting and soaking-refining-washing-softening-drying-refining wool.
Description
Technical field
The present invention relates to natural wool refinement technology, is a kind of wool micronization processes liquid and processing method specifically.This processing method utilization activation biology enzyme Decrement Technique, is processed into more fine wool or superfine wool by common fine wool.
Background technology
Wool is a kind of important textile raw material, the characteristic such as there is good springiness, hygroscopicity is strong, warmth retention property good, be difficult for staiing, gloss is soft, and its fabric also has unique style and uses function.Especially (m) (the frivolous worsted fabric of top grade that diameter 15～8 μ m) are processed into is the main product of current high-grade wool textile to diameter 18～21 μ to super-fine wool with super super-fine wool.But this animal fiber can only rely on nature to provide at present, due to natural conditions restriction, ramuscule and ultra-fine the few valency of wool yield are high, far can not meet actual needs.Therefore, in the world wool refinement technology has been carried out to large quantity research.
Wool refinement technology has two kinds of methods: one is mechanical stretching method; Another kind is decrement method.Decrement method comprises again chemical decrement and biochemistry decrement two class methods.The essence of its wool decrement refinement processing adopts conventional chemical or biochemical method exactly, destroy the disulfide bond (-S-S-) structure of angle protein in wool fibre, by wool superficial degradation, to improve Surface Machining performance and the wearability of wool, comprise felting property, feel, gloss ANTIPILLING and dyeing etc.Because fiber surface is degraded, objectively will make wool fibre attenuate.Keeping, under enough powerful prerequisite, how making wool obtain rational reduction rate, the modified effect that makes wool product obtain needs is the key of decrement micronization processes.
Protease decrement treatment is a kind of conventional wool by bio superalloy processing method.But in the ordinary course of things, wool need to be after preliminary treatment or pre-treatment, protease could have larger decrement activity to wool, otherwise the decrement of proteases on wool is very little.In other words, use merely Protease Treatment wool, be not enough to obtain obvious thinning effect.The preliminary treatment of Protease Treatment wool typically refers to be processed wool with oxidant or reductant.Conventional oxidant has: hydrogen peroxide, oxidizer containing chlorine, permonosulphuric acid and peracetic acid etc., wherein receive people's concern especially due to the good ecotype of hydrogen peroxide processing.The reductant that is usually used in wool reduction processing has sodium sulfite, sodium pyrosulfite, sodium hydrogensulfite, sodium dithionite etc.Oxidation pre-treatment can be opened being cross-linked in wool protein, thereby makes protein molecular more yielding, and to being conducive to enzymatic location orientation, promotes the increase of enzyme decrement.
According to existing theory, the Main Patterns of wool decrement is divided into two kinds, and one is hydrolysis pattern; Another kind is separation mode.Separation mode is a kind of Main Patterns of protein to wool hydrolysis.In this pattern, chemistry decrement is a wherein very little part, physics decrement is main, taking the form of of it contains the cells that come off from wool in a large number in treatment fluid, its reason is the epicuticula that protease is difficult to be hydrolyzed wool, and relatively easily carry out for the hydrolysis of globular preteins in wool cytoplasm CMC, therefore in the time of decrement treatment, cause coming off of whole cell.Because cytoplasm CMC has been subject to destruction, therefore very big for the mechanical performance impact of wool fibre in this pattern, in macroscopic view, show as powerful reduction obviously.Hydrolysis pattern requirement protease can be with speed hydrolysis faster for epicuticula albumen, and from current result of study, Activities of Some Plants protease exists the decrement potentiality of hydrolysis pattern.But this mode needs oxidation pre-treatment equally, to remove the long carbochain lipoid of wool surfaces, make protease can directly act on epicuticula albumen.
Traditional decrement method be wool top chlorination decrement method technique (Zhang Fukun etc. wool mercerising refinement technology (J). Shanghai Textile science and technology, 2002,30 (2): 12-14), be mainly to utilize oxidant (NaClO, Cl
2, DCCA etc.) oxidation chlorination effect in wool scale skin-S-S-key carries out oxydrolysis reaction; Meanwhile, main chain-peptide chain is oxidized fracture also, and main chain break and crosslinked destruction make wool scale outer layer of protein be decomposed into the hydrolysis of polypeptide and even amino acid, thereby by most of scale layer or all degrade removal.Chlorination decrement method technique combines with degree of depth soft treatment, can reach reduction wool fineness, obtains the object of high glaze wool fibre.The whole flow process of wool top chlorination decrement method technique (mercerization) is:
Wool top → chlorination processing → dechlorination → neutralization → cleaning → acid treatment → soft finish → dry → balling-up → twice grilling.
The advantage of tradition chlorination wool processing method is that cost is low, and the fabric anti-felting of production is effective, and gloss is soft bright, there is silk quality sense, and due to the removal of scale, can reduce or eliminate the prodding and itching feeling that wears next to the skin Woolens, exploitation autumn in summer fashionable dress is there is to the meaning of particular importance.But the method has deadly defect: (1) needs pretreating process, by scale layer and the interfibrous interaction of chlorination preliminary treatment, destruction wool surface, the follow-up textile process of wool is very easily sustained damage; (2) follow-up dyeing and finishing processing needs K cryogenic treatment, and price is more expensive, and easily make fabric yellowing and feel coarse; (3) in RESIN FINISH in processing procedure and subsequently, can produce the harmful substances such as the organic chloride (AOX) that can adsorb, environment and human body are had to irreversible infringement; (4) starting point of processing method is the mercerization of wool, but not for decrement refinement wool, wool fineness changes not obvious.
Protease Treatment is another wool decrement method of modifying, but because biology enzyme acts on the limitation of wool, in process, need to first be oxidized equally or chloride oxidation preliminary treatment after, then carry out the processing of wool decrement by the method for Protease Treatment.Preliminary treatment can make scale layer softening, and fiber surface hydrophiling is conducive to protease and enters fibrous inside from hydrophilic site and carry out heterogeneous reaction, and conventional have a H
2o
2,,method for pretreating, KMnO
4method, chloride oxidation method etc.The technological process of this processing method is:
Wool top or fabric → preliminary treatment (oxidation or chloride oxidation) → enzyme processing → go wool top or the fabric of enzyme processing (hot water inactivation) → washing → be dried → modification.
Protease adds process for chemically pretreating and corrodes due to surface and inside simultaneously, can reach wool is shunk attenuate, fabrics feel soft, gloss softly become clear, machine washable and free from environmental pollution.But it is few that the wool fibre average diameter of this method processing reduces, and can only reduce at the most by 1.5 μ m, and owing to still needing first to carry out pretreating process, the problems that exist equally traditional chlorination wool processing method to exist.Protease adds process for chemically pretreating does not also have ripe industrial applications at present.
Existing wool decrement micronization processes technology (for example, Wang Shugen. enzymatic Treatment of wool (J). printing and dyeing assistant, 1996,13 (3), 5-8; Zhang Fukun etc. wool mercerising refinement technology (J). Shanghai Textile science and technology, 2002,30 (2): 12-14) shortcoming or deficiency be:
1. complex process, long flow path, has pollution.The method of current protease decrement refinement wool mainly contains two step method and three-step approach.No matter that method all needs preliminary treatment or pre-treatment process, complex process, long flow path, chlorination processing has pollution.
2. treatment effect is undesirable, can not solve refinement and the contradiction between powerful maintenance.Process with proteases on wool, can divest the scale of fiber surface, thereby subtract fibrillose diameter (fibre fineness can reduce by 2 μ m left and right), improve the fineness of wool, but after Modification by Protease is processed, the damage of wool is more serious, is unfavorable for follow-up textile process, also larger on the Practical Performance impact of final wool product.Therefore this decrement treatment neither a kind of desirable wool thinning method.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of wool micronization processes liquid and processing method are provided, and this treatment fluid is selected specific activator preparation, can use with bathing to process with biology enzyme, do not pollute, and preparation is simple; This processing method adopts activator and biological enzyme formulation with bathing one-step technology, is keeping under the condition that wool fundamental property is constant, make wool fineness improve a grade, and technique is simple, and efficiency is high, there is no environmental pollution.
The technical scheme that the present invention solves described treatment fluid technical problem is: design a kind of wool micronization processes liquid, it is characterized in that this treatment fluid is to process wool weight as 100 consist of: proteinase-10 .1-10%, activator 0.1-10%, water softener 0.1-10%, the pH value of micronization processes liquid is 4-10; Described activator is the one in urea, thiourea dioxide, glycerine, dithiothreitol (DTT), three carboxyethyl phosphines, beta-mercaptoethanol, carboxymethyl phosphoric acid, peregal-10, ABS, three propionitrile base phosphorus, three normal-butyl phosphorus and three (2-carboxy ethyl phosphine) hydrochloride; Described water softener is sodium phosphate trimer or calgon.
The technical scheme that the present invention solves described processing method technical problem is: design a kind of wool thinning processing method, this processing method is used wool micronization processes liquid of the present invention, and adopts a bath one-step method treatment process: processing technological flow is: scoured wool → wetting immersion → micronization processes → washing → soft treatment → oven dry → refinement wool; Described wetting soaking technology condition is: wetting agent consumption is the 0.1-10% that processes wool weight, soaking temperature 10-90 ℃, and soak time 0.1-2 hour, described wetting agent is anion surfactant or non-ionic surface active agent; Described micronization processes process conditions are: micronization processes liquid and the bath raio 1:100 that processes wool, by pH adjusting agent modulation micronization processes liquid pH value to 4-10, described pH adjusting agent is at least one in acetic acid, sodium acetate, sodium dihydrogen phosphate or sodium hydrogen phosphate, micronization processes temperature is 10-100 ℃, and the micronization processes time is 10-200 minute; Described washing, soft treatment and stoving process are same as prior art.
Compared with prior art, the designed wool micronization processes liquid of the present invention does not contain hazardous substance, and meets the requirement of current environmental protection, there is no pollution problem, belongs to green processing technology.Processing method of the present invention adopts wool micronization processes liquid of the present invention and one to bathe one-step method processing technology, traditional oxidation or reduction pretreatment technique are abandoned, shorten flow process, facilitate operation, wool diameter decreased average after treatment more than 10% (2～3 microns), thinning effect is obvious, reaches the level of a high grade wool, and has shrinkproof performance.For example, after the industrializing implementation of processing method of the present invention, the wool that fineness is 64 can reach 70-80 and prop up the level of wool fineness; After treatment, fineness can reach the level of 100 wool finenesses to 80 wools of fineness.The powerful maintenance of wool after micronization processes is good, can remain on the 70-80% of raw wool brute force; The elongation at break of micronization processes wool can keep the more than 80% of raw wool elongation at break, meets general spinning requirement; Meanwhile, the wool aggregated structure after micronization processes still keeps former a type configuration laniferous, can make to greatest extent the wool after micronization processes keep former characteristic properties laniferous, particularly good elasticity.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment.Embodiment is only in detail and illustrates the present invention, do not limit the claims in the present invention.
The wool micronization processes liquid (abbreviation treatment fluid) of the present invention design is to process wool weight as 100 consist of: proteinase-10 .1-10%, activator 0.1-10%, water softener 0.1-10%, and micronization processes liquid pH value is 4-10; Described activator is at least one in urea, thiourea dioxide, glycerine, dithiothreitol (DTT), three carboxyethyl phosphines, beta-mercaptoethanol, carboxymethyl phosphoric acid, peregal-10, ABS, three propionitrile base phosphorus, three normal-butyl phosphorus and three (2-carboxy ethyl phosphine) hydrochloride; Described water softener is sodium phosphate trimer or calgon.
The wool activation biology enzyme decrement wool technology of the present invention's innovation, main feature is in treatment fluid, to add specific biological (albumen) enzyme activator, this activator forms the specific wool decrement of a kind of tool integrated catalytic hydrolyzation system together with protease, i.e. described micronization processes liquid.Activating component action temperature in this system and, can process with bathing (one bathe) with protease, and not affect the performance of the hydrolysis of proteases on wool, activator itself can act on again wool simultaneously, further strengthens protease and act on the effect of wool.Therefore can improve wool micronization processes effect.
The present invention is designed wool thinning processing method (abbreviation processing method) simultaneously, this processing method is used treatment fluid of the present invention, and adopts as next bath one-step method treatment process: processing technological flow is: scoured wool → wetting immersion → micronization processes → washing → soft treatment → oven dry → refinement wool; Described wetting soaking technology condition is: wetting agent consumption is the 0.1-10% that processes wool weight, soaking temperature 10-90 ℃, soak time 0.1-2 hour, described wetting agent is anion surfactant or non-ionic surface active agent, the preferred penetrating agent JFC of wetting agent or the wetting agent EA of embodiment; Described micronization processes process conditions are: micronization processes liquid and the bath raio 1:100 that processes wool, by pH adjusting agent modulation micronization processes liquid pH value to 4-10, described pH adjusting agent is at least one in acetic acid, sodium acetate, sodium dihydrogen phosphate or sodium hydrogen phosphate, micronization processes temperature is 10-100 ℃, and the micronization processes time is 10-200 minute.PH value conditioning agent adopts two kinds of used times together, is conducive to form have the cushioning liquid of stablizing pH value.When two kinds of pH value conditioning agents use together, the combination of preferably phosphoric acid sodium dihydrogen and sodium hydrogen phosphate, or the combination of acetic acid and sodium acetate, its mixing or portfolio ratio are selected in well known range.
In processing technological flow described in processing method of the present invention, washing process, soft treatment technique and stoving process, be same as prior art substantially.Specifically: the washing agent that washing process uses is that the hair of commonly using can wait washing agent only, and bath raio is 1:10-100, wash temperature 10-90 ℃, wash time 1-90 minute; Soft treatment process conditions are: the softener bath raio in soft treatment liquid is 1:10-100, soft treatment temperature 10-90 ℃, soft treatment time 1-90 minute, described softener is silicone softening agent, comprises containing hydrogen silicone oil, amido silicon oil and modified silicon oil or their emulsion; Stoving process condition is: bake out temperature 70-90 ℃, drying time 3-10 minute.
Processing method of the present invention does not adopt traditional chlorination or oxidation chlorination pretreating process, does not therefore have conventional method, owing to using strong oxidizing property material, wool is caused to violent damage.Wool thinning processing method of the present invention is owing to having used treatment fluid of the present invention, thereby can adopt simple one to bathe one-step technology, can implement the refinement processing of wool and process, obtain the wool of obvious refinement, and kept wool inherent characteristic substantially constant.
The process equipment that processing method of the present invention is used is at present conventional hair dyeing and finishing process equipment, as wool washing machine, flock dyeing machine, yarn package dyeing machine etc., does not need new equipment, is easy to industrialization promotion and uses.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below: described embodiment is for describing the present invention in detail, rather than limits claim of the present invention.
Embodiment 1
Wool micronization processes liquid consists of: take the weight of processing wool as 100, the usage ratio of protease, three carboxyethyl phosphines and sodium phosphate trimer is respectively 5%, 3% and 1%.
The technological process of wool thinning processing method is:
Scoured wool → wetting immersion → micronization processes → washing → soft treatment → oven dry → refinement wool.Wherein, wetting soaking conditions is: wetting agent EA 1%(owf, implication is the percentage by weight of additive with respect to processed wool), bath raio 1:30,70 ℃ of soaking temperatures, soak time 60 minutes;
Micronization processes liquid treatment conditions are: micronization processes liquid and the bath raio 1:100 that processes wool weight, and pH value is adjusted to 6, micronization processes temperature 70 C, 60 minutes micronization processes time; PH value conditioning agent is sodium dihydrogen phosphate and sodium hydrogen phosphate (weight ratio is 6:3);
Wash conditions is: hair is 1%(owf only), bath raio 1:30,70 ℃ of wash temperatures, wash time 20 minutes;
Soft treatment condition is: silicone softening agent 1%(owf), bath raio 1:30, soft treatment temperature 50 C, 30 minutes soft treatment time.
Drying condition is: 80 ℃ of bake out temperatures, drying time 5 minutes.
Micronization processes the results are shown in table 1:
The situation of change table that table 1. wool is processed front and back fineness, brute force and extended
| 80 wools | (μ m) for fineness | Fineness dispersion degree (cv%) | Powerful (cN) | Extend (mm) |
| Before processing | 17.94 | 22.6 | 4.02 | 5.87 |
| After processing | 16.54 | 23.7 | 3.66 | 4.37 |
Embodiment 2
Micronization processes liquid consists of: protease 5%(owf), three propionitrile base phosphorus 3%(owf), sodium phosphate trimer 1%(owf).
Processing technological flow is with embodiment 1: wherein,
Wetting soaking conditions is: wetting agent EA 1%(owf), bath raio 1:30,60 ℃ of soaking temperatures, soak time 50 minutes;
Micronization processes condition is: micronization processes liquid with process the bath raio 1:100 of wool, micronization processes liquid pH value is adjusted to 5, micronization processes temperature 70 C, 70 minutes micronization processes time, pH value conditioning agent is acetic acid and sodium acetate (weight ratio is 3.9:3);
Wash conditions is: hair is 1%(owf only), bath raio 1:30,70 ℃ of wash temperatures, wash time 20 minutes;
Soft treatment condition is: silicone softening agent 1%(owf), bath raio 1:30, soft treatment temperature 50 C, 30 minutes soft treatment time;
Drying condition is: 80 ℃ of bake out temperatures; Drying time 5 minutes
Micronization processes the results are shown in table 2:
The situation of change that table 2 wool is processed front and back fineness, brute force and extended
| 66 wools | (μ m) for fineness | Fineness dispersion degree (cv%) | Powerful (cN) | Extend (mm) |
| Before processing | 21.22 | 26.3 | 6.68 | 5.65 |
| After processing | 19.20 | 28.2 | 5.60 | 3.57 |
Embodiment 3
Micronization processes liquid consists of: protease 4%(owf), the three normal-butyls 3%(owf that sees), sodium phosphate trimer 1%(owf).
Processing technological flow is with embodiment 1: wherein,
Wetting soaking conditions is: wetting agent EA 1%(owf), bath raio 1:30,50 ℃ of soaking temperatures, soak time 50 minutes;
Micronization processes condition is: micronization processes liquid with process the bath raio 1:100 of wool, pH value is adjusted to 7, micronization processes temperature 60 C, 60 minutes micronization processes time, pH value conditioning agent is sodium dihydrogen phosphate and sodium hydrogen phosphate (weight ratio is about 5:3);
Wash conditions: hair is 1%(owf only), bath raio 1:30,70 ℃ of wash temperatures, wash time 20 minutes;
Soft treatment condition: silicone softening agent 1%(owf), bath raio 1:30, soft treatment temperature 50 C, 30 minutes soft treatment time;
Drying condition: 80 ℃ of temperature, 5 minutes time;
Result is listed in table 3:
The situation of change that table 3 wool is processed front and back fineness, brute force and extended
| 100 wools | (μ m) for fineness | Fineness dispersion degree (cv%) | Powerful (cN) | Extend (mm) |
| Before processing | 16.47 | 23.1 | 3.29 | 5.68 |
| After processing | 15.31 | 24.4 | 2.92 | 4.08 |
Embodiment 4
Micronization processes liquid composition: protease 3 %(owf), the three carboxyethyls 2%(owf that sees), sodium phosphate trimer 1%(owf).
Processing technological flow is with embodiment 1.Wherein,
Wetting soaking conditions is: wetting agent EA 1%(owf), bath raio 1:30,50 ℃ of soaking temperatures, soak time 30 minutes;
Micronization processes treatment conditions: micronization processes liquid and the bath raio 1:100 that processes wool, micronization processes liquid pH value is adjusted to 7, micronization processes temperature 50 C, 30 minutes micronization processes time, pH value conditioning agent is sodium dihydrogen phosphate and sodium hydrogen phosphate (weight ratio is about 5:3);
Wash conditions: hair is 1%(owf only), bath raio 1:30,60 ℃ of wash temperatures, wash time 30 minutes
Soft treatment condition: silicone softening agent 1%(owf), bath raio 1:30, soft treatment temperature 50 C, 30 minutes soft treatment time;
Drying condition: 80 ℃ of bake out temperatures, drying time 5 minutes;
Result is listed in table 4:
The situation of change that table 4 wool is processed front and back fineness, brute force and extended
| Cashmere | (μ m) for fineness | Fineness dispersion degree (cv%) | Powerful (cN) | Extend (mm) |
| Before processing | 15.37 | 22.8 | 3.41 | 4.02 |
| After processing | 14.48 | 25.1 | 3.39 | 4.01 |
Claims (4)
1. a wool micronization processes liquid, is characterized in that this treatment fluid is to process wool weight as 100 consist of: proteinase-10 .1-10%, activator 0.1-10%, water softener 0.1-10%, and the pH value of micronization processes liquid is 4-10; Described activator is the one in urea, thiourea dioxide, dithiothreitol (DTT), three carboxyethyl phosphines, beta-mercaptoethanol, carboxymethyl phosphoric acid, ABS, three propionitrile base phosphines, tri-n-butyl phosphine and three (2-carboxy ethyl phosphine) hydrochloride; Described water softener is sodium phosphate trimer or calgon.
2. a wool thinning processing method, this processing method right to use requires the wool micronization processes liquid described in 1, and adopts a bath one-step method treatment process: processing technological flow is: scoured wool → wetting immersion → micronization processes → washing → soft treatment → oven dry → refinement wool; Described wetting soaking technology condition is: wetting agent consumption is the 0.1-10% that processes wool weight, soaking temperature 10-90 ℃, and soak time 0.1-2 hour, described wetting agent is anion surfactant or non-ionic surface active agent; Described micronization processes process conditions are: micronization processes liquid and the bath raio 1:100 that processes wool, by pH adjusting agent modulation micronization processes liquid pH value to 4-10, described pH adjusting agent is at least one in acetic acid, sodium acetate, sodium dihydrogen phosphate or sodium hydrogen phosphate, micronization processes temperature is 10-100 ℃, and the micronization processes time is 10-200 minute; Described washing, soft treatment and stoving process are same as prior art.
3. wool thinning processing method according to claim 2, is characterized in that described wetting agent is penetrating agent JFC or wetting agent EA.
4. wool thinning processing method according to claim 2, while it is characterized in that two kinds of described pH value conditioning agents use together, adopts the combination of sodium dihydrogen phosphate and sodium hydrogen phosphate, or the combination of acetic acid and sodium acetate.
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| CN101220355A (en) * | 2008-01-18 | 2008-07-16 | 浙江雀屏纺织化工股份有限公司 | Biological complex enzyme and use method of the enzyme on woollen sweater shrink-resistant finish |
| CN102102293A (en) * | 2010-12-23 | 2011-06-22 | 北京中纺化工股份有限公司 | Shrink-resistance machine-washable finishing method of slenderized wool |
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