TW464700B - Method for producing fiber with anti-mould, antibacterial and de-odoring effects - Google Patents

Abstract

The present invention relates to a method for producing a fiber with anti-mould, antibacterial and de-odoring effects by mixing natural chitin or chitosan and cellulose. A product according to the present invention can be used in clothing, food and pharmaceutical use to reduce the probability of a human or product from being contaminating microorganism while reducing odor. The invented method uses a wet spinning method and comprises dissolving chitin and cellulose in an oxidized methylmorpholine solution which has been adjusted by an acid into a gel solution; extruding the gel solution through a spinneret into a filament; regenerating and washing the filament with water; drying and winding the filament into a fiber with anti-mould, antibacterial and de-odoring effects or cutting the fiber into short fibers or cotton. The present invention uses a mixture solvent of an oxidized methylmorpholine and acid to uniformly dissolve chitin and cellulose. The product has been proved to have anti-mould, antibacterial and de-odoring effects.

Description

A7 B7 464700 V. Description of the invention (/) The present invention is a method for producing fibers with anti-mildew, antibacterial and deodorizing effects, especially a kind of natural chitin polymer mixed with cellulose, using oxidized methyl marine and The mixed solution of the acid solution is a solvent, so that chitin and cellulose are evenly mixed to make a fiber with antifungal, antibacterial and deodorizing effects. If this product is used in clothing, food, medical product packaging, etc., it can reduce the human body or The product will be infected by microorganisms to ensure the safety of consumers. And the raw materials used in this technology are all composed of natural polymers, which can be naturally decomposed after use, and are environmentally conscious materials. This technology belongs to the technical field of biological and functional fibers. As people ’s requirements for quality of life have increased, the antibacterial mechanisms related to fibers and textiles have been valued at home and abroad. Their technology can be roughly classified as follows: (1) Organic antibacterial methods, such as alcohol, phenol, phenolic acid, and biguanide Department of organic chemicals and fiber combined to achieve antibacterial effect, its antibacterial effect is often reduced by washing out and dissolved organic matter, and it is easy to cause skin irritation. (2) Inorganic antibacterial method, such as metal silver, copper, magnesium, zinc or metal complex polymer or fourth-grade amine salt antibacterial materials are mixed with fibers to develop antibacterial fibers. The antibacterial effect is poor but the effect on the skin is relatively small. small. (3) Antibacterial methods of natural materials, such as antibacterial fibers made of natural glycyrrhizic acid, hinokitiol, chitin, and seed extract combined with various natural fibers. The antibacterial effect varies depending on the combination method. Natural materials are less harmful to the human body and have a better texture than other antibacterial materials. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ------- ^ --- J ---- Ί--; order-^ ----- 唆 I, ( Please read the notes on the back ^^ before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 47 0 0 at 1 " ~ ***** ™ '* ....... & quot * * — *…. ·· ---- .. ·--Description of the invention (Z) The technology of the present invention is a natural antibacterial method, and the chitin polymer used on the earth is second only to cellulose The natural polymer mainly uses waste shrimp and crab shells as raw materials, and can be separated and purified after acid and alkali treatment. The newly made chitin polymer is academically called chitin, which is composed of N-acetylglucos amine and N-glucos amine. Six N-acetylammonium glucosamine and one N-glucosamine are connected. After chitin is treated with hot alkali, the N-acetyl group can be removed to form chitosan. Deacetylation degree can be increased or decreased by controlling NaOH concentration, heating temperature and processing time. The deacetylation degree of chitosan is between 50 ~ 99%. Chitin and chitosan have a wide range of applications, and their main uses include coagulants, health foods, food additives, medical equipment, and can also be used as precipitants and adsorbents for wastewater and sewage treatment. Chitin polymers have free amino groups (~ NH3 +), and the surface of general microorganisms is negatively charged. Under the influence of chitin polymers, it will cause microbial growth interference and achieve the effect of inhibiting microbial growth. Currently in agriculture and The food industry has been widely used in food preservatives, enhancing plant disease resistance and promoting the growth of cultivated crops. ： ；: The present invention uses non-toxic solvents and natural polymers to make anti-mildew, anti-bacteria, and deodorizing fibers. Different from general similar products, various antibacterial agents must be added Ί η or the antibacterial effect can be achieved by surface coating. This product uses a number of materials and process settings to make the product have special anti-mildew, antibacterial and deodorizing effects. Its formula, process and product features are as follows: ', Ί Μ- 纸张 paper scale station state national standard umbrella (CNq Λ. Called. · ΙΐίΤ7 卩 Λ6 47 Ο Ο ^ ii7 λ ·, information statement (3)-one (1) the present invention is made of natural chitin polymer (chitin or chitosan) and cellulose Functional fiber 1 is a pure natural material that has both anti-mildew, antibacterial and deodorizing effects. ^-(Please read the precautions on the back. R page) (2) The process of the present invention uses non-toxic oxidized methyl marine and acid The liquid mixed solution can dissolve the chitin polymer and cellulose into a glue solution at the same time and then perform the wet fiber manufacturing method, which can produce a very uniform distribution effect. The fiber produced by water washing, regeneration and drying can withstand water washing more than 10 times. Still hold The anti-mold, anti-bacterial and deodorizing ability is more than 90%. (3) The fiber of the present invention can be made into continuous long fiber by winding, or cut into short fiber or cotton according to demand. (4) This study After washing out the solvent, it can be recycled and reused through the concentrating equipment, which not only saves costs, but also does not cause environmental pollution. It is a process that attaches importance to environmental protection. (5) The manufacturing of this fiber can be based on customer requirements. Adjust the content ratio of chitin and cellulose to achieve the highest effect and economic benefits. In order to make your members understand the features and implementation effects of this invention, please refer to the figure below for details:.; 丨: Graphic part: li. 1 Table 1 ': The process flow diagram of the present invention regarding the production of anti-mildew, anti-magnetism and deodorizing fibers. Ί The second diagram: The chemical structure diagram of the oxidized methyl marlen used in the present invention. I- _ »The good X branch crosses the Sichuan ten 囡 correction γ standard ((>: s) 8 4 see the prevention (: M () on the factory public 犮) 4 6 47 0 0 i 丨 Description (+) The present invention is a kind of anti-mildew 2. Manufacturing method of antibacterial and deodorizing fiber The manufacturing process is explained as follows: A: cellulose ν'ί; ί-; ί ·-· ν '&. ^. ^. Ή. The cellulose used in the present invention is a-cellulose containing more than 90% long fibers Or short-fiber wood pulp, wood pulp needs to be pulverized before dissolving to increase the dissolving effect. B: Chitin polymer order --- The line is colorless, non-toxic and tasteless biodegradable polymer, mainly seafood. Animal wastes, such as shrimp and crab shells, are used as sources. Treatment with common acid and alkali shrimp and crab shells can complete the separation and purification of chitin polymers. The crude chitin polymer is called chitin (chi tin ), Which can be made into chitosan after deacetylation with strong alkali treatment, and the chitin polymer powder collected in the present invention includes two kinds of chitin and chitosan. C: Oxidized methyl malin mixed acid solution. The main solvent used in the present invention is N-methylmorpholine N-oxide (NMMO). The chemical structure is shown in the second figure, and NMM0 is highly hygroscopic. Chemicals, generally commercially available NMM0 is a 50% solution in water. In order to achieve the best dissolving effect of this solvent, the NMM0 solvent needs to be concentrated under reduced pressure to remove most of the water, and then its pH is adjusted with an acid solution. In order to achieve the best dissolution of cellulose and chitin polymers at the same time. 464700 A7 \ {-..........._ · — ·., · '_ · ,, j VIII. · The invention is called (f' 1 D: cellulose and chitin polymer mixed glue Liquid ----- pumping! (Mf first read the back and then pay attention. Γ page} The present invention mixes the above-mentioned cellulose, chitin polymer and oxidized methyl marine mixed acid solution at one time and Heat and stir until the solid powder. The product obtained is a transparent glue liquid, which can be used for subsequent processing. E: Spinning, regeneration, washing, and drying. Finished yarn can be made through the spinning spinning port, regeneration water tank, water washing tank, and drying wheel, which is a well-known wet spinning process. _ F: Winding- > Become a long-fiber textile fiber. G: Cut—Short fiber or cotton finished yarn can be cut according to the required length and added with Crimp to make short fiber or cotton. Η: Solvent recovery and regeneration The solvent used in the present invention can be used Generally, it is concentrated and reused under reduced pressure, which will not only cause environmental pollution, but also reduce the cost of product production. ;; Your reviewers can further understand the innovative effects of the present invention. Several examples are given below. The examples below are intended to be inclusive of the present invention.

I I '; It is exemplified that there is no intention to limit the scope of the present invention, and a statement is made in this regard. 464700 H7 A-, Description of the invention (f) Example 1: According to the formula table No. 1 ~ 6 formula (see Table 1), chitosan with a degree of deacetylation (DD92) of 92% is chitin Wen ih Note for the first time to read this page Molecularly mixed cellulose (DP = 900) and oxidized methyl marlin mixed acid solution at a constant temperature of 90aC, and stirring at 60 rpm for 30 minutes to dissolve the solids. After forming a brown transparent glue solution, the glue solution is pumped through a spinning gear assembly (0.09 mm 0 X92 holes) into a spinning gear, and then passed through a reeling machine (80 m / min) Take up the finished yarn, and the samples obtained above are numbered 1 to 6, and evaluate the anti-mildew, antibacterial and deodorizing effects. Example 2: Change the chitosan from dege e of deacetylation (DD92) in Example 1 to chitosan with degee of deacetylation (DD85) of 85% Polymers are made of fibers, and product samples are numbered 7-11. Example 3: The chitosan in Example 1 was changed to chitin for spinning and manufacturing. Product samples No. 12-16. a | 'Example 4: Cut samples 6, 11 and 16 into staple fibers with a length of 30 mm and make them into staple fibers by carding. Product numbers 17, 18, and 19. '· «Tv ς« ίΐ fl I .. Paper hate is also suitable for the standard of Sichuan prisoners () Λ · 4 Regulations (Sichuan 丨 Bei Gongchao.T 464700 i. The invention is called (rj). Example 5 : Evaluation of anti-mildew and antibacterial effect This evaluation uses heart fl / O / ococcw ·? IiwreM ·? Subs Ρ. Ί 2ΜΓί? Μ · ϊ 1〇451 as the test strain, the number of bacteria was first cultured on the medium to 5 ~ 70M05 / mL Take 0.2 mL of the test bacteria solution and evenly spread it on a 0.2 g sample, place it in a sterilized capped sample bottle, and incubate at 35 ° C to 37 ° C for 18 hours. Then add 20 mL of sterilized buffered saline, Vigorously shake by hand for 25 to 30 times to disperse the test bacteria in the solution, take the solution and dilute it appropriately, take 1 mL for agar broth culture, and culture conditions at 35 ° C to 37 ° C for 48 hours, and then calculate the colony The number of growth, and finally the dilution number and volume can be calculated to calculate the actual number of bacteria on the sample. The above experiment was repeated 6 times, after the average number of total bacteria was calculated, the antibacterial and antibacterial effect of the sample can be determined according to the following formula :

β Q

Increment or decrement = log (-)-log (-)

A A A: No chitosan is added to the sample. After the test bacterial solution is coated on the sample, the sample is immediately cultured in saline to obtain the number of bacteria. B: No chitosan was added to the sample, and the test bacterial solution was cultured on the sample for 18 hours. The sample was cultured in saline to obtain the number of bacteria. C: Chitosan is added to the sample, the test bacterial solution is coated on the sample, and then cultured for 18 hours. The sample is cultured with saline to obtain the number of bacteria. According to the test standard, samples with an increm nt of 1.6 or higher have the so-called antibacterial effect. The evaluation results of each sample are shown in Table 2. -__________ ··· ----- · — ^ — " —. _______ r .. From Zhang Chiquan Tongchuan Shiji _ Jia detailed rate (< ·. Aunt) λ training, grid (~ ―factory first ^ '" cater for it ... ϊϊ ^ ψ' " · ^: page)

464700 A. 佟 Ming said (g) Example 6: Evaluation of deodorizing effect This evaluation of deodorizing effect uses ammonia and hydrogen sulfide as the deodorizing target to investigate the deodorizing ratio of deodorizing fibers (deodorizing ratio (% )) 'The method and design are roughly as follows: a sealed bottle is filled with a certain concentration of the test gas, a fixed amount of deodorizing fiber is placed in the bottle to adsorb the gas for i hours, and the deodorization is measured by a gas chromatograph (GC). The gas concentration before and after the fiber is placed, and the (initial gas concentration-residual gas concentration) Wu Wu _ The deodorization evaluation of each sample of the initial gas concentration is shown in Table 3. Example 7: Washing resistance test Each sample was rinsed in 70 ° C hot water containing 5g / L of laundry detergent for 45 minutes and 10 times, and each of the samples was subjected to anti-mold and antibacterial experiment and deodorizing effect evaluation again. The results obtained are as follows: Tables 4 and 5 show. (M first read the precautions on the back before t this page)

Table 1: Glue solution manufacturing formula Table formula Chitin polymer (g) Cellulose (g) Oxidized methyl marlin solution (g) 1 0 1000 9000 2 2.5 997.5-9000 3 5 995 9000 4 10 990 9000 5 20 980 9000 6 50 950 9000 I (^ 1 · owed, paper CN-(I quasi 1 ^ 464700

Λ 7 Η7 / "Invention description (Xi) Table 2 The antifungal and antibacterial effect test of raw silk Sample No. Chitin polymer Increment The effect evaluation accounts for the total weight of the fiber or (Yes / No) Percent Decrement 1 0 1-2 0.2 5% DD 9 2 1.55 No 3 0.5% DD 9 2 1.83 Yes 4 1% DD 9 2 2.22 Yes 5 2% DD 9 2 2.55 Yes 6 5% DD 9 2 2.85 Yes 7 0.2 5% DD 8 5 1.5 1 No 8 0.5% DD 8 5 1.8 1 Yes 9 1% DD 8 5 2.21 Yes 10 2% DD 8 5 2.49 Yes 1 1 5% DDB 5 2.80 Yes 12 0.2 5% chiti η 1.03 No 13 0.5% chiti η 1.45 No 14 1% chitin 1.7 1 Yes 15 2% chitin 2.13 Yes 16 5% chitin 2.32 Yes 17 5% DD 9 2 2.82 Yes 18 5% DD 8 5 2.7 1 Yes 19 5% chi 11 n 2.28 Yes Note: DD92 is 92% chitin Glycan, DD85 is deacetylated 85% chitosan, and chitin is chitin. (&Quot; Read the note of WA " ~ ^ ', j'.within V)

46 47 Ο Ο

J1V ---------- · '----------------------.... _______ _____ A ________ ______________ i. Description of the invention ( ί.) Table 3 Evaluation of deodorizing effect Sample No. Chitin polymer deodorizing rate (%) Percentage of total fiber weight H2S 1 0 13.1 10.3 2 0.25% DD92 43,2 29.3 3 0.5% DD 9 2 74.2 55.1 4 1% DD 9 2 80.1 '64 .2 5 2% DD 9 2 85.3 83.1 6 5% DD 9 2 88.1 87.3 7 0.2 5% DD 8 5 42.7 25.3 8 0.5% DD 8 5 69.5 59.5 9 1% DD 8 5 73.4 62.3 10 2% DD 8 5 82.1 81.2 11 5% DD 8 5 85.1 82.3 12 0.2 5% chiti η 38.1 20.3. 13 0,5% chiti η 55.2 47.3 14 1% chitin 65.4 53.2 ^ Γ 15 2% chitin 79.3 69.7 (* 1 4 f '/ 16 5% chitia 8 1.2 75.3 li is called 17 5% DD 9 2 86.3 85.1' Ί V! L \ 18 5% DD 8 5 85.5 79.3 j .1! '19 5% chitin 79.2 7 0.2' 丨Ί lJ 丨: 丨 Note: DD92 is 92% chitosan with deacetylation, DD85 is 85% chitosan with deacetylation ------------ --------- ---------., Chitin is chitin. Μιν 张定政 圯tMin Net home sample quasi-CNS) (2 i (i · 4 6 4? A7 by Li ^ 7 ^ /. 7 printed by the negative consumer and consumer cooperatives B7 V. Description of the invention (π) Table 4 Anti-mildew and antibacterial effect test after washing 1 | Sample No. Chitin Macromolecule Increment Effect Evaluation 1 1 Percent of total fiber weight (yes / no) 1 1 Percent Decrement Please read back 1 1 1 2 0 0.2 5% DD 9 2 1.50 No I 1 i 1 3 0.5% DD92 1.75 Yes 1 4 1% DD 9 2 2.17 Yes No 1 1 1 5 2% DD 9 2 2.50 Yes r Book 1 Pack 6 5% DD 9 2 2.63 Yes Page 1 | 7 0.25% DD85 1.47 No 1 I 8 0.5% DDB 5 1.79 Yes 1 1 1 9 1% DD85 2.21 Yes 1 Order 10 2% DD85 2.39 Yes 1 1 11 5% DD85 2.53 Yes 1 1 12 0.25% chitin 1.04 No 1 [13 0.5% chitin 1.38 No line 1 14 1% chitin 1.69 Yes! 1 15 2% chitin 2.03 Yes 1 I 16 5% chitin 2.33 Yes 1 1 17 5% DD 9 2 2.53 Yes 1 I 18 5% DD85 2.47 Yes 1! I 19 5% chi tin 2.27 is 1 Note: DD92 is 92% chitosan without ethyl acetate, DD85 is 85% chitosan without ethyl acetate, and chitin is chitin1 1 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 6 4 7 0 0 A7 Printed by B7, Intellectual Property Co., Ltd., Ministry of Economic Affairs, M Industrial Cooperative, Co., Ltd. V. Description of invention (/ top) Table 5 Evaluation of the deodorization effect of the raw silk after 10 washings. Sample No. Chitin polymer as a percentage of the total weight of the fiber. Air deodorization rate (%). Hydrogen sulfide 1 0 12.5 9.8 2 0.2 5% DD 9 2 4 1.3 25.8 3 0.5 % DD 9 2 72.5 47.3 4 1% DD 9 2 76.2 54.5 5 2% DD 9 2 8 1.5 79.2 6 5% DD 9 2 86.3 84.3 7 0.2, 5% DD 8 5 39.7 21.5 8 0.5% DD 8 5 66.3 54.9 9 1% DD 8 5 65.4 55.8 10 2% DD 8 5 72.3 74.3 11 5% DD 8 5 83.2 80.3 12 0.2 5% chiti η 29.2 19.2 13 0 · 5% chiti η 52.3 45.3 14 1% ch 11 in 60.2 5 1.1 15 2% chitin 69.3 62.3 16 5% chitin 78.2 73.3 17 5% DD92 84.3 83.9 18 5% DD 8 5 83.1 79.8 19 5% chitin 77.5 72.5 Note: D92 is deacetylated 92% chitosan and DD85 is Chitin is a chitin with a degree of acetic acid of 85%. --------- ^ ------ ir ------ line (please read the notes on the back before K, ^ this page) This paper size applies to China National Standard (CNS) Α4 Specification (210 × 297 mm) 6 d 47 0 0 A7 B7 V. Description of the invention (β) The test results of the antifungal and antibacterial effect of the filaments shown in Table 2 show 'if the chitosan (DD92 or DD8S) is used for the fiber produced by the process of the present invention Its content only needs to account for more than 0.5% of the total fiber weight to achieve the anti-mildew effect. If chitin is used, its content needs to account for more than 1% of the total fiber weight to achieve the anti-mildew effect. If the finished silk is cut, Broken into staple fiber or cotton (samples 17 to 19), its anti-mold and anti-bacterial effect is almost the same as that of long fibers. The example in Table 2 proves that this product and process can indeed achieve anti-mold and anti-bacterial effects. The evaluation of the deodorant effect of the raw silk shown in Table 3 shows that the fibers produced by the process of the present invention have a good adsorption effect on ammonia and hydrogen sulfide gas 'especially when the chitin polymer content is above 0.5%' and its adsorption effect on odor Both can reach more than 50%. Compared with pure cellulose fibers that do not contain chitin polymer, the adsorption effect is 5 to 8 times. At the same time, the short fibers produced by this process also have excellent deodorizing effects. The washing resistance tests shown in Tables 4 and 5 show that after the fiber produced in this process has been treated with hot water and detergent for 10 times, its original anti-mildew, antibacterial and deodorizing effects still retain more than 90% of the original silk effect. This result proves that the product of the present invention is indeed a long-acting anti-mildew, antibacterial and deodorant fiber, and its effect is far more than that of ordinary fibers on the market with surface treatment or adding antibacterial or deodorant. ^ In summary, the present invention uses chitin polymer and cellulose to produce fiber with anti-mildew's antibacterial and deodorizing function. Without the addition of other organic or inorganic antibacterial or deodorant, the product can effectively inhibit Microbial growth and this paper size are applicable to China National Standard (CNS) A4 (210X297 mm) (read the precautions on the back before J_ VT page) Printed 4 6 4 7 〇 〇, Ming Ming said (丨 year) can absorb odors to reduce the chance of pollution to the human body and the object to be protected and the occurrence of odor, and the invention has been proven to be a long-acting fiber, Its degree of resistance to washing is more unmatched by ordinary commercial products. The present invention uses chitin polymer and cellulose as materials, and uses a non-toxic and recoverable solvent, which are the key technologies of the above-mentioned invention process. The manufacturing method is simple and special, and the formula results can achieve the expected effect, while the process quality is stable. ,low cost. The present invention is indeed the creation of a new technology, and similar inventions or publications have not been seen in similar process technologies. They should have met the requirements for invention patents, and have submitted patent applications in accordance with the law. (Notes for reading 'M ^ between me and r this page)

.!: Paper hate standard suitable for Sichuan H 闼 family standards ((.: NS) AW, Grid (21U ... Gong 犮)

Claims (1)

A8 B8 C8 D8 464700 No. 0811115308 The manufacturing method of the fiber with anti-mildew, antibacterial and deodorizing function is applied for the amendment of the patent scope 1. A method for manufacturing the fiber with anti-mildew, antibacterial and deodorizing function After the polymer and cellulose are dissolved in the mixed solution of oxidized methyl marlin and acid solution, the glue solution is heated and stirred to form a glue solution, and then the glue solution is sent by a gear pump, a spinning port, a regeneration water tank, and a washing tank drying wheel. The resulting fiber can be rolled into long fibers, and the fibers can be cut into short fibers or cotton:. Among them, chitin polymer and cellulose are solid components, accounting for 5% to 15% of the total weight of the glue. The temperature of the heating and stirring is 80 to liot. The heating time is 5 to 45 minutes, so that the chitin polymer and cellulose are fully dissolved to form a glue solution. At this time, the pH value of the glue solution is 6.9 to 3. Among them, the non-solvent 1 using water as the regeneration water tank for spinning is controlled at a temperature of 20 to 60 ° C, and the winding speed of the fiber is 50 meters to 500 meters per minute. 2. The method according to item 1 of the scope of patent application, wherein the chitin polymer is obtained by refining shrimp and crab shells, and the composition is chitin or chitosan, of which chitosan The degree of deacetylation is 75% to 99%, and the chitin polymer accounts for 0.5% to 5% of the total weight of the fiber. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Order A8 B8 CS D8 Ministry of Economic Affairs, Smart Finance and Industry Bureau, Industry Consumption # 4范围 、 Scope of patent application 3. The method described in item 1 of the scope of patent application, wherein the cellulose is a long- or short-fiber pulp containing more than 90% of α-cellulose, and the degree of polymerization of cellulose is 600 to 1100,... The pulp is pulverized by a pulverizer before dissolving to increase the dissolving efficiency. 4. The method as described in item I of the scope of patent application 'wherein N-methy Imorphoine N-oxide needs to be removed by vacuum heating to make it 90% to 97% pure, and By adjusting the pH value of the acid solution to 6.9 to 3, the best effect of dissolving the chitin polymer and cellulose is achieved. 5. The method described in item 4 of the scope of patent application, the acid solution used is organic acid such as hydrochloric acid, formic acid ', acetic acid, propionic acid, phosphoric acid, lactic acid, malic acid, succinic acid, nitric acid' oxalic acid, adipic acid, etc. Inorganic acid. This paper size is applicable to China National Standard (CNS) A4 specification (210X297). (Please read the precautions on the back before filling this page>