CN1552988A - Machine cleanable woolen fabrics with nano structure on wool fiber surface and preparation thereof - Google Patents
Machine cleanable woolen fabrics with nano structure on wool fiber surface and preparation thereof Download PDFInfo
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- CN1552988A CN1552988A CNA031371418A CN03137141A CN1552988A CN 1552988 A CN1552988 A CN 1552988A CN A031371418 A CNA031371418 A CN A031371418A CN 03137141 A CN03137141 A CN 03137141A CN 1552988 A CN1552988 A CN 1552988A
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Abstract
A method for treating nano woolen fabrics with chitin in finishing process is carried out by putting fabrics into a treating chamber to treat in low temperature unpolymerable gas plasma at 10-170Pa and power of 10-300W to obtain woolen fabrics with nano-grade concave-convex surface; soaking in aqueous chitin solution of 0.5-10g/L at 25-40 deg.C, squeezing out solution of 70-90%, pre-roasting at 70-90 deg.C, and roasting at 100 - 160 deg.C. Furthermore, a softening agent of 20 - 60g/L can be added into the said chitin solution. Non-yellowing and soft feeling and machine washable woolen fabrics can be obtained, with good profits and without AOX discharge.
Description
Technical field
The invention belongs to the functional manufacture field of textiles, relate in particular to by the wool fabric that fiber surface is had nanostructured and carry out machine washable wool fabric and the preparation method that the chitin arrangement obtains.
Background technology
Wool is as a kind of natural fabric, because it is soft, quality is strong and have good curling elasticity and warmth retention property, gloss is soft naturally, is the textile raw material than higher gears always, is subjected to liking of consumers in general deeply.But special scale structure that the wool surface has and rubbing effect thereof make wool fabric produce the felting phenomenon in water-washing process, influence its style and DIMENSIONAL STABILITY.
The method of preventing felting and shrinking of wood fabric has chemical degradation method and polymer deposition methods such as chloridizing, oxidizing process, biological enzyme.Chloridizing is with chloride compound under suitable condition, destroys the scale on wool surface, plays shrinkproof effect, but the difficult control of chlorination degree, fibre strength reduces, and contains in a large number in the waste water of generation to absorb organohalogen compounds AOX, serious environment pollution.Oxidizing process is to improve the coefficient of friction of fiber with oxidants such as potassium permanganate, reduce the rubbing effect, produce shrinkproof result, but cause fibrous elasticity and powerful decline usually, shortened the service life of handling fabric, and be prone to problems such as handling inequality, scent of, easy yellowing, often follow color and luster to change.And as the Chinese patent publication number when to be that CN 1170448A is disclosed handle fiber surface with enzyme because enzyme can cause cuticula and the hydrolysis of cortical layer macro-molecular protein to the fibrous inside diffusion, therefore cause fiber strength than macrolesion.The polymer deposition method is to form high molecular polymer at wool fibre or fabric face, play the effect of motion mutually between the scale surface that stops by covering scale, or between fiber and fiber, produce crosslinked, bond together mutually, thereby make fibre immobilized and can not move, the rubbing effect can not work.Anti-piping compound commonly used in the polymer deposition method has Lauxite, melamine resin, silicones, ethene polymers, esters of acrylic acid and polyurethane resin etc., but these synthetic resin are more or less harmful to human body and environment when synthesizing, handling and taking, and biological degradability is poor.
Effective shrinkproof processing commonly used at present is that chemical degradation method and polymer deposition method are combined, " chlorination/resin treatment method " known as everybody, it by first chlorination after the method for resin treatment give wool fabric desirable shrinkproof performance, can reach the shrinkproof standard of machine washable.Wool fibre is through after the chloridized, and its scale wedge angle is softening and destroy, and resin is filled in the scale angle or some injury region, and scale is isolated and ineffective mutually, thereby eliminates the rubbing effect of wool, reduces the felting phenomenon.Simultaneously chloridized is removed the fatty-acid layer that the scale top layer joins, and increases the hydrophily of wool fibre greatly, promotes resin in the stretching, extension of fiber surface and to the diffusion of fibrous inside, improves the compatibility of resin to fabric.But this processing method is bigger to the damage of wool, and contains a large amount of absorbable organic chlorides in the waste water of discharging, and causes serious environmental to be polluted.
Chitin has the collagen in the higher mammal tissue and the biological function of the fiber in the higher plant tissue, belong to natural polymer, has good film forming, not only have functions such as antibiotic, smelly, the hemostasis of disappearing, anti-inflammatory, and possesses good moisture preserving, nontoxic, non-stimulated to human body, with people's contact skin good affinity is arranged, and can biodegrade.
China is as ocean big country, although chitin series of products output and production capacity are considerable, but most of is that semi-finished product or bulk article are exported back to China with refining inner wrapping more at high price by foreign vendor's bargain purchase, causes resource loss, and economic benefit is impaired.
Summary of the invention
One of purpose of the present invention is to provide a kind of shrinkproof result machine washable wool fabric that good wool surface has nanostructured.
A further object of the present invention provides the preparation method that a kind of wool surface has the machine washable wool fabric of nanostructured, by using Low Temperature Plasma Treating, at wool surface structure nanoscale concaveconvex structure, make the wool surface produce hydrophilic radical, with the chitin arrangement, realize that non-environmental-pollution prepares machine washable wool fabric of the present invention again.
The present invention carries out glow discharge with low temperature plasma to wool fabric earlier and handles, and puts in order with the chitin finishing agent then, obtains the machine washable wool fabric that fiber surface of the present invention has nanostructured.Promptly by physics and chemical modification being carried out in the wool surface with Low Temperature Plasma Treating, at first, increase the specific area of wool fibre greatly, improve the coefficient of friction of fiber at wool surface structure nanoscale concaveconvex structure, reduce the rubbing effect, and the contact area of increase and chitin; Generate as new active groups such as carboxyl, hydroxyl, amino at fiber surface simultaneously, promote the chitin that uses in the subsequent handling in the stretching, extension of fiber surface and to the diffusion of fibrous inside, improve the absorption affinity of fiber to chitin, chitin is firmly bonded on the fiber more, thereby reaches the machine washable purpose.
When utilizing the Low Temperature Plasma Treating fabric, various active particle such as the ion that contains in the low temperature plasma, excited state molecule, free radical and fiber surface carry out various interactions.This is handled and can produce corrosion function to fiber surface, and its reason has two kinds substantially: a kind of is the sputter erosion of the particle hits fiber surfaces such as electronics, ion in the plasma.Another kind is that chemism kind in the plasma is to the chemical erosion of fiber surface.Be exactly that these two kinds of corrosion functions make wool surface produce the nanoscale concaveconvex structure.Low Temperature Plasma Treating can make fiber surface layer produce a large amount of free radicals effectively simultaneously, and this free radical just converts hydrophilic radicals such as carboxyl, amino, hydroxyl to after touching air.These active groups promote the chitin that uses in subsequent handlings in the stretching, extension of fiber surface and to the diffusion of fibrous inside, improve the absorption affinity of fiber to chitin, and chitin is firmly bonded on the fiber more.
Wool surface of the present invention has the machine washable wool fabric of nanostructured, is meant at the fiber surface with nanoscale concaveconvex shape structure that constitutes wool fabric to be adsorbed with one deck chitin.
The shape of described nanoscale concaveconvex structure has varied, the diameter of its recess or wide be 30～200nm.
Wool surface of the present invention has the preparation method of the machine washable wool fabric of nanostructured, and step comprises:
(1). wool fabric is put into the Low Temperature Plasma Treating chamber, the pressure in the process chamber is evacuated to is less than or equal to 10Pa then, the pressure that feeds in the non-polymerization gas regulation process chamber is 10～170Pa, preferred 26～130Pa, more preferably 26～85Pa; Low Temperature Plasma Treating is carried out in discharge then; Power is 10～300W, preferred 30～200W, more preferably 50～100W, processing time 1～60min, preferred 1.5～30min, more preferably 5～20min;
(2). the wool fabric that the fiber surface that step (1) is obtained has the nanoscale concaveconvex structure further carries out the chitin arrangement, it is the chitin water soluble liquid of 0.5～10g/L that described chitin arrangement is to use concentration, with 1: 20～1: 60 bath raio, under 25～40 ℃ of temperature with textile impregnation 20～40min, take out mangle, pick-up rate is 70～90%, preliminary drying 5～20min under 70～90 ℃ of temperature then, and under 100～160 ℃ of temperature, cure 1～4min.
When Low Temperature Plasma Treating, if vacuum is low excessively, the mean free path of electronics is little, electronics energy from the external electric field acquisition in a collision cycle is little, thereby energy is high enough to excite the number of electrons of ionized gas molecule or atom few, the number of active particle is few in the plasma atmosphere, and energy is low, acts on the weak effect behind the wool surface; If vacuum is too high, gas is thin, and number of particles itself is just few, the number of particles that can be used for exciting, ionization generates active particle just still less, thereby the number of particles that acts on the wool surface is few, and two opposite factors make when vacuum is moderate, just can obtain best treatment effect.During Low Temperature Plasma Treating, if discharge power is too little, the then required processing time is long; If power is too big, and discharge instability reacts bad control.If processing time does not have effect too short; If long, bigger to fibre damage.
The gas of described feeding is non-polymerization gas or their any mists such as air, oxygen, nitrogen, carbon dioxide, argon gas, helium, ammonia.But preferably use air from the simplification and the cost consideration of operation.
Described chitin water soluble liquid is with commercially available or homemade chitin, and adds acetic acid etc. and be dissolved in the water and make.Do not do special restriction.
In above-mentioned chitin dressing liquid, can further contain softener or other additive, to improve its wearability.Can use the concentration of 20～60g/L when containing softener in the dressing liquid.This softener can use that buy from market or homemade as common softeners such as amido organosilicon class softener, fatty acid acyl amine softener, organic silicon modified by polyether class softener or polymeric fatty alcohols softeners.
Preferred dressing liquid prescription is: contain the chitin of 1.5～2.5g/L, contain the amido organosilicon class softener of 25～35g/L.
Preferred finishing technique is: with textile impregnation 25～35min, take out mangle under 35～40 ℃ of temperature, pick-up rate is 80～90%, preliminary drying 5～10min under 80～90 ℃ of temperature then, and under 110～150 ℃ of temperature, cure 1～2min.
Low Temperature Plasma Treating is a dry process technology, does not use that any chemical reagent, technology are simple, non-wastewater discharge, non-environmental-pollution, energy savings.And chitin is a degradability natural polymer raw material.Therefore can obtain eco-friendly machine washable wool fabric according to the present invention, have remarkable economic efficiency and social benefit.
The present invention carries out glow discharge with low temperature plasma to wool fabric earlier, obtains the wool fabric that fiber surface has the nanoscale concaveconvex structure, puts in order with the chitin finishing agent then, obtains machine washable wool fabric of the present invention.Promptly by physics and chemical modification being carried out in the wool surface with Low Temperature Plasma Treating, at first, increase the specific area of wool fibre greatly, improve the coefficient of friction of fiber at wool surface structure nanoscale concaveconvex structure, reduce the rubbing effect, and the contact area of increase and chitin; Generate as new active groups such as carboxyl, hydroxyl, amino at fiber surface simultaneously, promote the chitin that uses in the subsequent handling in the stretching, extension of fiber surface and to the diffusion of fibrous inside, improve the absorption affinity of fiber to chitin, chitin is firmly bonded on the fiber more, thereby reaches the machine washable purpose.Low Temperature Plasma Treating is a dry process technology, does not use that any chemical reagent, technology are simple, non-wastewater discharge, non-environmental-pollution, energy savings.And chitin is a degradability natural polymer raw material.Therefore can obtain eco-friendly machine washable wool fabric according to the present invention.
Description of drawings
The be untreated electron scanning micrograph of wool fibre of Fig. 1 comparative example 1.
Fig. 2 embodiment 1 Low Temperature Plasma Treating rear surface has the electron scanning micrograph of the wool fibre of nanostructured.
The x-ray photoelectron spectroscopy of Fig. 3 wool fibre
(a) comparative example 1 is untreated; (b) wool fibre of embodiment 1 Low Temperature Plasma Treating rear surface with nanostructured.
The C of Fig. 4 wool surface
1sSpectrum
(a) comparative example 1 is untreated; (b) wool fibre of embodiment 1 Low Temperature Plasma Treating rear surface with nanostructured.
Further specify the present invention below in conjunction with embodiment and comparative example, but the present invention is not limited thereto.
The specific embodiment
Embodiment 1
Low Temperature Plasma Treating: it is indoor that wool fabric is put into reaction of low temperature plasma, vacuumize, when the reative cell internal pressure reaches 4Pa, begin bubbling air and make that vacuum is equilibrated at 26Pa in the reative cell, carry out glow discharge then, carry out the discharge process of 30min with 100W power.
Arranging process: the wool fabric 30min in the dressing liquid of the chitin that contains 2g/L after 35 ℃ of above-mentioned Low Temperature Plasma Treating of dipping, take out mangle, pick-up rate is 90%, preliminary drying 8min under 90 ℃ of temperature then, and under 130 ℃ of temperature, cure 2min.
Embodiment 2
Low Temperature Plasma Treating: it is indoor that wool fabric is put into reaction of low temperature plasma, carries out the Low Temperature Plasma Treating identical with the foregoing description 1.
Arranging process: except the amino modified silicone softener of AV-910 that in dressing liquid, further contains 30g/L, carry out the arrangement identical with the foregoing description 1.
Embodiment 3
Low Temperature Plasma Treating: Low Temperature Plasma Treating: it is indoor that wool fabric is put into reaction of low temperature plasma, vacuumize, when the reative cell internal pressure reaches 7Pa, begin aerating oxygen and make that vacuum is equilibrated at 160Pa in the reative cell, carry out glow discharge then, carry out the discharge process of 60min with 50W power.
Arranging process: the wool fabric 25min in the dressing liquid of the chitin that contains 2.5g/L after 40 ℃ of above-mentioned Low Temperature Plasma Treating of dipping, take out mangle, pick-up rate is 80%, preliminary drying 10min under 80 ℃ of temperature then, and under 110 ℃ of temperature, cure 3min.
Embodiment 4
Low Temperature Plasma Treating: it is indoor that wool fabric is put into reaction of low temperature plasma, vacuumize, when the reative cell internal pressure reaches 7Pa, begin to feed helium/nitrogen (volume ratio is 6/4) and make that vacuum is equilibrated at 67Pa in the reative cell, carry out glow discharge then, carry out the discharge process of 1min with 300W power.
Arranging process: the wool fabric 40min in the dressing liquid of the amino modified silicone softener of the AV-65 of chitin that contains 5g/L and 20g/L (advanced Co., Ltd produces) after 40 ℃ of above-mentioned Low Temperature Plasma Treating of dipping, take out mangle, pick-up rate is 70%, preliminary drying 15min under 70 ℃ of temperature then, and under 150 ℃ of temperature, cure 1min.
Comparative example 1
Get a wool fabric, do not carry out any processing.
Comparative example 2
Get a wool fabric, only do the Low Temperature Plasma Treating identical, do not carry out arranging process with embodiment 1.
Comparative example 3
Get a wool fabric, do not do Low Temperature Plasma Treating, only do the arranging process identical with embodiment 1.
Comparative example 4
Get a wool fabric, in dressing liquid, do not contain the chitin, do Low Temperature Plasma Treating and the arranging process identical with embodiment 2.
The fiber surface structural analysis
Use JSM-6700F type electronic scanner microscope to observe the wool surface texture.
Comparison diagram 1 can know that with Fig. 2 the wool surface after Low Temperature Plasma Treating produces the nanoscale concaveconvex structure, the diameter of its recess or wide be 30～200nm.This concaveconvex structure will increase the specific area of wool fibre greatly, improve the coefficient of friction of fiber, reduce the rubbing effect, and the contact area of increase and chitin.
X-ray photoelectron spectroscopy (XPS) is analyzed
The ESCALAB 220-IXL type x-ray photoelectron spectroscopy that adopts VG company to produce writes down the signal of different samples.
The element ratio of components of the wool surface that is calculated by the peak value of the XPS figure of Fig. 3 is shown in table 3.
Table 3
| The element ratio | ????O/C | ????N/C | ????S/C |
| It is treated to be untreated | ????0.16 ????0.46 | ????0.10 ????0.21 | ????0.04 ????0.08 |
As can be seen from Table 3, the wool fabric surface after Low Temperature Plasma Treating is compared when being untreated, and its O/C, N/C, S/C value are increased to 2～3 times, illustrates that polarity strengthens.
C from Fig. 4
1sAs can be seen, carbon-oxygen bonds such as the carboxyl on the wool fabric surface after Low Temperature Plasma Treating, carbonyl increase greatly among the figure.Be exactly that these active groups promote the chitin that uses in subsequent handlings in the stretching, extension of fiber surface and to the diffusion of fibrous inside, improve the absorption affinity of fiber, chitin is firmly bonded on the fiber more chitin.
Shrinkproof performance test methods
Shrinkproof performance uses YG 701D type full-automatic textile fabric shrinkage test machine to test according to the 5A program of IWS TM31.The result represents with percentage reduction of area.That is:
Percentage reduction of area (%)=[1-(a ' * b ')/(a * b)] * 100%
Wherein a is the mean value of the preceding wool fabric longitudinal direction 3 director's degree of washing; B is the mean value of the preceding transverse direction 3 director's degree of washing; A ' is the mean value of the wool fabric longitudinal direction 3 director's degree after washing; B ' is the mean value of washing rear cross bar to 3 director's degree.The percentage reduction of area (%) of fabric and the appearance characteristics of processing back fabric are shown in table.
Table 1
| Percentage reduction of area (%) after washing 1 time | Percentage reduction of area (%) after washing 2 times | Appearance characteristics | |
| Embodiment 1 | ????0.33 | ????2.30 | Not yellowing, feel still can |
| Embodiment 2 | ????1.69 | ????2.94 | Not yellowing, soft |
| Embodiment 3 | ????1.42 | ????2.50 | Not yellowing, feel still can |
| Embodiment 4 | ????2.12 | ????2.89 | Not yellowing, soft |
| Comparative example 1 | ????7.56 | ????9.47 | Soft |
| Comparative example 2 | ????2.89 | ????5.41 | Feel still can |
| Comparative example 3 | ????1.53 | ????4.38 | Soft |
| Comparative example 4 | ????2.27 | ????5.22 | Soft |
From last table 1, can know, 2 of comparative examples are done the wool fabric of Low Temperature Plasma Treating or 3 of comparative examples and are done the wool fabric of chitin arrangement and all can not get desirable shrinkproof result, and the wool fabric that carries out carrying out the softener arrangement after the Low Temperature Plasma Treating of comparative example 4 also can not get ideal results.And the wool fabric of handling through the present invention, the percentage reduction of area behind once washing is less than 2%, even less than 1%, and the percentage reduction of area after washing again has excellent machine washable performance less than 3%.And machine washable wool fabric of the present invention is soft, not yellowing.
Claims (10)
1. machine washable wool fabric that wool surface has nanostructured is characterized in that: described machine washable wool fabric is to be adsorbed with one deck chitin at the fiber surface with nanoscale concaveconvex shape structure that constitutes wool fabric.
2. machine washable wool fabric as claimed in claim 1 is characterized in that: the diameter of the recess of described fiber surface nanoscale concaveconvex shape or the wide 30～200nm of being.
3. preparation method as each described machine washable wool fabric of claim 1～2, it is characterized in that: preparation method's step of described machine washable wool fabric comprises:
(1). wool fabric is put into the Low Temperature Plasma Treating chamber, the pressure in the process chamber is evacuated to is less than or equal to 10Pa then, the pressure that feeds in the non-polymerization gas regulation process chamber is 10～170Pa; Low Temperature Plasma Treating is carried out in discharge then; Power is 10～300W, and processing time 1～60min obtains the wool fabric that fiber surface has nanoscale concaveconvex shape structure;
(2). the wool fabric that the fiber surface that step (1) is obtained has the nanoscale concaveconvex structure further carries out the chitin arrangement, it is the chitin water soluble liquid of 0.5～10g/L that described chitin arrangement is to use concentration, with 1: 20～1: 60 bath raio, under 25～40 ℃ of temperature with textile impregnation, take out mangle, pick-up rate is 70～90%, preliminary drying under 70～90 ℃ of temperature then, and under 100～160 ℃ of temperature, cure.
4. method as claimed in claim 3 is characterized in that: described non-polymerization gas is air, oxygen, nitrogen, carbon dioxide, argon gas, helium, ammonia or their any mist.
5. method as claimed in claim 3 is characterized in that: the pressure in the described feeding non-polymerization gas regulation process chamber is 26～85Pa.
6. method as claimed in claim 3 is characterized in that: described discharge power is 50～100W.
7. method as claimed in claim 3 is characterized in that: described carrying out further contains softener at chitin when arrangement in the dressing liquid.
8. method as claimed in claim 7 is characterized in that: the working concentration of described softener is 20～60g/L.
9. as claim 7 or 8 described methods, it is characterized in that: described softener is amido organosilicon class softener, fatty acid acyl amine softener, organic silicon modified by polyether class softener or polymeric fatty alcohols softener.
10. method as claimed in claim 3, it is characterized in that: described carrying out chitin when arrangement, further add softener and carry out textile finishing, in the dressing liquid of the amido organosilicon class softener that contains the chitin of 1.5～2.5g/L, 25～35g/L, with textile impregnation, take out mangle under 35～40 ℃ of temperature, pick-up rate is 80～90%, preliminary drying under 80～90 ℃ of temperature then, and under 110～150 ℃ of temperature, cure.
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| CN 03137141 CN1233896C (en) | 2003-06-05 | 2003-06-05 | Machine cleanable woolen fabrics with nano structure on wool fiber surface and preparation thereof |
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| CN 03137141 CN1233896C (en) | 2003-06-05 | 2003-06-05 | Machine cleanable woolen fabrics with nano structure on wool fiber surface and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826944A (en) * | 2020-05-27 | 2020-10-27 | 江阴兴吴呢绒科技有限公司 | After-finishing method for improving hand feeling of wool loose-structure fabric |
| CN111826956A (en) * | 2020-05-27 | 2020-10-27 | 江苏烨天羊绒科技有限公司 | After-finishing method of washable cashmere scarf |
| CN112160163A (en) * | 2020-08-14 | 2021-01-01 | 闽江学院 | Preparation method of intelligent fiber |
-
2003
- 2003-06-05 CN CN 03137141 patent/CN1233896C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826944A (en) * | 2020-05-27 | 2020-10-27 | 江阴兴吴呢绒科技有限公司 | After-finishing method for improving hand feeling of wool loose-structure fabric |
| CN111826956A (en) * | 2020-05-27 | 2020-10-27 | 江苏烨天羊绒科技有限公司 | After-finishing method of washable cashmere scarf |
| CN112160163A (en) * | 2020-08-14 | 2021-01-01 | 闽江学院 | Preparation method of intelligent fiber |
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| CN1233896C (en) | 2005-12-28 |
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Denomination of invention: Machine cleanable woolen fabrics with nano structure on wool fiber surface and preparation thereof Effective date of registration: 20100415 Granted publication date: 20051228 Pledgee: The Beijing branch of Company limited by guarantee Pledgor: Beijing Deshifeng Clothing & Necktie Co., Ltd. Registration number: 2010990000736 |
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