CN100485098C - Modified viscose fibre and its producing method - Google Patents
Modified viscose fibre and its producing method Download PDFInfo
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- CN100485098C CN100485098C CN 200610016426 CN200610016426A CN100485098C CN 100485098 C CN100485098 C CN 100485098C CN 200610016426 CN200610016426 CN 200610016426 CN 200610016426 A CN200610016426 A CN 200610016426A CN 100485098 C CN100485098 C CN 100485098C
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Abstract
The present invention relates to one kind of modified viscose fiber and its producing process. The modified viscose fiber consists of hydroxyethyl chitosan 0.5-20 wt%, fibroin 5-30 wt%, and cellulose 60-94.5 wt%. The hydroxyethyl chitosan has viscosity average molecular weight of 20-500 KD and hydroxyethyl radical substituting degree of 10-90 %, and the fibroin has viscosity average molecular weight of 10-80 KD. The production process of the modified viscose fiber includes the following steps: 1. preparing fibroin solution; 2. preparing viscous solution of hydroxyethyl chitosan xanthate via alkalizing and esterification with xanthanic acid; and 3. mixing the components in the recipe, filtering, defoaming, curing to obtain spinning dope and spinning. The modified viscose fiber has excellent antibacterial and skin care function.
Description
Technical field
The present invention relates to a kind of chemical fibre manufacturing technology, be specially the viscose with good antibiotic skin-protecting function and the manufacture method thereof of a kind of hydroxyethyl chitosan-fibroin-cellulose ternary blend, international Patent classificating number intends being Int.Cl DO1F 2/08 (2006.01).
Background technology
Viscose has advantages such as sucting wet air permeability is good, snugness of fit is good as a kind of regenerated fiber, is widely used.In order to satisfy the many-sided requirement of people to fiber, can be by in the spinning process of viscose, adding the exploitation that some functional components realize functional viscose fiber, as Fire resistant viscose fiber, anion viscose fibre, antibacterial viscose fiber etc.
Shitosan is the very abundant natural macromolecular materials of a kind of natural resources, has many-sided advantages such as broad spectrum antibacterial, biocompatibility, biological degradability, utilizes chitin modified other fiber to become fiber functionalization research focus to obtain anti-microbial property.Simultaneously, because shitosan and cellulosic molecule structural similarity, therefore chitin modified cellulose fibre has more feasibility.The industrial production of cellulose fibre especially also mainly depends on viscose in China at present.The main way of utilizing chitosan modified viscose fiber is by certain form the appropriate format and the viscose glue blending of shitosan to be made spinning solution, as U.S. Pat P Re.35151 disclose a kind of with shitosan pulverize for particle diameter less than the particulate of 5 μ m and sneak into the method for carrying out spinning in the viscose glue; Chinese patent 02160199.2 and U.S. Pat P5756111 then disclose shitosan have been carried out after the xanthic acid esterification method with the viscose glue blending spinning.This method has improved shitosan and cellulosic dispersiveness, has improved the performance of fiber.But because the reactivity worth of the xanthic acid esterification of shitosan is poor, the content of ash impurities is very big to its reactivity worth influence in the raw material, content of ashes that need to point out shitosan among the U.S. Pat P5756111 is less than the 0.2% shitosan xanthate that just can make the performance homogeneous, promptly the purity to shitosan has proposed very harsh requirement, need carry out very strict making with extra care to the shitosan raw material.This method efficient is low, the cost height, and difficult quality guarantee not too is suitable for large-scale industrial production.Meanwhile, in order to improve the anti-microbial property of shitosan, a series of chitosan derivatives are developed.Hydroxyethyl chitosan is as a kind of hydroxyethyl modified product of shitosan, has that antibiotic property is good, the reactivity worth advantages of higher.But do not see the report that hydroxyethyl chitosan is used for the viscose glue modified fibre before.
Fibroin is that silk silk capsule protein forms water miscible peptide material through degraded, research has shown that it contains 18 seed amino acids, water-soluble better, can promote the skin activation, have delay skin aging, whiten, effects such as skin moisten, isolation ultraviolet ray, its preparation textiles has good skin effect.Utilize fibroin that hydroxyethyl chitosan is carried out modification, help improving the skin effect of viscose, and it is smooth, soft to give the feel of viscose, performances such as moisture absorption.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of modified viscose fiber and manufacture method thereof are provided, and this viscose has good antibacterial property, biocompatibility, hygroscopicity and skin effect, and feel is smooth, soft, has actual application value; The manufacturing approach craft of this viscose is simple, and condition control easily, and is with low cost, is suitable for industrial applications.
The technical scheme that the present invention solves described viscose technical problem is: design a kind of modified viscose fiber, its mass percent prescription is:
Hydroxyethyl chitosan 0.5-20%;
Fibroin 5-30%;
Cellulose 60-94.5%, each component sum equals 100%;
The viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10～90%;
The viscosity average molecular weigh of described fibroin is 1～80,000.
The technical scheme that the present invention solves described viscose manufacture method technical problem is: design a kind of modified viscose fiber manufacture method, this manufacture method is a foundation with viscose mass percent prescription of the present invention, and adopts following processing step:
1. preparation fibroin solution: it is that 40～60 ℃, concentration are in 1～8% the sodium hydrate aqueous solution that fibroin is dissolved in temperature, after the filtration, the initator hydrogen peroxide that in this solution, adds fibroin quality 0.1～1%, press 10～20% of fibroin quality again and add polyvinyl alcohol, under 35～45 ℃, stir, make the fibroin solution of concentration 2-7%;
2. preparation hydroxyethyl chitosan xanthate viscosity solution: 1. alkalization process: with the hydroxyethyl chitosan of particle diameter≤4mm under 10～40 ℃, in 10～50% sodium hydrate aqueous solution, soak 30～600min; bath raio is 1:5～30, get hydroxyethyl chitosan alkalization product; 2. xanthic acid esterification reaction: 1. middle gained hydroxyethyl chitosan alkalization product is placed the capping still, the carbon disulfide that adds hydroxyethyl chitosan quality 20～80%, keeping reaction temperature is-10～22 ℃, reacted 1～8 hour, and then add 2～10 times of water to hydroxyethyl chitosan and stir, obtain hydroxyethyl chitosan xanthate viscosity solution;
3. co-blended spinning: according to formula rate of the present invention, resulting hydroxyethyl chitosan xanthate viscosity solution during resulting fibroin solution, the 2nd goes on foot in the 1st step and viscose glue blending is even, deaeration and maturing process after filtration,, obtain modification rayon spinning stoste, utilize rayon spinning technology to carry out spinning again, can obtain modified viscose fiber of the present invention.
Compare with present antibacterial viscose fiber technology, modified viscose fiber of the present invention is to adopt hydroxyethyl chitosan and two kinds of compositions of fibroin that viscose is carried out modification, resultant is the modified viscose fiber of hydroxyethyl chitosan-fibroin-cellulose ternary blend, has multiple advantageous feature, particularly based on the characteristic of hydroxyethyl chitosan and fibroin, modified viscose fiber of the present invention has good antibiotic skin-care health-care function, has excellent biological compatibility simultaneously, dyeability, hygroscopicity and biological degradability, and feel is smooth, softnesses etc. are suitable for actual applying.
The present invention designs and adopts the antibiotic skin-care modifier of hydroxyethyl chitosan as fiber, and utilizes shitosan different as the manufacture method of antiseptic in the document of present existence: owing to introduced-CH on the strand of hydroxyethyl chitosan
2CH
2The OH group, its reactivity worth improves greatly, thereby make modified viscose fiber of the present invention not only the antibiotic skin-care performance increase, and its manufacture method also reduces greatly to the purity of raw materials for production, the requirement of reaction condition, and the solubility property of hydroxyethyl chitosan xanthate, strainability are all better, and industrially scalable is used easy to implement.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment.
A kind of modified viscose fiber (the following viscose that is called for short) of the present invention's design, its percentage by weight prescription is: hydroxyethyl chitosan is 0.5-20%; Fibroin is 5-30%; Cellulose is 60-94.5%, and each component sum equals 100%; The viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10～90%; The viscosity average molecular weigh of described fibroin is 1～80,000.
Hydroxyethyl chitosan of the present invention and fibroin and preparation method thereof this as prior art, but then be original creation of the present invention as viscose modifier with hydroxyethyl chitosan and fibroin.Design adopts hydroxyethyl chitosan and fibroin that viscose is carried out modification, makes modified viscose fiber of the present invention have antibiotic simultaneously and multi-functional effect skin care, meets people to taking the demand trend of fiber.How much what the present invention filled a prescription described each constituent content depends on the product design needs.In the reality, the recipe ingredient material can specifically be chosen or design in described mass percent as required.Compared with prior art, the antibiotic property of hydroxyethyl chitosan and reactivity worth are better than shitosan.Studies show that the hydroxyethyl chitosan viscosity average molecular weigh has stronger antibiotic property in 2～500,000 scopes, especially viscosity average molecular weigh can show very strong anti-microbial property at 4～150,000 o'clock.The hydroxyethyl chitosan viscosity average molecular weigh of the embodiment of the invention preferred 4～150,000.The substitution value of hydroxyethyl chitosan also has considerable influence to its reactivity worth, and hydroxyethyl chitosan used in the present invention is characterised in that its substitution value is designed to 10～90%; The viscosity average molecular weigh of fibroin preferred 1～80,000.The design that exceeds formula rate scope of the present invention be not feasible scarcely, but effect is undesirable.
The present invention has designed the manufacture method of described modified viscose fiber simultaneously.This manufacture method is according to the described modified viscose fiber prescription of invention, and the following processing step of employing:
1. preparation fibroin solution: it is that 40～60 ℃, concentration are in 1～8% the sodium hydrate aqueous solution that fibroin is dissolved in temperature, after the filtration, adds the initator hydrogen peroxide (H of fibroin quality 0.1～1%
2O
2) after, add polyvinyl alcohol again by 10～20% of fibroin quality, under 35～45 ℃, stir, make concentration and be 2～7% fibroin solution; The excessive concentration of fibroin solution (greater than 7%) is implemented difficulty and is strengthened unfavorable application on the technology; And fibroin solution concentration low excessively (less than 2%), the products obtained therefrom effect is undesirable, also unfavorable application.Generally speaking, the higher design of fibroin solution concentration is comparatively desirable.
2. preparation hydroxyethyl chitosan xanthate viscosity solution: 1. alkalization process: with the hydroxyethyl chitosan of particle diameter≤4mm under 10～40 ℃, in 10～50% sodium hydrate aqueous solution, soak 30～600min; bath raio is 1:5～30, can get hydroxyethyl chitosan alkalization product; 2. xanthic acid esterification reaction: 1. middle gained hydroxyethyl chitosan alkalization product is placed the capping still, and add the carbon disulfide (CS of hydroxyethyl chitosan quality 20～80% (or 0.2～0.8 times)
2), keeping reaction temperature is-10～22 ℃, reacts 1～8 hour, and then adds 2～10 times of water to hydroxyethyl chitosan and stir, and can obtain hydroxyethyl chitosan xanthate viscosity solution; When described reaction temperature was negative value, though reaction effect is better, the reaction time was long partially, and the commercial Application equipment investment increases, and should weigh consideration during commercial Application.
3. co-blended spinning: according to the formula rate of modified viscose fiber of the present invention, with the fibroin solution that obtains in the 1st step, the hydroxyethyl chitosan xanthate viscosity solution and the viscose glue blending that obtain are even in the 2nd step, deaeration and maturing process after filtration,, can obtain modification rayon spinning stoste, utilize rayon spinning technology to carry out spinning again and can obtain modified viscose fiber of the present invention.
The further feature of the manufacture method of modified viscose fiber of the present invention is, in the 2. xanthic acid esterification reaction of described the 2nd step preparation hydroxyethyl chitosan xanthate viscosity solution, after earlier the alkalization product of described hydroxyethyl chitosan being squeezed 2～8 times to the hydroxyethyl chitosan raw material weight, insert again in the capping still and react.The design of squeezing process helps removing part alkali solubility impurity, improves the effect of shitosan xanthic acid esterification reaction.Squeezing process is originally as known technology.
The modification rayon spinning stoste of utilizing described in the viscose manufacture method of the present invention adopts rayon spinning technology to carry out spinning originally as known technology, and the technology adjustment is few, and in those of ordinary skills' scope as can be known.But hydroxyethyl chitosan and fibroin technology suitably be incorporated into be contribution of the present invention in viscose prescription and the spinning manufacture method thereof.Introduced on the strand of hydroxyethyl chitosan of the present invention-CH
2CH
2Behind the OH group, reactivity increases, and reactivity worth improves, and obtained modified viscose fiber is a kind of with antibiotic and multi-functional viscose skin care effect.
Characteristics such as the anti-microbial property of viscose of the present invention, dyeability, hygroscopicity, biocompatibility, biological degradability have raising, and are applicable to weaving processing, can be used for making underwear, dormitory articles and medical textile etc.
The present invention does not address part and is applicable to prior art.
Below provide specific embodiments of the invention.The present invention is not subjected to the restriction of specific embodiment.
Embodiment 1
Fibroin is dissolved under 40 ℃ in 2% the NaOH solution, after the filtration, adds the H of fibroin quality 0.1%
2O
2After, add the polyvinyl alcohol of fibroin quality 10% again, stir under 40 ℃, obtain concentration and be 5% fibroin solution; Under 15 ℃, caustic dip is 600 minutes in 15% the NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:30; Gained alkalization product is transferred in the capping still, and is added the CS of 0.7 times of hydroxyethyl chitosan quality through squeezing 7 times for raw material weight
2, 0 ℃ of down reaction 7 hours, and then add 9 times of water and stir to hydroxyethyl chitosan, can obtain hydroxyethyl chitosan xanthate viscosity solution; Fibroin solution, hydroxyethyl chitosan xanthogenate solution and the viscose glue of gained are carried out blend, making initial hydroxyethyl chitosan, fibroin and cellulosic mass ratio is 0.5:5:94.5, carry out spinning according to traditional rayon spinning technology, can obtain the modified viscose fiber of above-mentioned component ratio.
Embodiment 2
Fibroin is dissolved under 50 ℃ in the 5%NaOH solution, adds the H of fibroin quality 0.1%
2O
2After, add the polyvinyl alcohol of fibroin quality 20% again, stir under 40 ℃, obtaining concentration is 6% fibroin solution; Under 30 ℃, caustic dip is 300 minutes in 25% the NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:25; Transfer in the capping still, and add the CS of 0.7 times of hydroxyethyl chitosan quality
20 ℃ of down reaction 6.5 hours, and then add 8 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan; Fibroin solution, hydroxyethyl chitosan xanthogenate solution and the viscose glue of gained are carried out blend, making initial hydroxyethyl chitosan, fibroin and cellulosic mass ratio is 5:15:80, carry out spinning according to traditional rayon spinning technology, can obtain the modified viscose fiber of above-mentioned component ratio.
Embodiment 3
Fibroin is dissolved under 50 ℃ in 3% the NaOH solution, after the hydrogen peroxide that adds fibroin quality 0.8% after filtering causes, add 20% polyvinyl alcohol again according to the fibroin quality, stir, obtain concentration and be 5% fibroin solution; Under 15 ℃, caustic dip is 600 minutes in the 15%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:30, and gained alkalization product, is transferred in the capping still for 7 times of raw material weights through squeezing, and adds the CS of 0.7 times of hydroxyethyl chitosan quality
20 ℃ of down reaction 6 hours, and then add 5 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan; Fibroin solution, hydroxyethyl chitosan xanthogenate solution and viscose glue are carried out blend, making initial hydroxyethyl chitosan, fibroin and cellulosic mass ratio is 1.5:20:78.5, carry out spinning according to traditional rayon spinning technology, can obtain the modified viscose fiber of above-mentioned component ratio.
Embodiment 4
Fibroin is dissolved under 55 ℃ in 8% the NaOH solution, obtain the fibroin spinning solution after filtration, after the hydrogen peroxide of adding fibroin quality 1% causes, polyvinyl alcohol according to fibroin quality adding 19%, stir, obtain concentration and be 4% fibroin spinning solution; Under 30 ℃, caustic dip is 300 minutes in the 25%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:25, transfers in the capping still, and adds the CS of 0.7 times of hydroxyethyl chitosan quality
20 ℃ of down reaction 8 hours, and then add 3 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan; Fibroin solution, hydroxyethyl chitosan xanthogenate solution and viscose glue are carried out blend, making initial hydroxyethyl chitosan, fibroin and cellulosic mass ratio is 8:15:87, carry out spinning according to traditional rayon spinning technology, can obtain the modified viscose fiber of above-mentioned component ratio.
Embodiment 5
Fibroin is dissolved under 48 ℃ in 6% the NaOH solution, obtain the fibroin spinning solution after filtration, after the hydrogen peroxide of adding fibroin quality 0.7% causes, polyvinyl alcohol according to fibroin quality adding 16%, stir, make concentration and be 2% fibroin spinning solution.Under 30 ℃, caustic dip is 300 minutes in the 25%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:25; Transfer in the capping still, and add 0.35 times CS
215 ℃ of down reactions 5 hours, and then add 10 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan; Fibroin solution, hydroxyethyl chitosan xanthogenate solution and viscose glue are carried out blend, making initial hydroxyethyl chitosan, fibroin and cellulosic mass ratio is 5:12:83, carry out spinning according to traditional rayon spinning technology, can obtain the modified viscose fiber of above-mentioned component ratio.
Embodiment 6
Fibroin is dissolved under 42 ℃ in 2% the NaOH solution, obtain the fibroin spinning solution after filtration, after the hydrogen peroxide of adding fibroin quality 0.5% causes, polyvinyl alcohol according to fibroin quality adding 18%, stir, make concentration and be 7% fibroin spinning solution; Under 15 ℃, caustic dip is 600 minutes in the 15%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1:30, and gained alkalization product is transferred in the capping still, and adds the CS of 0.3 times of hydroxyethyl chitosan quality
220 ℃ of down reactions 6 hours, and then add 2 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan.With this viscosity solution and viscose glue with the 10:90 quality than blend and filter, deaeration, maturation process, obtain modification rayon spinning liquid, utilize traditional adhering process that above-mentioned modification rayon spinning liquid is carried out spinning again, simultaneously the fibroin spinning solution adds with injection system before spinning, and makes that content is hydroxyethyl chitosan in the modified viscose fiber: fibroin: cellulose=12:10:88.
Embodiment 7
Fibroin is dissolved under 40 ℃ in 5% the NaOH solution, obtain the fibroin spinning solution after filtration, after the hydrogen peroxide of adding fibroin quality 0.1 ‰ causes, polyvinyl alcohol according to fibroin quality adding 10%, stir, make concentration and be 6% fibroin spinning solution; Hydroxyethyl chitosan under 10 ℃, is soaked in the 35%NaOH aqueous solution and alkalized in 240 minutes, transfer in the capping still, and add the CS of 0.4 times of hydroxyethyl chitosan quality
218 ℃ of down reactions 3 hours, and then add 6 times of water and stir, can obtain hydroxyethyl chitosan xanthate viscosity solution to hydroxyethyl chitosan; With the viscosity solution of gained and viscose glue with the 5:95 quality than blend and filter, deaeration, maturation process, obtain modification rayon spinning liquid; Utilize traditional adhering process that above-mentioned modification rayon spinning liquid is carried out spinning again, simultaneously the fibroin spinning solution adds with injection system before spinning, and makes that content is hydroxyethyl chitosan in the modified viscose fiber: fibroin: cellulose=6:12:82.
Claims (4)
1. modified viscose fiber, its mass percent prescription is:
Hydroxyethyl chitosan 0.5-20%;
Fibroin 5-30%;
Cellulose 60-94.5%, each component sum equals 100%;
The viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10～90%; The viscosity average molecular weigh of described fibroin is 1～80,000.
2. modified viscose fiber according to claim 1, the viscosity average molecular weigh that it is characterized in that described hydroxyethyl chitosan is 4～150,000.
3. manufacture method of modified viscose fiber as claimed in claim 1 or 2, it adopts following processing step:
(1) preparation fibroin solution: it is that 40～60 ℃, concentration are in 1～8% the sodium hydrate aqueous solution that fibroin is dissolved in temperature, after the filtration, the initator hydrogen peroxide that adds fibroin quality 0.1～1%, add polyvinyl alcohol again by 10～20% of fibroin quality, under 35～45 ℃, stir, make concentration and be 2～7% fibroin solution;
(2) preparation hydroxyethyl chitosan xanthate viscosity solution: 1. alkalization process: with the hydroxyethyl chitosan of particle diameter≤4mm under 10～40 ℃, in 10～50% sodium hydrate aqueous solution, soak 30～600min; bath raio is 1:5～30, get hydroxyethyl chitosan alkalization product; 2. xanthic acid esterification reaction: 1. middle gained hydroxyethyl chitosan alkalization product is placed the capping still, the carbon disulfide that adds hydroxyethyl chitosan quality 20～80%, keeping reaction temperature is-10～22 ℃, reacted 1～8 hour, and then add 2～10 times of water to hydroxyethyl chitosan and stir, obtain hydroxyethyl chitosan xanthate viscosity solution;
(3) co-blended spinning: according to claim 1 or 2 described modified viscose fiber formula rates, the hydroxyethyl chitosan xanthate viscosity solution and the viscose glue blending that obtain in the fibroin solution that obtains in (1), (2) is even, deaeration and maturing process after filtration,, obtain modification rayon spinning stoste, utilize rayon spinning technology to carry out spinning again, can obtain described modified viscose fiber.
4. according to the manufacture method of the described modified viscose fiber of claim 3, it is characterized in that in the 2. xanthic acid esterification reaction of described (2) preparation hydroxyethyl chitosan xanthate viscosity solution, after earlier the alkalization product of described hydroxyethyl chitosan being squeezed 2～8 times to the hydroxyethyl chitosan raw material weight, insert again in the capping still and react.
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| CN101649505B (en) * | 2009-09-10 | 2011-09-14 | 山东省花生研究所 | Composite fiber of isolated peanut protein and preparation method thereof |
| CN102277640A (en) * | 2010-06-12 | 2011-12-14 | 罗莱家纺股份有限公司 | Hydroxyethyl chitosan modified viscose and manufacturing method thereof |
| CN102286881A (en) * | 2010-06-17 | 2011-12-21 | 罗莱家纺股份有限公司 | Pupa albumen fiber and production process thereof |
| CN102304783B (en) * | 2011-07-07 | 2012-10-10 | 狄友波 | Preparation method of antibacterial anti-flaming protein viscose fiber |
| CN102505170B (en) * | 2011-10-26 | 2013-12-18 | 阜宁澳洋科技有限责任公司 | Method for preparing silk protein composite cellulose fibers |
| CN103835022B (en) * | 2014-03-07 | 2014-10-29 | 宏远纺织科技（泉州）有限公司 | Cellulose blended fibers and preparation method thereof |
| CN105803568A (en) * | 2014-12-30 | 2016-07-27 | 上海水星家用纺织品股份有限公司 | Preparation method of silk protein fibers |
| CN104862819A (en) * | 2015-06-15 | 2015-08-26 | 湖州市菱湖重兆金辉丝织厂 | High-strength degradable regenerated silk protein fiber and preparation method thereof |
| CN105821518B (en) * | 2016-05-13 | 2018-02-06 | 广东艺森地毯顾问实业有限公司 | A kind of preparation method of pupa albumen/lotus cellulose composite fiber |
| CN108708060A (en) * | 2018-06-08 | 2018-10-26 | 苏州印丝特纺织数码科技有限公司 | A kind of preparation method of low-cost and high-performance antibiotic fabric |
| CN108707991B (en) * | 2018-06-12 | 2020-02-21 | 江苏金太阳纺织科技股份有限公司 | Preparation method of natural dye dyeable regenerated cellulose fiber |
| CN110453300A (en) * | 2019-07-24 | 2019-11-15 | 郑州家善环保科技有限公司 | A kind of production method of bread or the protein modified viscose fiber of brewer's yeast |
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