CN111647955A - Stable-forming superfine-rate attenuated wool based on molecular slip mechanism and preparation method thereof - Google Patents
Stable-forming superfine-rate attenuated wool based on molecular slip mechanism and preparation method thereof Download PDFInfo
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- CN111647955A CN111647955A CN202010452570.XA CN202010452570A CN111647955A CN 111647955 A CN111647955 A CN 111647955A CN 202010452570 A CN202010452570 A CN 202010452570A CN 111647955 A CN111647955 A CN 111647955A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
- D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
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Abstract
The invention discloses a molecular slip mechanism-based stable-forming superfine rate attenuated wool and a preparation method thereof. The wool is prepared by opening the cross-linking of disulfide bonds in macromolecular chains of wool fibers in the pretreatment of the attenuation compound liquid, so that the wool fibers are stably attenuated, and slippage occurs among macromolecules, thereby generating the attenuated wool with a fiber stretching curve platform region still retaining a middle-section yield region. The preparation method comprises the following steps: treating the undrawn wool in a pretreatment solution; heating the attenuated compound liquid to the temperature of the attenuated compound liquid to open chemical bonds in the wool fibers; stretching the treated wool to make the fiber diameter thin; the thinned wool fibers are respectively treated in the primary setting liquid and the secondary setting liquid, and the thinned wool fibers are stably set. The molecular slip mechanism research method adopted by the invention has good effect on the high added value utilization of the ultrashort wool or cashmere fibers.
Description
Technical Field
The invention relates to a method for researching a refining mechanism of wool fibers, in particular to superfine rate attenuated wool which is formed stably based on a molecular slip mechanism and a preparation method thereof.
Background
Wool is an important textile raw material, has the characteristics of good elasticity, good heat retention, strong hygroscopicity, difficult contamination, soft luster and the like, is a material for various high-grade clothes and rare ornaments, and is also widely applied to fabrics in various seasons with strong heat retention. In recent years, with the increase of demand for living quality, wool fabrics having both warmth retention and lightness and thinness have become popular with consumers, and therefore lightness and thinness of wool fabrics have become an important research direction, and reduction of fineness by stretching and thinning is a scientific and effective solution. The boiling water shrinkage rate of the existing wool refining material is generally 12% -40%, namely the main mechanism of the stretching refinement is caused by the transformation from an alpha spiral macromolecular structure to a beta folding macromolecular structure, and through a stretching test, the slow elastic section on the wool stretching curve disappears, generally 0% -3%, the fiber becomes rigid, the integral breaking elongation of the fiber is only 10% -13%, so that the strength of the fiber is not more than 20%, and the fineness of the fiber is not more than 5.5 μm or more than 26%.
Many studies on wool fibers have been carried out, mainly focusing on the following aspects:
the first category relates to the process of wool stretch refining. A knitting yarn of wool draw and thin color spinning A70-648s/2 and its processing technology (patent application No. 201110291393.2) adopts the immersion reduction softening agent, twisting composite drawing technology and permanent shaping technology for 56s short wool, and utilizes the principle that the alpha helical structure is converted into beta folding structure. A technology for drafting and thinning wool (201210389495.2) features that the colloid is used to coat wool for drafting by one time at most according to the easily broken wool in its stretching process. A method for stretch refining and non-permanent shaping of colored and uncolored wool (patent application No. 201310326438.4; 201310326437.X) comprises stretch refining colored or colorless wool having a fineness of 14.7-28.0 μm to a non-permanent shape of 12.7-22.7 μm, and then shrinking the wool under a wet heat condition of 90 ℃ or higher. A method of stretch refining and permanent setting of uncolored wool (patent application No. 201310326446.9) is also to refine wool of the above-mentioned fineness to 12.7 μm to 22.7 μm, and unlike the non-permanent setting, the refined wool is given a set and the strength of the wool can be increased by 20%. The maximum stretching amount of the stretching and thinning process is 100 percent, and the principle is based on the conversion of an alpha helical structure to a beta folding structure, the slippage of a molecular layer is not achieved, and the method is far from the invention.
The second type is the reagent formulation used for wool refining. The chemical treatment agent for wool stretching (patent application No. 01112860.7), the setting treatment agent for refined wool stretching (patent application No. 01112859.3), the multifunctional setting agent and setting process for refined wool stretching (patent application No. 200410024653.X) and the chemical treatment agent for wool stretching and setting (patent application No. 01112858.5) are mainly used in the formula of the chemical treatment agent for the wool stretching and refining treatment process. However, the formulation used in the present invention is very different from the aforementioned formulations. Although the formula can stretch wool, the slippage on the molecular layer surface is not easy to achieve in the stretching process, and stable superfine wool is not easy to form. The invention can further obtain the structural change in the wool fiber stretching process, and obtain the superfine wool by adjusting the relationship among the twist, the drafting speed and the holding distance.
The third type relates to a method for manufacturing a machine dedicated to the fine stretching. A wool top thinning, twisting and stretching test apparatus (patent application No. 200810053074.6) mainly passes through the experimental model and means of stretching wool under the wet and hot condition, the diameter of the wool thinning given in the example is reduced by 3.3 μm or 15% at most. A wool draw false twisting device with a heat pipe (patent application No. 200720018151.5) is a device for improving the false twisting degree and the drawing fineness of wool fibers by utilizing the heat resources of a factory. A wool stretching and setting device and a wool stretching and setting process (patent application number: 201510366668.2) provide the wool stretching and setting device and the wool stretching and setting process, the setting process is wet-heat setting (the temperature is 80-100 ℃ and the relative humidity is 90-100%), the stretching times are not mentioned in the patent, and only the strip discharging speed is limited. A wool stretching auxiliary agent blending and conveying device (patent application number: 201420296122.5) only realizes blending and conveying of auxiliary agents and does not relate to the principle and process of stretching and refining. A wool continuous stretching device (application number: 201420434896.X) is mainly used for the continuous production of the wool by physical refining, and a specific refining method and stretching times are not given in the patent. The maximum theoretical stretching ratio of the special machine (patent application number: 200410025087.4) for thinning and stretching wool and various animal fibers (or fabrics) is 70%. The special stretching machines of the types have the outstanding characteristics of low stretching and thinning rate and difficult formation of superfine wool. Compared with the present invention, the invention principle provided by the present invention is completely different from the above examples, and the stretching and thinning degree is greatly improved, and the thinning effect is far better than that of the above materials.
In conclusion, the existing wool refining materials still have the defect of low refining efficiency. Therefore, the patent proposes a method for drawing and refining wool fibers with ultra-fine rate by combining the transformation of alpha helix to beta sheet structure and the 'partial slip refining' to solve the above-mentioned defects.
Disclosure of Invention
The invention aims to solve the problems that: how to realize the stable superfine of wool under the condition of low stretching and thinning rate at present.
In order to solve the technical problems, the invention provides drawn wool with a stable superfine rate formed based on a molecular sliding mechanism, which is characterized in that the wool is drawn wool with a high refining rate and a fiber stretching curve platform area with non-decreasing and non-increasing strength and a middle-section yield area remained in the drawing wool, wherein the wool is formed by opening the cross-linking of disulfide bonds in the macromolecular chains of wool fibers (the disulfide bonds among macromolecules are completely opened and the disulfide bonds among the sections of spiral molecular chains are less opened) in the pretreatment of drawing compound liquid, so that the wool fibers are smoothly drawn and thinned, and the slippage occurs among the macromolecules.
Preferably, the attenuation compound liquid comprises a pretreatment liquid, a primary sizing liquid and a secondary sizing liquid.
More preferably, the pretreatment solution comprises at least one of sodium bisulfite, thioglycolic acid, a surfactant, triethanolamine and an EDTA salt; the primary sizing solution comprises at least one of potassium persulfate, acetic acid, zinc acetate and hexamethylenetetramine; the secondary shaping liquid is a resin liquid of magnesium chloride.
Preferably, the mass concentration of the attenuation compound liquid is 1-5%.
Preferably, the fiber diameter of the wool before treatment is 18-25 μm, and within the diameter range, the thicker the wool, the more obvious the thinning effect is, and the upper limit of diameter thinning can be realized.
Preferably, the superfine rate means that the diameter of the treated wool is 20-32% of that of the wool before treatment; the increase rate of the fiber stretching degree of the wool is 8 to 40 percent; the elongation at break of the wool fiber is 15 to 20 percent; the platform area of the wool fiber after the tensile curve passes through the yield point still has 5-12% of elastic elongation, and the crimp elastic recovery rate of the wool is 20-50%.
More preferably, the fiber diameter of the wool is thinned by 5 to 7.5 μm after treatment.
The invention also provides a preparation method of the superfine rate attenuated wool with stable forming based on the molecular slip mechanism, which is characterized by comprising the following steps:
step 1): treating the undrawn wool in a pretreatment solution; heating the attenuated compound liquid to the temperature of the attenuated compound liquid to open chemical bonds in the wool fibers;
step 2): stretching the treated wool to make the fiber diameter thin;
step 3): the thinned wool fibers are respectively treated in the primary setting liquid and the secondary setting liquid, and the thinned wool fibers are stably set.
Preferably, the process parameters of the stretching in the step 2) are as follows: the twist is 10-30 twist/m, the stretching speed is 30-50%/min, and the stretching rate is 80-120%.
Preferably, the stretching process in the step 2) includes two parts of conversion of alpha helix to beta sheet structure and slippage of microstructure blocks.
The evaluation mechanism of the present invention is based on the following:
the wool can be stretched and refined by the molecular structure of the wool, the structure of the wool microfibril is formed by adding a circle of 9 basic fibrils and two middle basic fibrils, the basic fibrils are generally considered to be formed by 3 helices or 2+2 repeated helices of macromolecules, the macromolecules are bonded together through disulfide bonds, the disulfide bonds among the macromolecules can be completely opened through a chemical method, and the slippage among the macromolecules can be generated by stretching. In the process of producing yarn, the drawing and thinning of the top or roving are caused by slippage between fibers. However, the macromolecules are not only bonded together by disulfide bonds, but also salt bonds, hydrogen bonds, and van der waals forces are present. The average length of every three amino acid residues in the wool fiber is
Thus, the average length of each α amino acid residue is
When the fiber is stretched by drawing, the molecular arrangement can be converted into β folded structure with repeating unit length
From the peptide chain structure, the length of the repeating molecular chain can be calculated, and the straightening times of the molecular chain when the secondary structure of wool is changed from α type to β type are as follows:
the results indicate that the maximum stretching multiple of the wool fiber is 93% if the wool fiber is converted only from the α -helical structure to the β -sheet structure during the refining process.
In fact, it is impossible and not desirable for the wool fibers to completely convert the α -helical structure into the β -sheet structure during the thinning process. As an impossibility, one is that there is no possibility of a complete alpha helical conformation in the fiber, but that there are alpha, non-alpha and beta structures; secondly, the network cross-linking structure will cause part of the alpha structure to be unable to transform into beta structure. The X-ray diffraction results show that the transformation of alpha structure to beta structure always occurs in the wool fibers in the yield zone and the strengthening zone (Bendit E G.A qualitative X-ray diffraction basis of the alpha-beta transformation in wood fiber. textileRes. J.,1960,30(8): 547-555); thirdly, the defects and weak nodes of the fiber structure can not realize the alpha-beta transformation of an ideal perfect structure (Yu W, Postle R, Yan H. geological and mechanical characteristics of the week-points of wood fibers, Pro.6th ATC. hong Kong.2001-08-22-24.4). As an unforeseeable principle, firstly, the properties of the fibers are different, the respective stretching multiples are different, and the requirement of the theoretical stretching multiple cannot be met on the whole; secondly, after the alpha structure is completely converted into the beta structure, the molecular structure of the refined wool is unstable, and the beta structure can be partially retracted into the alpha structure under the damp and hot condition, so that the refining effect is difficult to stabilize.
It can be seen from the above analysis that when the wool fiber stretch ratio is increased to be greater than the transition from the α -helical structure to the β -sheet structure, the internal forming mechanism is converted to a molecular slip mechanism.
The shrinkage of the wool fiber treated by boiling water is not more than 10 percent, namely the dimensional stability of the wool fiber is far superior to that of the prior refined wool. The wool prepared by the invention can be used as a material for clothes such as high-grade western-style clothes, trousers, sweaters and the like.
The invention provides stable superfine rate attenuated wool formed based on a molecular slip mechanism and a preparation method thereof, and is characterized in that the research method of the stretching mechanism has good effect on high added value utilization of ultrashort wool or cashmere fibers.
Compared with the prior art, the invention has the beneficial effects that:
(1) the two-time shaping method can respectively fix disulfide bond cross-linking and macromolecular chains, thereby increasing the stability of the microstructure;
(2) the two mechanisms of conversion from alpha helix to beta folded structure and slippage of the microstructure block act at the same time, and the obtained refined wool has good stability;
(3) the invention has wide application range and can be used for the processing technology of high added value of wool short velvet, cashmere short velvet and fibrilia.
Drawings
Fig. 1 is a schematic diagram of structural transformation during the stretching of wool fibers.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The percentages in examples 1 to 3 are by mass unless otherwise specified.
Example 1
Pretreating wool fibers in 1 wt% of sodium bisulfate treatment liquid at 80 ℃, opening disulfide bonds and salt bonds among spiral macromolecules, then stretching on a stretcher, setting the stretched and set wool tops in 5% of potassium persulfate and 2% of zinc acetate solution, setting in secondary setting liquid of 2% of magnesium chloride resin liquid, drying and baking to obtain refined wool tops, wherein the twist number is 45 twists/m, the stretching speed is 50%/min, and the stretching rate is 80%. The results show that the disulfide bonds between macromolecules of wool fibers are opened during the stretching process, and the slippage of microstructure blocks is also realized besides the transformation of an alpha helical structure into a beta folded structure. Through test, the diameter of the obtained wool fiber is thinned from 22.5 mu m to 18 mu m, the strength of the fiber is increased from 12.7cN/tex to 14.6cN/tex, the elongation of the fiber is 35%, the shrinkage of the thinned wool after boiling water treatment is 7%, and the crimp elastic recovery of the wool is 30%.
Example 2
Pretreating wool fibers in 3 wt% of sodium bisulfate treatment liquid at 75 ℃, opening disulfide bonds and salt bonds among spiral macromolecules, then stretching on a stretcher, setting the stretched and set wool tops in 6.5% of potassium persulfate and 1.5% of zinc acetate solution, setting in secondary setting liquid of 3% of magnesium chloride resin liquid, drying and baking to obtain refined wool tops, wherein the twist is 30 twists/m, the stretching speed is 50%/min, and the stretching rate is 100%. The results show that the disulfide bonds between macromolecules of wool fibers are opened during the stretching process, and the slippage of microstructure blocks is also realized besides the transformation of an alpha helical structure into a beta folded structure. Through test, the diameter of the obtained wool fiber is reduced from 22.5 mu m to 13.5 mu m, the strength of the fiber is increased from 12.7cN/tex to 19.0cN/tex, the elongation of the fiber is 17%, the shrinkage of the fiber after the refined wool is treated by boiling water is 9%, and the crimp elastic recovery of the wool is 48%.
Example 3
Pretreating wool fibers in 5 wt% of sodium bisulfate treatment liquid at 70 ℃, opening disulfide bonds and salt bonds among spiral macromolecules, then stretching on a stretcher, setting the stretched and set wool tops in 5.5% of potassium persulfate and 2.5% of zinc acetate solution, setting in secondary setting liquid of 4% of magnesium chloride resin liquid, drying and baking to obtain refined wool tops, wherein the twist is 15 twists/m, the stretching speed is 30%/min, and the stretching rate is 90%. The results show that the disulfide bonds between macromolecules of wool fibers are opened during the stretching process, and the slippage of microstructure blocks is also realized besides the transformation of an alpha helical structure into a beta folded structure. Through test, the diameter of the obtained wool fiber is reduced from 22.5 mu m to 15.8 mu m, the strength of the fiber is increased from 12.7cN/tex to 17.2cN/tex, the elongation of the fiber is 20%, the shrinkage of the fiber after the refined wool is treated by boiling water is 6%, and the crimp elastic recovery of the wool is 35%.
Claims (10)
1. A stable superfine rate attenuated wool formed based on a molecular slip mechanism is characterized in that the wool is obtained by opening the cross-linking of disulfide bonds in macromolecular chains of wool fibers in the pretreatment of an attenuated compound liquid, so that the wool fibers are smoothly attenuated, and slippage occurs among macromolecules, thereby generating the attenuated wool with a fiber tensile curve platform region still retaining a middle-section yield region.
2. The method of claim 1, wherein the attenuating compound fluid comprises a pretreatment fluid, a primary sizing fluid, and a secondary sizing fluid.
3. The method of forming a stabilized superfine wool stream based on molecular slip mechanism according to claim 2 wherein the pretreatment solution comprises at least one of sodium bisulfite, thioglycolic acid, surfactant, triethanolamine and EDTA salt; the primary sizing solution comprises at least one of potassium persulfate, acetic acid, zinc acetate and hexamethylenetetramine; the secondary shaping liquid is a resin liquid of magnesium chloride.
4. The method according to any one of claims 1 to 3, wherein the mass concentration of the attenuated composite liquid is 1 to 5%.
5. The method according to claim 1 or 2, wherein the fiber diameter of the wool before the treatment is 18 to 25 μm.
6. The method according to claim 1 or 2, wherein the superfine rate of the formed wool is 20-32% of the diameter of the wool before the treatment; the increase rate of the fiber stretching degree of the wool is 8 to 40 percent; the elongation at break of the wool fiber is 15 to 20 percent; the platform area of the wool fiber after the tensile curve passes through the yield point still has 5-12% of elastic elongation, and the crimp elastic recovery rate of the wool is 20-50%.
7. The method according to claim 6, wherein the fiber diameter of the wool is reduced by 5 to 7.5 μm.
8. The method of producing ultrafine rate attenuated wool formed stably based on the molecular slip mechanism according to any of claims 2 to 7, comprising the steps of:
step 1): treating the undrawn wool in a pretreatment solution; heating the attenuated compound liquid to the temperature of the attenuated compound liquid to open chemical bonds in the wool fibers;
step 2): stretching the treated wool to make the fiber diameter thin;
step 3): the thinned wool fibers are respectively treated in the primary setting liquid and the secondary setting liquid, and the thinned wool fibers are stably set.
9. The method for preparing ultrafine rate attenuated wool with stable formation based on molecular slip mechanism as claimed in claim 8, wherein the process parameters for stretching in step 2) are: the twist is 10-30 twist/m, the stretching speed is 30-50%/min, and the stretching rate is 80-120%.
10. The method for preparing ultrafine rate attenuated wool with stable formation based on molecular slip mechanism according to claim 8, wherein the stretching process in step 2) comprises two parts of conversion of alpha helix to beta sheet structure and slippage of microstructure blocks.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323935A (en) * | 2001-05-11 | 2001-11-28 | 东华大学 | Chemical process for fining and settling wool |
| CN1916263A (en) * | 2006-09-04 | 2007-02-21 | 大连轻工业学院 | Method for drawing and modifying wool fibre |
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- 2020-05-26 CN CN202010452570.XA patent/CN111647955A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323935A (en) * | 2001-05-11 | 2001-11-28 | 东华大学 | Chemical process for fining and settling wool |
| CN1916263A (en) * | 2006-09-04 | 2007-02-21 | 大连轻工业学院 | Method for drawing and modifying wool fibre |
Non-Patent Citations (1)
| Title |
|---|
| 唐芙菊: "拉伸细化羊毛二级结构的分析与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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