CN102304783B - Preparation method of antibacterial anti-flaming protein viscose fiber - Google Patents
Preparation method of antibacterial anti-flaming protein viscose fiber Download PDFInfo
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Abstract
The invention discloses a preparation method of an antibacterial anti-flaming protein viscose fiber. The preparation method comprises the following steps of preparing fire retardant slurry, a protein glue liquid and a chitosan solution, mixing uniformly the fire retardant slurry, the protein glue liquid and the chitosan solution with a viscose spinning solution before spinning, preparing the antibacterial anti-flaming protein viscose fiber through wet spinning, and carrying out soft arrangement on the prepared fiber. According to the preparation method of the antibacterial anti-flaming protein viscose fiber, disclosed by the invention, the antibacterial anti-flaming protein viscose fiber is prepared from hexaphenoxy cyclotriphosphazene as a fire retardant, alkyl polyglycoside as an emulsifier of the fire retardant, animal protein as a protein raw material, and chitosan as an antibacterial agent, has excellent flame retardant property and is up to the national textile anti-flaming standard; and meanwhile, the service performance and antibacterial property are excellent, the wet strength of the fiber is improved by more than 20%, the initial modulus is reduced by more than 30%, and the bulking intensity is improved by more than 8%.
Description
Technical field
The invention belongs to the textile fabric technical field, relate to a kind of preparation method of viscose, particularly relate to a kind of preparation method who has the composite viscose fiber of antibiotic, fire resistance simultaneously.
Background technology
Viscose has and the very similar character of some performance of cotton fiber; As good hygroscopicity, easily dyeing, antistatic, be easy to weaving processing etc.; The pattern fabric of processing is bright-coloured, and is comfortable and easy to wear, is particluarly suitable for the hot area dress of weather; And the fiber number of viscose and length can be regulated according to the requirement of purposes, therefore receive people's welcome.
The maximum shortcoming of viscose is easy burning, promptly directly burns behind the common viscose fiber contact flame, withdraws still sustained combustion behind the burning things which may cause a fire disaster, and burning velocity is fast, and it is few to leave over ash content after the burning.The inflammability of viscose has been brought very big obstruction to its application, and the anti-flammability that improves viscose can effectively reduce the fire incident loss and the number of casualties.
The common method of preparation FRC is before wet spinning, the fire retardant blend to be joined in the spinning solution.The fire retardant of present domestic use, as gather silicic acid, pyrophosphate based flame retardant etc., machinery brute force and feel that blend adds the FRC for preparing behind the spinning solution all have very big loss, when promoting fire resistance, have lost wearability.Solution to this problem generally is to select suitable finishing agent that FRC is carried out the back arrangement at present.
Before rayon spinning, add albumen glue (animal protein is dissolved in alkali lye and makes), the protein cellulose viscose that obtains shows good wearability.Fire retardant and protein liquid are joined in the rayon spinning liquid simultaneously, prepare fire-retardant protein cellulose viscose through wet spinning, its feel obviously is superior to FRC.Simultaneously, this fire-retardant albumen viscose glue combines with the modified amido silicone softening agent in back arrangement process easily, after arrangement, can obtain feel excellent fire retardant protein cellulose viscose, and wearability obtains significantly to promote.
Present existing animal protein viscose mainly is the pupa albumen fiber, and its color is golden yellow, is unfavorable for the dyeing and finishing processing in later stage, and does not have anti-flammability.Simultaneously; When the preparation protein cellulose viscose, the protein raw materials of interpolation is animal protein (like pupa albumen, a wool leftover bits and pieces), because one of main nutrient matter that protein is growth of microorganism to be needed; Especially in wet environment, go mouldy easily, therefore need carry out antimicrobial treatment it.
The same fire retardant of chitosan antimicrobial agent, albumen glue are together added in the spinning solution, can prepare antibiotic fire-retardant protein cellulose viscose.This kind fiber has overcome the inflammable shortcoming of viscose, and excellent wearability and anti-microbial property is provided simultaneously, and fiber is a white, is easy to carry out dyeing and finishing processing.
Summary of the invention
The objective of the invention is technical deficiencies such as inflammable to viscose, that the FRC wearability is poor, protein cellulose viscose is perishable; A kind of preparation method of antibiotic fire-retardant protein cellulose viscose is provided; Both had the excellent wearability of protein cellulose viscose to produce, had the fire-retardant protein cellulose viscose of Multifunction composite antibiosis of fire resistance and anti-microbial property simultaneously.
The preparation method of the antibiotic fire-retardant protein cellulose viscose of the present invention is: after chitosan solution, albumen glue and the blend according to a certain percentage of fire retardant slurry, join in the rayon spinning liquid, through wet spinning, prepare antibiotic fire-retardant protein cellulose viscose.Wherein be animal protein to be dissolved in obtain the albumen glue in the alkali lye; With the hexaphenoxycyclotriphosphazene is fire retardant, is emulsifying agent with APG (APG), mixes to obtain the fire retardant slurry.
The preparation method of the antibiotic fire-retardant protein cellulose viscose of the present invention specifically comprises the steps:
1. prepare the fire retardant slurry
With the hexaphenoxycyclotriphosphazene is fire retardant, and APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 3～8 adds industrial soft water, wet processes 2～8 hours, and processing flame retardant agent content is the fire retardant slurry of 10～25wt%;
2. prepare the albumen glue
Put into wool leftover bits and pieces 10～30 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 70～90 weight portions; 60～80 ℃ are stirred down, dissolved 15～30 minutes; Placed 2～4 hours, and got Aqueous Solution of Keratin, solution is passed through the gauze coarse filtration earlier; Filter through 400 order bag filters again, make the albumen glue that protein content is 10～30wt% (by the protein content of reality dissolving) after the filtrating dialysis;
3. preparation chitosan solution
Shitosan, citric acid and inferior sodium phosphate are added in the 3wt% acetum, be heated to 70～90 ℃, fully stir and make its dissolving; Add penetrating agent JFC; Stirred 30～60 minutes, and made the thick solution of shitosan, remove by filter insoluble matter and obtain chitosan solution; Contain 1.5～5wt% shitosan in the chitosan solution that obtains, 3～5wt% citric acid, 2～6wt% inferior sodium phosphate and 0.2～5wt% penetrating agent JFC;
4. wet spinning
Fire retardant slurry, albumen glue and chitosan solution are added in the viscose spinning mother liquor; Stir; Viscose spinning mother liquor is satisfied contain the fire retardant slurry of 6～10wt%, the albumen glue of 2～6wt% and the chitosan solution of 2～6wt%, vacuumize defoaming treatment after 60 minutes, according to conventional viscose spinning process; Spray silk, plasticization drawing shaping through acid coagulating bath; To become silk to clean twice with 40～45 ℃ of water, feeds carry out the desulfurization processing in 10～25wt% aqueous sodium carbonate of 40～45 ℃ after, obtain antibiotic fire-retardant protein cellulose viscose.
Wherein, the preferred super-fine powder of fire retardant hexaphenoxycyclotriphosphazene that uses among the present invention specifically is that the mass ratio that fire retardant and mill are situated between with 1 ︰ 20 is mixed, through the high-performance nano impact grinding impact and grinding after, obtain the fire retardant super-fine powder.
The present invention can also use the modified amido silicone softening agent to carry out the back arrangement to the antibiotic fire-retardant protein cellulose viscose for preparing, concrete grammar is:
With washed with de-ionized water twice, the bath raio according to 1 ︰ 10 adds deionized water then, regulates the pH value to 6 of water-bath with glacial acetic acid with the antibiotic fire-retardant protein cellulose viscose for preparing; Regulate water temperature and reach 30～50 ℃, add the modified amido silicone softening agent, make its concentration reach 3～10wt%; Handle 10～30min, take out viscose, after the dehydration; 70～90 ℃ of constant temperature dryings obtain soft antibiotic fire-retardant protein cellulose viscose.
The antibiotic fire-retardant protein cellulose viscose that the present invention prepares can be applied to make products such as viscose filament yarn, staple fibre and cord fabric.
Shown in Figure 1 is the infrared spectrum that does not add the common viscose fiber of fire retardant, the infared spectrum for the antibiotic fire-retardant protein cellulose viscose behind the interpolation fire retardant shown in Figure 2.Comparison diagram 1 and Fig. 2 can find to add antibiotic fire-retardant protein cellulose viscose sample behind the fire retardant at 900～700cm of fingerprint region
-1The place has occurred and the visibly different characteristic peak of common viscose fiber, lays respectively at 850cm
-1, 794cm
-1And 775cm
-1, this is a phenyl ring C-H out-of-plane bending vibration absworption peak.Though fire retardant 1268cm
-1, 1179cm
-1The P-N stretching vibration absworption peak and the 1196cm at place
-1, 953cm
-1The P-O-C characteristic absorption peak at place is all covered by the absworption peak of cellulose in the viscose itself, but the characteristic peak that above-mentioned fingerprint region occurs is enough to also confirm that fire retardant has been attached on the viscose.
Antibiotic fire-retardant protein cellulose viscose preparation method of the present invention has following beneficial effect:
1) the present invention joins hexaphenoxycyclotriphosphazene in the rayon spinning liquid as fire retardant first; And the APG (APG) of application and cellulose macromolecule structural similarity carries out the emulsification dispersion to fire retardant; Efficiently solve big, the dispersed bad problem of fire retardant particle diameter; Prepared the FRC with lasting flame retardant effect, the antibiotic fire-retardant protein cellulose viscose cross section Electronic Speculum appearance structure of Fig. 3 shows, under 3000 times of Electronic Speculum, observes; Fire retardant is fine hair shape structure at fibrous inside, is evenly distributed.The adding of protein liquid makes between fire proofing and the big molecule of viscose glue and has formed structure closely, and this structure has certain influence to brute force and the toughness that improves viscose;
2) the present invention adds the albumen glue when in rayon spinning liquid, adding fire retardant; Cooperate APG and cellulose macromolecule to form and twine network structure and intermolecular hydrogen bonding structure; Make the fire-retardant protein cellulose viscose that makes than common FRC mechanical property with take performance large increase arranged; Wet strength improves more than 20%, is brought up to more than the 0.99cN/dtex by the 0.83cN/dtex of conventional FRC;
3) shitosan of employing of the present invention and cellulosic molecule structural similarity adds rayon spinning liquid as antiseptic, prepares antibiotic fire-retardant protein cellulose viscose, obtains water-fastly washing, fastness is good, the fiber of bacteriostasis rate more than 90%;
4) preparation method of the present invention in the wet spinning process during desulfurization used auxiliary agent be sodium carbonate, solved the protein loss problem in the production process of viscose fiber;
5) FRC of preparation adopts soft finish after the desulfurization washing, and its smooth pliability increases greatly, and initial modulus has reduced more than 30%.
The inventive method is applicable to the multi-functional compound preparation of the long and short fiber of viscose glue, has improved the wearability and the Application Areas of fiber, is convenient to follow-up processing, and technology is simple, and is easy to operate, is convenient to implement.Antibiotic fire-retardant protein cellulose viscose each item index function admirable of preparation, even dyeing, good spinnability, moisture absorption are ventilative, soft, and fire resistance reaches national textiles flame-retardant standard, and significant antibacterial bacteriostatic function is arranged.The products obtained therefrom performance indications: fiber LOI value is greater than 27; Bacteriostasis rate reaches more than 90%; Wet breaking strength has improved more than 20% than conventional FRC, and initial modulus has reduced more than 30% than conventional FRC, and bulkiness has improved more than 8% than conventional FRC.
Description of drawings
Fig. 1 is the infared spectrum that does not add the common viscose fiber of fire retardant.
Fig. 2 is the infared spectrum of the prepared antibiotic fire-retardant protein cellulose viscose of the present invention, and fire retardant has the obvious characteristics peak in the fingerprint region.
Fig. 3 is the fire-retardant protein cellulose viscose cross section appearance structure of the present invention's preparation, and the display fibers structure is tight, and fire retardant is the fine hair shape and evenly distributes.
The specific embodiment
Further set forth the present invention below in conjunction with the specific embodiment.Following examples only are used to explain the present invention, and are not used in restriction scope of the present invention.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 6 adds industrial soft water; Wet processes 4.5 hours is processed flame retardant agent content and is 17.5% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 23 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 77 weight portions; 65 ℃ are stirred down, dissolved 20 minutes; Placed 3.5 hours, Aqueous Solution of Keratin, filtering and making protein content after the dialysis is 21% albumen glue.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 75 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 40 minutes; Filtration makes chitosan solution, contains 4% shitosan in the chitosan solution that obtains, 3% citric acid, 2.5% inferior sodium phosphate and 0.4% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 9.2%, with respect to the albumen glue of glue weight 3.8% with respect to the chitosan solution of glue weight 3%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 16%, protein content is 8%, shitosan content is 1.2% antibiotic fire-retardant protein cellulose viscose.Adopt 15% aqueous sodium carbonate under 40 ℃, to carry out desulfurization and handle, consumption be sample heavy 2%.Antibiotic fire-retardant protein cellulose viscose after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 35 ℃; Add modified amido silicone softening agent 4% and handle 30 min, take out dehydration; With 70 ℃ of constant temperature dryings, obtain soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value (according to GB/T5454-1997 " textile combustion performance measurement-limiting oxygen index determination method " standard detection) is 29.5;
Bacteriostasis rate (according to GB 4789.2-2010 " microbiological test of food hygiene total plate count mensuration " standard detection) is 90%;
Wet breaking strength (according to GB/T 14463-93 " viscose staple fibre " standard detection): conventional FRC: 0.83 cN/dtex; Product of the present invention: 1.03cN/dtex;
Initial modulus (according to GB/T 14463-93 " viscose staple fibre " standard detection): conventional FRC: 48.59 cN/dtex; Product of the present invention: 33.36cN/dtex;
(adopt compression method that viscose is carried out bulkiness measures bulkiness.Randomly draw fiber 100g, pull into the filament shape, to guarantee the state consistency of fiber before compression, at standard state (20 ℃, relative humidity 65%) held 8h with the hand method of tearing.Ready sample is accurately taken by weighing 5g (being accurate to 0.01g), and putting into the diameter that has scale is the appearance tube of 6.5cm, and applies 20g/cm to fiber
2Pressure and keep 30s, write down the initial compression height A respectively, mm; Then pressure is added to 100g/cm
2, and keep this pressure to lower compression 1min, record compression height B at this moment, mm; Remove all loads, make fiber resilience 10min in the appearance tube, record fiber rebound height C, mm.Same lot sample article parallel test 5 times; The result is with 5 times arithmetic average value representation; And by formula
calculates bulkiness d, %.): conventional FRC: 7.86%; Product of the present invention: 14.54%.
Embodiment 2.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 5 adds industrial soft water; Wet processes 5 hours is processed flame retardant agent content and is 20% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 20 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 80 weight portions; 80 ℃ are stirred down, dissolved 20 minutes; Placed 4 hours, Aqueous Solution of Keratin, filtering and making protein content after the dialysis is 18% albumen glue.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 90 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 30 minutes; Filtration makes chitosan solution, contains 4.5% shitosan in the chitosan solution that obtains, 3.8% citric acid, 2.5% inferior sodium phosphate and 1% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 6%, with respect to the albumen glue of glue weight 3% with respect to the chitosan solution of glue weight 4%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 12%, protein content is 5.4%, shitosan content is 1.8% antibiotic fire-retardant protein cellulose viscose.Adopt 10% aqueous sodium carbonate to carry out desulfurization and handle, consumption be sample heavy 3%, 45 ℃ of temperature.Antibiotic fire-retardant protein cellulose viscose after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 40 ℃, add modified amido silicone softening agent 6%, handle 20min; Take out; Dehydration with 85 ℃ of constant temperature dryings, obtains soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value is 28; Bacteriostasis rate is 94%;
Wet breaking strength: conventional FRC: 0.83cN/dtex; Product of the present invention: 1.05cN/dtex;
Initial modulus: conventional FRC: 48.59cN/dtex; Product of the present invention: 28.77cN/dtex
Bulkiness: conventional FRC: 7.86%; Product of the present invention: 15.88%.
Embodiment 3.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 8 adds industrial soft water; Wet processes 3.5 hours is processed flame retardant agent content and is 12.5% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 16 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 84 weight portions; 70 ℃ are stirred down, dissolved 25 minutes; Placed 3 hours, Aqueous Solution of Keratin, filtering and making protein content after the dialysis is 15% albumen glue.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 80 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 45 minutes; Filtration makes chitosan solution, contains 5% shitosan in the chitosan solution that obtains, 4% citric acid, 6% inferior sodium phosphate and 3% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 7.2%, with respect to the albumen glue of glue weight 2.4% with respect to the chitosan solution of glue weight 2.8%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 9%, protein content is 3.6%, shitosan content is 1.4% antibiotic fire-retardant protein cellulose viscose.Adopt 20% aqueous sodium carbonate to carry out desulfurization and handle, consumption be sample heavy 1.5%, 40 ℃ of temperature.Antibiotic fire-retardant protein cellulose viscose after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 45 ℃, add modified amido silicone softening agent 8%, handle 15min; Take out; Dehydration with 80 ℃ of constant temperature dryings, obtains soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value is 27; Bacteriostasis rate is 92.4%;
Wet breaking strength: conventional FRC: 0.83cN/dtex; Product of the present invention: 1.02cN/dtex;
Initial modulus: conventional FRC: 48.59cN/dtex; Product of the present invention: 25.49cN/dtex;
Bulkiness: conventional FRC: 7.86%; Product of the present invention: 14.97%.
Embodiment 4.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 4 adds industrial soft water; Wet processes 5.5 hours is processed flame retardant agent content and is 22.5% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 28 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 72 weight portions; 75 ℃ are stirred down, dissolved 20 minutes; Placed 4 hours, and got Aqueous Solution of Keratin, make the albumen glue that protein content is 25wt% after the filtration dialysis.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 78 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 30 minutes; Filtration makes chitosan solution, contains 3.6% shitosan in the chitosan solution that obtains, 5% citric acid, 4.2% inferior sodium phosphate and 4% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 6.7%, with respect to the albumen glue of glue weight 2.4% with respect to the chitosan solution of glue weight 3.5%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 15%, protein content is 6%, shitosan content is 1.3% antibiotic fire-retardant protein cellulose viscose.Adopt 15% aqueous sodium carbonate to carry out desulfurization and handle, consumption be sample heavy 2.5%, 40 ℃ of temperature.The antibiotic antibiotic fire-retardant protein cellulose viscose that will prepare after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 38 ℃, add modified amido silicone softening agent 5%, handle 25 min; Take out; Dehydration with 90 ℃ of constant temperature dryings, obtains soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value is 29; Bacteriostasis rate is 91.5%;
Wet breaking strength: conventional FRC: 0.83cN/dtex; Product of the present invention: 1.00cN/dtex;
Initial modulus: conventional FRC: 48.59cN/dtex; Product of the present invention: 29.24cN/dtex;
Bulkiness: conventional FRC: 7.86%; Product of the present invention: 15.33%.
Embodiment 5.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 7 adds industrial soft water; Wet processes 4 hours is processed flame retardant agent content and is 15% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 30 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 70 weight portions; 60 ℃ are stirred down, dissolved 30 minutes; Placed 4 hours, Aqueous Solution of Keratin, filtering and making protein content after the dialysis is 28% albumen glue.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 70～90 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 30～60 minutes; Filtration makes chitosan solution, contains 3.2% shitosan in the chitosan solution that obtains, 3.2% citric acid, 4.5% inferior sodium phosphate and 0.5% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 9%, with respect to the albumen glue of glue weight 2.5% with respect to the chitosan solution of glue weight 5%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 13.5%, protein content is 7%, shitosan content is 1.6% antibiotic fire-retardant protein cellulose viscose.Adopt 25% aqueous sodium carbonate to carry out desulfurization and handle, consumption be sample heavy 1%, 40 ℃ of temperature.The antibiotic antibiotic fire-retardant protein cellulose viscose that will prepare after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 50 ℃, add modified amido silicone softening agent 7%, handle 20 min; Take out; Dehydration with 75 ℃ of constant temperature dryings, obtains soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value is 28.5; Bacteriostasis rate is 93%
Wet breaking strength: conventional FRC: 0.83cN/dtex; Product of the present invention: 1.10cN/dtex;
Initial modulus: conventional FRC: 48.59cN/dtex; Product of the present invention: 28.18cN/dtex;
Bulkiness: conventional FRC: 7.86%; Product of the present invention: 16.06%.
Embodiment 6.
The preparation of fire retardant slurry: with the hexaphenoxycyclotriphosphazene is fire retardant; APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 3 adds industrial soft water; Wet processes 6 hours is processed flame retardant agent content and is 25% fire retardant slurry.
The preparation of albumen glue: put into wool leftover bits and pieces 12 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 88 weight portions; 78 ℃ are stirred down, dissolved 25 minutes; Placed 2.5 hours, Aqueous Solution of Keratin, filtering and making protein content after the dialysis is 10% albumen glue.
The preparation of chitosan solution: shitosan, citric acid and inferior sodium phosphate are added in 3% acetum; Be heated to 85 ℃, fully stir and make its dissolving, add penetrating agent JFC; Stirred 45 minutes; Filtration makes chitosan solution, contains 2.4% shitosan in the chitosan solution that obtains, 3.6% citric acid, 5.1% inferior sodium phosphate and 1.5% penetrating agent JFC.
In rayon spinning liquid, add fire retardant slurry with respect to glue weight 7.6%, with respect to the albumen glue of glue weight 5.5% with respect to the chitosan solution of glue weight 5.8%; Stirring mixes it; Carry out defoaming treatment, the theoretical content (by 10% first fibre) that spinning makes fire retardant is 19%, protein content is 5.5%, shitosan content is 1.4% antibiotic fire-retardant protein cellulose viscose.Adopt 12.5% aqueous sodium carbonate to carry out desulfurization and handle, consumption be sample heavy 2.4%, 40 ℃ of temperature.The antibiotic antibiotic fire-retardant protein cellulose viscose that will prepare after the desulfurization with washed with de-ionized water twice, is added deionized water (bath raio 1:10) then, regulate pH value to 6 with glacial acetic acid; Regulate water temperature and reach 42 ℃, add modified amido silicone softening agent 5.5%, handle 25 min; Take out; Dehydration with 85 ℃ of constant temperature dryings, obtains soft antibiotic fire-retardant protein cellulose viscose.
The products obtained therefrom performance indications:
Fiber LOI value is 30; Bacteriostasis rate is 92%
Wet breaking strength: conventional FRC: 0.83cN/dtex; Product of the present invention: 1.01cN/dtex;
Initial modulus: conventional FRC: 48.59cN/dtex; Product of the present invention: 33.94cN/dtex
Bulkiness: conventional FRC: 7.86%; Product of the present invention: 14.21%.
Claims (7)
1. the preparation method of an antibiotic fire-retardant protein cellulose viscose comprises the steps:
A. prepare the fire retardant slurry
With the hexaphenoxycyclotriphosphazene is fire retardant, and APG is an emulsifying agent, and the mass ratio mixing according to Ruization Ji ︰ fire retardant=1 ︰ 3～8 adds industrial soft water, wet processes 2～8 hours, and processing flame retardant agent content is the fire retardant slurry of 10～25wt%;
B. prepare the albumen glue
Put into animal protein raw material 10～30 weight portions of clean dry in the 1mol/L sodium hydroxide solution of 70～90 weight portions; 60～80 ℃ are stirred down, dissolved 15～30 minutes; Placed 2～4 hours, and got the thick solution of albumen, the thick solution of albumen is passed through the gauze coarse filtration earlier; Filter through 400 order bag filters again, make the albumen glue that protein content is 10～30wt% after the filtrating dialysis;
C. prepare chitosan solution
Shitosan, citric acid and inferior sodium phosphate are added in the 3wt% acetum, be heated to 70～90 ℃, fully stir and make its dissolving; Add penetrating agent JFC; Stirred 30～60 minutes, and made the thick solution of shitosan, remove by filter insoluble matter and obtain chitosan solution; Contain 1.5～5wt% shitosan in the chitosan solution that obtains, 3～5wt% citric acid, 2～6wt% inferior sodium phosphate and 0.2～5wt% penetrating agent JFC;
D. wet spinning
Fire retardant slurry, albumen glue and chitosan solution are added in the viscose spinning mother liquor; Stir; Viscose spinning mother liquor is satisfied contain the fire retardant slurry of 6～10wt%, the albumen glue of 2～6wt% and the chitosan solution of 2～6wt%, vacuumize defoaming treatment after 60 minutes, according to conventional viscose spinning process; Spray silk, plasticization drawing shaping through acid coagulating bath; To become silk to clean twice, feed in 40～45 ℃ the desulfurizing assistant agent after the desulfurization processing, obtain antibiotic fire-retardant protein cellulose viscose with 40～45 ℃ of water.
2. the preparation method of antibiotic fire-retardant protein cellulose viscose according to claim 1 is characterized in that also comprising the antibiotic fire-retardant protein cellulose viscose for preparing is carried out the back arrangement, and method is:
With washed with de-ionized water twice, the bath raio according to 1 ︰ 10 adds deionized water then, regulates the pH value to 6 of water-bath with glacial acetic acid with the antibiotic fire-retardant protein cellulose viscose for preparing; Regulate water temperature and reach 30～50 ℃, add the modified amido silicone softening agent, make its concentration reach 3～10wt%; Handle 10～30min, take out viscose, after the dehydration; 70～90 ℃ of constant temperature dryings obtain soft antibiotic fire-retardant protein cellulose viscose.
3. the preparation method of antibiotic fire-retardant protein cellulose viscose according to claim 1; It is characterized in that the fire retardant hexaphenoxycyclotriphosphazene that uses is super-fine powder; Specifically be that the mass ratio that fire retardant and mill are situated between with 1 ︰ 20 is mixed; After the nanometer impact grinding is impacted and ground, obtain the fire retardant super-fine powder.
4. the preparation method of antibiotic fire-retardant protein cellulose viscose according to claim 1 is characterized in that described animal protein raw material is one or more in wool, wool leftover bits and pieces, wool powder, the cashmere waste material.
5. the preparation method of antibiotic fire-retardant protein cellulose viscose according to claim 1 is characterized in that in the described wet spinning process, the desulfurizing assistant agent of use is 10～25wt% aqueous sodium carbonate.
6. the antibiotic fire-retardant protein cellulose viscose for preparing of claim 1 or 2 said preparation methods.
7. the antibiotic fire-retardant protein cellulose viscose of claim 6 application that is used to make viscose filament yarn, staple fibre and cord fabric.
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| CN104611910B (en) * | 2015-02-03 | 2016-08-24 | 马晓均 | A kind of preparation method of the flame-retardant silk fabric of environmental protection |
| EP3673030A1 (en) | 2017-08-23 | 2020-07-01 | Ecolab USA, Inc. | Elemental sulfur dispersant to control fouling in water systems |
| CN107653511A (en) * | 2017-10-17 | 2018-02-02 | 高俊 | A kind of preparation method of viscose staple fibre |
| CN107881578A (en) * | 2017-11-06 | 2018-04-06 | 成都天府轨谷科技有限公司 | The method of yarn is made with it in a kind of abrasion resistant fire blocking antibacterial composite fibers and preparation method thereof |
| CN108166157B (en) * | 2017-12-25 | 2020-07-10 | 合肥洁诺无纺布制品有限公司 | Moisture-absorbing and bacteriostatic spunlace non-woven fabric beauty mask base cloth and preparation method thereof |
| CN109285618B (en) * | 2018-09-25 | 2020-04-28 | 青岛长城巨龙电缆有限公司 | High-flame-retardant fire-resistant low-smoke halogen-free cable and preparation method thereof |
| ES2950905T3 (en) * | 2019-02-22 | 2023-10-16 | Basf Se | Method for producing a viscose solution and a viscose solution thereby produced and a method for producing viscose fiber |
| CN110158176A (en) * | 2019-05-30 | 2019-08-23 | 叶小文 | A kind of preparation method of flame retardant viscose fiber |
| CN110359101B (en) * | 2019-07-19 | 2020-10-02 | 嘉兴学院 | Gel spinning method for manufacturing chitosan fiber |
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| CN100485098C (en) * | 2006-11-01 | 2009-05-06 | 天津工业大学 | Modified viscose fibre and its producing method |
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