CN1261111A - Antibacterial fibres containing chitin and its derivatives, and preparing process thereof - Google Patents
Antibacterial fibres containing chitin and its derivatives, and preparing process thereof Download PDFInfo
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- CN1261111A CN1261111A CN 00100160 CN00100160A CN1261111A CN 1261111 A CN1261111 A CN 1261111A CN 00100160 CN00100160 CN 00100160 CN 00100160 A CN00100160 A CN 00100160A CN 1261111 A CN1261111 A CN 1261111A
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Abstract
An antibacterial fibre contains chitin and its derivative (0.5-15 wt.%) in granularity of 0.5-5 microns. Said fibre has linear density of 1.5-12 dtex, breaking strength of 1.2-4.5 CN/dtex and breaking elongation of 5-40%. Its advantages are strong killing and suppression action to colibacillus, no poison and irritation, and high biologic compatibility, comfortableness and air permeability.
Description
The invention relates to a kind of anti-bacterial fibre and preparation method thereof, anti-bacterial fibre and the manufacture method about containing chitin and derivative thereof more particularly, this anti-bacterial fibre can be made articles for use such as finery such as underwear, underpants, Training wear, socks, bedding, filtering material.
In the prior art, the prior art of relevant antibiotic fabric is more, discloses complex copper ion and Viride Nitens on polyacrylonitrile in Chinese patent CN-87100231, thereby has made fabric have antibiotic property, but this patent can only obtain polyacrylonitrile fibre, and color and luster is green.Further, general liquor argenti nitratis ophthalmicus dipping or the interpolation inorganic compound (Al of adopting before the present invention
2O
3, SiO
2, MnO
2, MgO
2, TiO
2), metal ion (Ag, Cu) etc. makes antibacterial synthetic.
Though the made antibacterial synthetic of these additives has certain antibiotic or bacteriostasis, but these inorganic compounds or organic compound more or less have toxicity and skin are had excitant, therefore adopting natural antibacterial additives is the development that conforms with the modern life, is functional health clothing products only way.
Chitin and derivative thereof are a kind of nitrogenous polysaccharide natural macromolecular materials that is distributed widely in occurring in nature, are the main components of shells such as the cell membranes of various fungies and shrimp, crab, insect.Chitin and derivative thereof not only have very strong chemical reaction performance, and have nonpoisonous and tasteless, alkaline-resisting corrosion resistance characteristic; Have excellent biological compatibility, cohesiveness, flexibility and become fibre, film forming ability; Have functions such as antibacterial bacteriostatic, anti-mould and anti-moth, moisture-absorbing moisture-keeping, therefore greatly cause the attention of society and scientist's concern.
This patent inventor has illustrated that in the CN-1149093A patented invention employing wet spinning produces deacetyl chitin fiber with deacetyl chitin and solvent composition deacetyl chitin slurries, and it is as the raw material of making medical materials such as artificial skin, hemostatic cotton; If as dress material, the effect of its antibacterial bacteriostatic deodorization is fabulous with deacetyl chitin fiber, but its appropriate litigation fees costliness, ordinary consumer can't be born.
The object of the present invention is to provide a kind of have good natural antibacterial characteristic and the cheap and good-quality anti-bacterial fibre that contains chitin and derivative thereof.
Second purpose of the present invention is to provide a kind of anti-bacterial fibre preparation method who contains chitin and derivative thereof.
The 3rd purpose of the present invention provides the conventional fibre-forming polymer blend of a kind of chitin and derivative and other thereof prepares anti-bacterial fibre by wet spinning method.
The 4th purpose of the present invention is to provide a kind of and prepares chitin derivative through the chemical reaction mode, prepares the method for anti-bacterial fibre then with conventional fibre-forming polymer co-blended spinning.
These purposes of the present invention and other purposes will further be set forth and illustrate by following detailed description.
The anti-bacterial fibre that contains chitin and derivative thereof of the present invention, the content of chitin and derivative thereof is 0.5%～15% of fibre weight in the fiber, granularity is 0.5～5 μ m, fiber linear density is 1.5～12dtex, fracture strength is 1.2～4.5CN/dtex, and elongation at break is 5%～40%.
Further, the anti-bacterial fibre that contains chitin and derivative thereof of the present invention, chitin and derivative thereof evenly mix with spinning slurry, adopt freezing comminuting method to pulverize chitin and derivative thereof, obtain granularity 0.5～5 μ m chitin and derivative thereof, freezing comminuting method is the liquefied ammonia freezing.
The anti-bacterial fibre that contains chitin and derivative thereof of the present invention can prepare by the following method, comprises that the mixed liquor that chitin and derivative thereof and auxiliary agent are formed mixes with spinning slurries such as acetate fiber, acrylic fiber, viscoses afterwards to produce anti-bacterial fibre with the wet spinning shaping.
Further, the manufacture method that contains the anti-bacterial fibre of chitin and derivative thereof of the present invention, comprising that the mixed liquor that chitin and derivative thereof and auxiliary agent are formed mixes with spinning slurries such as acetate fiber, acrylic fiber, viscoses afterwards produces anti-bacterial fibre with the wet spinning shaping, the content of chitin and derivative thereof is 0.5%～15% of fibre weight in the fiber, granularity is 0.5～5 μ m, fiber linear density is 1.5～12dtex, fracture strength is 1.2～4.5CN/dtex, and elongation at break is 5%～40%; Described auxiliary agent can be sodium sulfocyanate, acetone, water, NaOH etc.; Viscose spinning technique condition is: spinning bath is soaked long 0.5～2.5 meter, and normal temperature, coagulating bath component are sulfuric acid, sodium sulphate, zinc sulfate, and the spinning head hole count is 5000～20000 holes, aperture 0.07～0.1mm, 10～25 meters/minute of spinning speeds; Anti-bacterial fibre can be made underwear, underpants, Training wear, socks etc.
The present invention at first pulverizes chitin and derivative thereof with mechanical crusher or high velocity air breaking method, and the granular size of being pulverized chitin and derivative thereof is 0.5～5 μ m.When adopting wet spinning to be shaped, with particle be 0.5～5 μ m chitin and derivative thereof through grind, be dispersed in with stirring pure water, sodium hydroxid, acetone, acetic acid, thiocyanic acid one of are received etc. or admixture solvent in, make it not precipitate, mix with rayon spinning slurries, cellulose acetate spinning slurry, polyacrylonitrile spinning slurry etc. respectively in proportion then, and, enter coagulating bath by spinning head ejection thread.At this moment solvent spreads in coagulating bath in the thread, and meanwhile, coagulating bath is then permeated in thread, thereby thread formation fiber, just makes the anti-bacterial fibre that contains chitin and derivative thereof through post processings such as drawing-off, washings again.
Certainly, as possible, the present invention also can carry out chemical treatment to chitin and derivative thereof earlier, comprises alkalization, sulfonation, acidylate, acetylation or the like, is beneficial to its further dispersion.
Product of the present invention is the raw material of antibacterial underwear, underpants, socks, bedding of pure natural etc., it has nonpoisonous and tasteless, alkaline-resisting decay resistance, have excellent biological compatibility, cohesiveness, flexibility, have antibioticly anti-itch, functions such as anti-mould and anti-moth, moisture-absorbing moisture-keeping.After testing, Escherichia coli (8099), staphylococcus aureus (ATCC6538), Candida albicans twenties kinds of bacteriums such as (ATCC10231) there are strong inhibitory or killing effect,
In the present invention, all raw materials, half product all can be buied from market, chitin and derivative thereof are conventional commercially available prod, can be Chinese patent ZL-94116666, CN-95119358, CN-96113888, cited among the ZL-96205886, above-mentioned patent is incorporated herein by reference, and the present invention can think the continuity of above-mentioned patent.
Non-in the present invention refering in particular to, all parts, amount are the unit of weight of gross weight for the basis.
Below further specify the present invention by specific embodiment, but embodiment only be used for the explanation can not limit the scope of the invention.
Example 1:
Chitin is ground into 100～200 order particles (being equivalent to 100～120 microns) through mechanical crushing (FS-93-1 type), with the high velocity air comminuting method 100～120 order particles is ground into 9000～12500 order particles (being equivalent to 1～3 μ m) then.
Example 2:
Be that 4.5～5.5 deacetyl chitin (chitin and derivative thereof) is ground into 100～200 order particles (being equivalent to 100～120 microns) through mechanical crusher (FS-93-1 type) with logarithmic viscosity number, then 100～120 order chitin inputs are filled in the container of pure water and carry out 3～8 hours swellings, chitin after the swelling drops in the centrifuge, remove moisture, the swelling chitin of gained is pulverized through liquid nitrogen frozen vibrating head grinding machine, is ground into the above particle of 12500 orders (it is following to be equivalent to 1 μ m).
Example 3:
The chitin of 5 kilograms of pulverizing and derivative (1 μ m is following) thereof are put in the sodium thiocyanate solution (concentration is 30%), and ratio is by 1: 4 (weight ratio), makes it to be dispersed in the sulphur hydracid and receives in the solution stand-by through grinding to stir.
Then polyacrylonitrile spinning slurry (weight ratio 13%～17%) and chitin and derivative thereof, sodium thiocyanate solution are mixed in proportion, mixed proportion (weight ratio) is 1: 30.
The spinning technique condition that contains the antibacterial acrylic fibre fiber of chitin and derivative thereof is that long 0.5～2m is soaked in spinning bath, bathes 10～15 ℃ of temperature, and the spinning head hole count can adopt 3000～20000 holes, and aperture 0.08～0.1mm, spinning speed are 5～40 meters/minute.Behind the solidification forming, carry out one-off drawing or carry out succeeding stretch with boiling water with steam, draw ratio is 5～10 times, and bathing temperature is 92～95 ℃, after fiber goes out last stretch bath, washs in 60～80 ℃ of hot water.Last HEAT SETTING promptly makes the antibacterial acrylic fibre fiber that contains chitin and derivative thereof, fibre single thread fiber number 1.8dtex, fracture strength 2.0～2.2cN/dtex, elongation 25%～40% (dry state).Fiber can be made into natural antibacterial underwear, underpants, Training wear, socks etc. through processing.
Example 4:
With the chitin and the derivative (about 1 μ m) thereof of 3 kilograms of pulverizing, put in the acetone soln (concentration is 60%), 1: 6 in proportion (weight ratio) makes it to be dispersed in the acetone soln stand-by through grinding stirring.
Then cellulose acetate spinning slurry (5%～15% weight ratio) and chitin and derivative acetone soln thereof are mixed in proportion, mixed proportion (weight ratio) is 1: 20, the spinning technique condition that contains the antibiotic acetate fiber of chitin and derivative thereof is: long 0.5～2.5m is soaked in spinning bath, bathe Wen Changwen, the coagulating bath component is water or ethanol water or isopropanol water solution, the spinning head hole count is 5000～20000 holes, and aperture 0.07～0.1mm, spinning speed are 10～25 meters/minute.Behind the solidification forming, again through water washing, acetone on the flush away fiber, ethanol, isopropyl alcohol and other soluble impurity, can make the antibiotic cellulose acetate fiber that contains chitin and derivative thereof, fibre single thread fiber number 1.5dtex, fracture strength is 2.1～2.6cN/dtex, elongation 5%～50% (dry state), and fiber can be made into filtering material etc. through processing.
Example 5:
With the chitin and the derivative (about 1 μ m) thereof of 8 kilograms of pulverizing, put in the pure water, 1: 3 in proportion (weight ratio) makes it to be dispersed in the aqueous solution stand-by through grinding stirring.
After then cellulose viscose glue (9%～16% weight ratio) and chitin and the derivative aqueous solution thereof being mixed in proportion, mixed proportion (weight ratio) is 1: 15.
The spinning technique condition that contains the antibacterial viscose fiber of chitin and derivative thereof is: long 0.5～2.5m is soaked in spinning bath, bathe Wen Changwen, the coagulating bath component is sulfuric acid, sodium sulphate and zinc sulfate (weight ratio is conventional ratio), the spinning head hole count is 5000～20000 holes, aperture 0.07～0.1mm, spinning speed are 10～25 meters/minute.Behind the solidification forming, again through water washing, sulfuric acid on the flush away fiber, carbon disulfide, sulfate and other soluble impurity, can make the antibacterial viscose fiber that contains chitin and derivative thereof, fibre single thread fiber number 1.5dtex, fracture strength is 2.1～2.6cN/dtex, elongation 30%～50% (dry state), and fiber can be made into natural antibacterial underwear, underpants, Training wear, socks etc. through processing.
Example 6:
Chitin (logarithmic viscosity number is 4.5～5.5 deacetyl chitin) is put into 37%～50% sodium hydrate aqueous solution,, make alkaline chitin reacting 2 hours about 25 ℃ or under the lower condition.
Then alkaline chitin is added and mix (weight ratio is 1: 10) in the ice bath, temperature is remained on below 0 ℃, put into carbon disulfide, mix.The addition of carbon disulfide generally is no more than 1/4～1/2 of chitin content, and the reaction time is 2～6 hours.This is the process that a chitin sulfonation obtains the chitin sulphonic acid ester.Whole process must keep low temperature, and the time of staying can be 12～16 hours, and is complete in order to sulfonation.Filter deaeration then, make it to become the chitin sulphonic acid ester solution that can carry out spinning.When the chitin sulphonic acid ester was used to prepare chitin class article, its composition preferably contained hydroxide and receives 5%～9%, chitin 6%～8%.
The spinning technique condition that contains the antibacterial viscose fiber of chitin and derivative thereof is: long 2.0m is soaked in spinning bath, bathe Wen Changwen, the coagulating bath component is sulfuric acid, sodium sulphate and zinc sulfate (weight ratio is 1: 2: 1.5), spinning head hole count 10000 holes, aperture 0.08mm, spinning speed are 15 meters/minute.Behind the solidification forming, again through water washing, sulfuric acid on the flush away fiber, carbon disulfide, sulfate and other soluble impurity, can make the antibacterial viscose fiber that contains chitin and derivative thereof, fibre single thread fiber number 1.6dtex, fracture strength is 2.0～2.6cN/dtex, elongation 30%～50% (dry state), and fiber can be made into natural antibacterial underwear, underpants, Training wear, socks etc. through processing.
Claims (8)
1, a kind of anti-bacterial fibre that contains chitin and derivative thereof, the content that it is characterized in that chitin in the fiber and derivative thereof is 0.5%～15% of fibre weight, granularity is 0.5～5 μ m, fiber linear density is 1.5～12dtex, fracture strength is 1.2～4.5CN/dtex, and elongation at break is 5%～40%.
2, the anti-bacterial fibre that contains chitin and derivative thereof as claimed in claim 1 is characterized in that chitin and derivative thereof evenly mix with spinning slurry.
3, the anti-bacterial fibre that contains chitin and derivative thereof as claimed in claim 1 is characterized in that pulverizing chitin and derivative thereof with freezing comminuting method, and obtaining granularity is 0.5～5 μ m chitin and derivative thereof.
4, the anti-bacterial fibre that contains chitin and derivative thereof as claimed in claim 3 is characterized in that freezing comminuting method is the liquefied ammonia freezing.
5, the manufacture method that contains the anti-bacterial fibre of chitin and derivative thereof as claimed in claim 1 is characterized in that mixing the back with spinning slurries such as acetate fiber, acrylic fiber, viscoses by the mixed liquor that chitin and derivative thereof and auxiliary agent are formed is shaped with wet spinning and produces anti-bacterial fibre.
6, the manufacture method that contains the anti-bacterial fibre of chitin and derivative thereof as claimed in claim 5, it is characterized in that mixing the back with spinning slurries such as acetate fiber, acrylic fiber, viscoses by the mixed liquor that chitin and derivative thereof and auxiliary agent are formed is shaped with wet spinning and produces anti-bacterial fibre, the content of chitin and derivative thereof is 0.5%～15% of fibre weight in the fiber, granularity is 0.5～5 μ m, fiber linear density is 1.5～12dtex, fracture strength is 1.2～4.5CN/dtex, and elongation at break is 5%～40%.
7, the manufacture method that contains the anti-bacterial fibre of chitin and derivative thereof as claimed in claim 5 is characterized in that described auxiliary agent can be sodium sulfocyanate, acetone, water, NaOH etc.
8, the anti-bacterial fibre that contains chitin and derivative thereof as claimed in claim 1 is characterized in that described anti-bacterial fibre can make underwear, underpants, Training wear, socks, filtering material etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100160A CN1099477C (en) | 2000-01-14 | 2000-01-14 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100160A CN1099477C (en) | 2000-01-14 | 2000-01-14 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1261111A true CN1261111A (en) | 2000-07-26 |
| CN1099477C CN1099477C (en) | 2003-01-22 |
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|---|---|---|---|
| CN00100160A Expired - Fee Related CN1099477C (en) | 2000-01-14 | 2000-01-14 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102968C (en) * | 2000-06-23 | 2003-03-12 | 上海士林纺织有限公司 | Modified viscose fibre containing super fine micro granular chitosan and its producing technology |
| CN1103387C (en) * | 2000-03-23 | 2003-03-19 | 上海士林纺织有限公司 | Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope |
| CN1303281C (en) * | 2002-12-19 | 2007-03-07 | 全球生技股份有限公司 | Yarn antibacterial treating method |
| CN1327079C (en) * | 2003-06-30 | 2007-07-18 | 陈良 | Processing method for down with antibacterid, antivirus, mould proof, off odour eliminating and health care functions and use |
| CN100388896C (en) * | 2003-05-29 | 2008-05-21 | 吴奕光 | Water soluble bactericidal skin totional transparent gloves containing chitin derivatives |
| CN102912475A (en) * | 2011-08-04 | 2013-02-06 | 周新民 | Method for preparing high-strength chitosan fiber from multi-component coagulated bath lotion |
| CN103159996A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Multifunctional protective clothing material in sports field and preparation method thereof |
| CN103159997A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Protective clothing material with self-repairing function in sports field and preparation method thereof |
| CN103160057A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Composite functional pad material for sporting goods and preparation method thereof |
| CN103205037A (en) * | 2012-01-17 | 2013-07-17 | 贾振勇 | Multifunctional protector material in field of sports, and preparation method thereof |
| CN104231356A (en) * | 2011-12-16 | 2014-12-24 | 李胜春 | Preparation method of protective clothing material with self-repairing function in sports field |
| CN104231357A (en) * | 2011-12-16 | 2014-12-24 | 李胜春 | Preparation method of multifunctional protective clothing material used in sports field |
| CN105908280A (en) * | 2016-07-10 | 2016-08-31 | 胡稳成 | Antibacterial viscose and preparation method thereof |
| CN106012076A (en) * | 2016-07-15 | 2016-10-12 | 吉林富博纤维研究院有限公司 | Wet spinning method for preparing cellulose acetate fiber |
| CN109943000A (en) * | 2019-02-27 | 2019-06-28 | 广州甚多服装有限公司 | A kind of preparation method of antibacterial textile material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068916C (en) * | 1995-12-08 | 2001-07-25 | 中国纺织大学 | Chitin fibers and production thereof |
| CN1129748A (en) * | 1995-12-08 | 1996-08-28 | 中国纺织大学 | Deacetyl chitin fiber and its manufacture and application |
| JP3413631B2 (en) * | 1996-07-16 | 2003-06-03 | 富士紡績株式会社 | Antibacterial cellulose regenerated fiber |
| CN1168861C (en) * | 1996-09-17 | 2004-09-29 | 三菱丽阳株式会社 | Chitosan-containing acrylic fibers and process for preparing the same |
-
2000
- 2000-01-14 CN CN00100160A patent/CN1099477C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103387C (en) * | 2000-03-23 | 2003-03-19 | 上海士林纺织有限公司 | Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope |
| CN1102968C (en) * | 2000-06-23 | 2003-03-12 | 上海士林纺织有限公司 | Modified viscose fibre containing super fine micro granular chitosan and its producing technology |
| CN1303281C (en) * | 2002-12-19 | 2007-03-07 | 全球生技股份有限公司 | Yarn antibacterial treating method |
| CN100388896C (en) * | 2003-05-29 | 2008-05-21 | 吴奕光 | Water soluble bactericidal skin totional transparent gloves containing chitin derivatives |
| CN1327079C (en) * | 2003-06-30 | 2007-07-18 | 陈良 | Processing method for down with antibacterid, antivirus, mould proof, off odour eliminating and health care functions and use |
| CN102912475A (en) * | 2011-08-04 | 2013-02-06 | 周新民 | Method for preparing high-strength chitosan fiber from multi-component coagulated bath lotion |
| CN103160057A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Composite functional pad material for sporting goods and preparation method thereof |
| CN103159997A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Protective clothing material with self-repairing function in sports field and preparation method thereof |
| CN103159996A (en) * | 2011-12-16 | 2013-06-19 | 李胜春 | Multifunctional protective clothing material in sports field and preparation method thereof |
| CN104231356A (en) * | 2011-12-16 | 2014-12-24 | 李胜春 | Preparation method of protective clothing material with self-repairing function in sports field |
| CN104231357A (en) * | 2011-12-16 | 2014-12-24 | 李胜春 | Preparation method of multifunctional protective clothing material used in sports field |
| CN103205037A (en) * | 2012-01-17 | 2013-07-17 | 贾振勇 | Multifunctional protector material in field of sports, and preparation method thereof |
| CN105908280A (en) * | 2016-07-10 | 2016-08-31 | 胡稳成 | Antibacterial viscose and preparation method thereof |
| CN105908280B (en) * | 2016-07-10 | 2018-06-05 | 胡稳成 | A kind of antibacterial viscose fiber and preparation method thereof |
| CN106012076A (en) * | 2016-07-15 | 2016-10-12 | 吉林富博纤维研究院有限公司 | Wet spinning method for preparing cellulose acetate fiber |
| CN106012076B (en) * | 2016-07-15 | 2018-06-19 | 吉林富博纤维研究院有限公司 | A kind of wet spinning preparation method of acetate fiber |
| CN109943000A (en) * | 2019-02-27 | 2019-06-28 | 广州甚多服装有限公司 | A kind of preparation method of antibacterial textile material |
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| CN1099477C (en) | 2003-01-22 |
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Assignee: Langsha Knitting Co., Ltd. Assignor: Donghua University|Shanghai University (Pudong) Key Laboratory pure biological material Co., Ltd. Contract fulfillment period: 2007.1.15 to 2017.1.14 contract change Contract record no.: 2008330001509 Denomination of invention: Antibacterial fibres containing chitin and its derivatives, and preparing process thereof Granted publication date: 20030122 License type: Exclusive license Record date: 20081030 |
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