KR101087264B1 - Manufacturing method of high efficiency hybrid heating fiber - Google Patents
Manufacturing method of high efficiency hybrid heating fiber Download PDFInfo
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- KR101087264B1 KR101087264B1 KR1020100029008A KR20100029008A KR101087264B1 KR 101087264 B1 KR101087264 B1 KR 101087264B1 KR 1020100029008 A KR1020100029008 A KR 1020100029008A KR 20100029008 A KR20100029008 A KR 20100029008A KR 101087264 B1 KR101087264 B1 KR 101087264B1
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- South Korea
- Prior art keywords
- fiber
- weight
- guanidine
- heat generation
- sodium
- Prior art date
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- 239000000835 fiber Substances 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000010438 heat treatment Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 41
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- -1 copper sulfide compound Chemical class 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000005749 Copper compound Substances 0.000 claims description 11
- 150000001880 copper compounds Chemical class 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 230000001698 pyrogenic effect Effects 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 7
- 229960004198 guanidine Drugs 0.000 claims description 7
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 7
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 6
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229940076286 cupric acetate Drugs 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 abstract description 26
- 230000005611 electricity Effects 0.000 abstract description 8
- 238000005485 electric heating Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004753 textile Substances 0.000 description 4
- 230000036760 body temperature Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
본 발명은 흡습발열 기능과 전기발열 기능을 동시에 나타내는 고효율 하이브리드 발열섬유의 제조방법에 관한 것이다. 본 발명의 발열섬유의 제조방법은 아크릴계 섬유에 강한 친수성기인 카르복시기를 도입하여 흡습발열 기능을 부여하는 제1처리 공정과 아크릴계 섬유에 황화구리 화합물을 결합시켜 전기전도성을 부여함으로써 전기발열 기능을 발현하게 하는 제2처리 공정으로 이루어지며, 제1처리 공정은 가교반응 단계 및 알칼리 가수분해반응 단계를 포함하고, 제2처리 공정은 구리이온 결합 단계 및 환원반응 단계를 포함하는 것을 특징으로 한다. 본 발명의 발열섬유의 제조방법에 의하면 일상적인 한랭 환경에서는 습기를 흡수하여 발열하는 흡습발열 기능에 의해 온도를 높여주고, 보다 극한의 한랭 환경에서 고발열이 필요한 경우에는 전기의 힘에 의한 발열 기능에 의해 온도를 높여줄 수 있으며, 흡습발열과 전기발열의 융합에 의해 배터리 등 전기의 소모량을 줄일 수 있는 고효율 발열 섬유제품의 제조가 가능하다.The present invention relates to a method for producing a highly efficient hybrid heating fiber which exhibits a hygroscopic function and an electric heating function. The method of manufacturing the exothermic fiber of the present invention introduces a carboxyl group, which is a strong hydrophilic group, to the acrylic fiber to impart a hygroscopic heat generation function, and combines a copper sulfide compound to the acrylic fiber to impart electric conductivity by expressing an electric heat generation function. It consists of a second treatment process, the first treatment process comprises a crosslinking reaction step and an alkali hydrolysis reaction step, the second treatment process is characterized in that it comprises a copper ion bonding step and a reduction reaction step. According to the manufacturing method of the exothermic fiber of the present invention, the temperature is increased by a hygroscopic heat generation function that absorbs moisture and generates heat in a daily cold environment, and when high heat generation is required in an extreme cold environment, the heat generation function by electric force is applied. By increasing the temperature, it is possible to manufacture high-efficiency heating fiber products that can reduce the consumption of electricity, such as batteries by the convergence of hygroscopic heat generation and electric heat generation.
Description
본 발명은 고효율 하이브리드 발열섬유의 제조방법에 관한 것이다. 구체적으로는 아크릴계 섬유를 알칼리로 가수분해하여 강한 친수성기인 카르복시기를 다량 도입하는 제1처리 공정 및 구리 화합물과 황을 포함하는 환원제로 처리하여 섬유 내부에 다량의 황화구리 화합물이 형성되도록 하는 제2처리 공정을 차례대로 거쳐서 흡습발열 기능과 전기발열 기능을 동시에 나타내도록 하는 발열섬유의 제조 방법에 관한 것이다.The present invention relates to a method for producing a high efficiency hybrid heating fiber. Specifically, the first process of hydrolyzing acrylic fibers with alkali to introduce a large amount of carboxyl groups, which are strong hydrophilic groups, and the second treatment of forming a large amount of copper sulfide compound inside the fibers by treating with a reducing agent containing a copper compound and sulfur. It relates to a method for producing a heating fiber to exhibit a hygroscopic heat generating function and an electric heat generating function at the same time through the step.
섬유는 의복으로 사용될 때 사용되는 환경에 따라 다양한 기능성을 필요로 한다. 특히 온도가 낮은 환경에서 의복은 주위 환경으로부터 체온을 유지해주는 보온 기능을 필요로 하며, 더 나아가 보다 온도가 낮은 한랭 환경에서는 온도를 올려주어 외부의 추위로부터 인체를 보호하는 적극적인 발열 기능이 필요해진다. Fibers require a variety of functionality depending on the environment used when used as a garment. Especially in low temperature environment, clothing needs warm function to keep body temperature from the surrounding environment, and furthermore, in cold environment with lower temperature, active heating function is needed to protect the human body from external cold by raising the temperature.
이렇게 섬유제품에 발열 기능을 부여하는 방법으로는 세라믹 등을 섬유에 결합하여 태양의 가시광선을 흡수해 원적외선으로 방출하여 의복 내부의 온도를 올리는 축열 기능 부여 방법, 섬유에 카르복시기와 같은 강한 친수성기를 다량 부여하여 인체로부터 발산되는 땀 등의 수분을 흡수하여 발열하도록 하는 흡습발열 기능 부여 방법, 및 금속 등 전도성 물질을 사용하여 와이어 형태 또는 시트의 형태로 만들어 의복에 부착하고 전기를 흘려주어 발열하도록 하는 선상발열체 또는 면상발열체를 이용하는 전기발열 기능 부여 방법 등이 있다. As a method of imparting heat generation function to textile products, a method of imparting heat storage function by absorbing the visible rays of the sun by releasing ceramics into fibers and releasing them as far infrared rays to raise the temperature inside the garment, and a large amount of strong hydrophilic groups such as carboxyl groups in the fiber The method of imparting hygroscopic heat generation function to absorb moisture such as sweat emitted from the human body to generate heat, and to form clothes in the form of wire or sheet using a conductive material such as metal and attach it to clothes and flow electricity by flowing electricity. And an electric heating function provision method using a heating element or a planar heating element.
상기 방법 중 축열 기능 부여 방법과 흡습발열 기능 부여 방법은 전기 등 별도의 동력이 필요 없이 태양빛이나 생리 활동에 따른 현상을 이용한다는 장점은 있지만, 발열 효과가 비교적 낮아 극한의 한랭 환경에서는 효과가 적어 용도가 제한적이라는 문제점이 있다. Among the above methods, the method of providing heat storage function and the method of providing moisture absorption heat generation have the advantage of using the phenomenon according to sunlight or physiological activity without the need for a separate power source such as electricity, but the effect of heat generation is relatively low, so it is less effective in extreme cold environment. There is a problem that the use is limited.
또한 선상발열체 또는 면상발열체를 이용하는 전기발열 기능 부여 방법은 높은 발열 효과를 기대할 수는 있어 극한 환경에도 적용이 가능하지만 배터리 등 외부의 전기적인 힘을 공급해주어야 하기 때문에 배터리가 떨어지면 발열성을 전혀 나타낼 수 없고, 오랜 시간 발열 효과를 나타내기 위해서는 배터리가 커져야 하므로 휴대성이 떨어진다는 단점이 있다. In addition, the electric heating function granting method using the linear heating element or the planar heating element can be expected to have a high heat generation effect, so it can be applied to the extreme environment, but since the external electric power such as the battery must be supplied, it can exhibit no heat generation at all. There is a disadvantage in that the portability is poor because the battery must be large in order to exhibit a long time heating effect.
본 발명은 상기와 같은 기존 방법의 문제점을 해결하기 위해 아크릴계 섬유를 알칼리로 가수분해하여 카르복시기를 형성시켜 흡습발열 기능을 부여하는 단계, 구리 화합물과 황을 포함하는 환원제로 처리함으로써 섬유 내부에 다량의 황화구리 화합물을 형성하여 전기발열 기능을 부여하는 단계를 차례대로 거침으로써 흡습발열 기능과 전기발열 기능을 동시에 부여하여 일상적인 한랭 환경에서는 흡습발열 기능에 의해 체온을 유지하고, 극한의 한랭 환경에서는 전기발열 기능에 의해 외부로부터 인체를 보호하며, 흡습발열 기능과의 복합 효과에 의해 배터리 소모량을 줄이고, 지속 시간을 늘릴 수 있도록 하는 고효율 하이브리드 발열섬유의 제조 방법을 제공하는 것을 목적으로 한다. The present invention is to solve the problem of the conventional method as described above, hydrolyzing the acrylic fiber with alkali to form a carboxyl group to give a hygroscopic heat generation function, by treating with a reducing agent containing a copper compound and sulfur a large amount inside the fiber By forming copper sulfide compound to give electric heating function in order, it gives moisture absorption function and electric heating function at the same time to maintain body temperature by moisture absorption heat generation function in ordinary cold environment, and electricity in extreme cold environment. An object of the present invention is to provide a method for manufacturing a highly efficient hybrid heating fiber which protects the human body from the outside by a heat generation function and reduces battery consumption and increases a duration by a combined effect with a moisture absorption heat generation function.
상기한 과제를 해결하기 위하여 본 발명의 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 아크릴계 섬유를 가교제로 처리하는 가교반응 단계 및 알칼리로 가수분해하여 카르복시기를 섬유에 도입하는 가수분해반응 단계를 포함하는 제1처리 공정; 및 상기 제1처리 공정을 거친 아크릴계 섬유를 구리 화합물로 처리하는 구리이온 결합 단계 및 황을 포함하는 환원제로 처리하여 섬유 내부에 다량의 황화구리 화합물이 형성되도록 하는 환원반응 단계를 포함하는 제2처리 공정을 포함한다.In order to solve the above problems, the method for producing a pyrogenic fiber according to an embodiment of the present invention includes a crosslinking step of treating acrylic fiber with a crosslinking agent and a hydrolysis step of introducing a carboxyl group into the fiber by hydrolysis with alkali. A first treatment step of performing; And a reduction reaction step of forming a large amount of copper sulfide compound in the fiber by treating the acrylic fiber having undergone the first treatment process with a copper ion bonding step of treating the copper fiber with a copper compound and a reducing agent including sulfur. Process.
본 발명의 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 제1처리 공정의 가교반응 단계에서 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 구아니딘, 구아니딘카보네이트, 구아니딘나이트레이트, 구아니딘하이드로클로라이드 및 구아니딘포스페이트로 이루어진 군에서 선택된 1종 이상을 섬유 중량에 대해 10 내지 100중량% 포함하는 가교제 수용액을 이용하여 아크릴계 섬유를 80 내지 120℃에서 30분 내지 3시간 처리하는 것을 특징으로 한다.Method for producing a pyrogenic fiber according to another suitable embodiment of the present invention, ethylenediamine, diethylenetriamine, triethylenetetramine, guanidine, guanidine carbonate, guanidine nitrate, guanidine hydrochloride in the crosslinking reaction step of the first treatment step And it is characterized in that the acrylic fiber is treated for 30 minutes to 3 hours at 80 to 120 ℃ using a crosslinking agent aqueous solution containing 10 to 100% by weight relative to the fiber weight of at least one selected from the group consisting of guanidine phosphate.
본 발명의 또 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 상기 가교제 수용액이 수산화나트륨, 수산화칼륨 및 탄산나트륨으로 이루어진 군에서 선택된 1종 이상의 화합물을 섬유 중량에 대해 10 내지 30중량% 더 포함하는 것을 특징으로 한다.Method for producing a pyrogenic fiber according to another suitable embodiment of the present invention, the crosslinking agent aqueous solution further comprises 10 to 30% by weight based on the weight of the fiber at least one compound selected from the group consisting of sodium hydroxide, potassium hydroxide and sodium carbonate. It is characterized by.
본 발명의 또 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 제1처리 공정의 가수분해반응 단계에서 수산화나트륨, 수산화칼륨 및 탄산나트륨으로 이루어진 군에서 선택된 1종 이상의 화합물을 섬유 중량에 대해 10 내지 100중량% 포함하는 알칼리 수용액으로 아크릴계 섬유를 80 내지 120℃에서 30분 내지 3시간 처리하는 것을 특징으로 한다.Method for producing a pyrogenic fiber according to another suitable embodiment of the present invention, at least one compound selected from the group consisting of sodium hydroxide, potassium hydroxide and sodium carbonate in the hydrolysis step of the first treatment step 10 to 10 by weight of the fiber It is characterized in that the acrylic fiber is treated with an aqueous alkali solution containing 100% by weight at 80 to 120 ° C. for 30 minutes to 3 hours.
본 발명의 또 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 상기 알칼리 수용액이 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 구아니딘, 구아니딘카보네이트, 구아니딘나이트레이트, 구아니딘하이드로클로라이드 및 구아니딘포스페이트로 이루어진 군에서 선택된 1종 이상을 섬유 중량에 대해 10 내지 60% 더 포함하는 것을 특징으로 한다.Method for producing a pyrogenic fiber according to another suitable embodiment of the present invention, the aqueous alkali solution is ethylenediamine, diethylenetriamine, triethylenetetramine, guanidine, guanidine carbonate, guanidine nitrate, guanidine hydrochloride and guanidine phosphate At least one member selected from the group consisting of characterized in that it further comprises 10 to 60% by weight of the fiber.
본 발명의 또 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 제2처리 공정의 구리이온 결합 단계에서 황산제2구리, 아세트산제2구리, 염화제2구리 중 선택된 1종 이상을 섬유 중량 대비 10 내지 50중량% 포함하는 구리 화합물 수용액으로 아크릴계 섬유를 80 내지 100℃에서 10분 내지 2시간 처리하는 것을 특징으로 한다.According to another suitable embodiment of the present invention, a method of manufacturing a pyrogenic fiber may include at least one selected from the group consisting of cupric sulfate, cupric acetate, and cupric chloride in the copper ion bonding step of the second treatment step. It is characterized in that the acrylic fiber is treated with an aqueous copper compound solution containing 10 to 50% by weight for 10 minutes to 2 hours at 80 to 100 ° C.
본 발명의 또 다른 적절한 실시 형태에 따른 발열섬유의 제조 방법은, 제2처리 공정의 환원반응 단계에서 티오아세트아마이드, 티오우레아, 황화나트륨, 티오황산나트륨, 아황산수소나트륨, 차아황산나트륨, 포름알데히드설폭실산나트륨 중 선택된 1종 이상을 섬유 중량에 대해 10 내지 50중량% 포함하는 환원제 수용액으로 아크릴계 섬유를 60 내지 100℃에서 30분 내지 5시간 처리하는 것을 특징으로 한다.Method for producing a pyrogenic fiber according to another suitable embodiment of the present invention, in the reduction reaction step of the second treatment step, thioacetamide, thiourea, sodium sulfide, sodium thiosulfate, sodium hydrogen sulfite, sodium hyposulfite, formaldehyde sulfoxylic acid It is characterized in that the acrylic fiber is treated at 60 to 100 ° C. for 30 minutes to 5 hours with a reducing agent aqueous solution containing 10 to 50% by weight of at least one selected from sodium.
본 발명의 제조 방법을 이용하여 제조된 고효율 하이브리드 발열섬유 소재를 의복 등에 적용하면, 일상적인 한랭 환경에서는 흡습발열 기능에 의해 체온을 유지하고, 극한의 한랭 환경에서는 전기발열 기능에 의해 외부로부터 인체를 보호하며, 흡습발열 기능과의 복합 효과에 의해 배터리 소모량을 줄이고, 지속 시간을 늘릴 수 있으므로 에너지 효율이 높고, 다양한 용도에 적용될 수 있으며, 외부 환경에 따라 적합한 온도 조절이 가능한 스마트 발열 섬유제품의 제조가 가능하다.When the highly efficient hybrid heating fiber material manufactured using the manufacturing method of the present invention is applied to clothing, etc., the body temperature is maintained by the hygroscopic heat generation function in the daily cold environment, and the human body from the outside by the heat generation function in the extreme cold environment. It is energy efficient, can be applied to various applications, and can be controlled according to the external environment. Is possible.
아크릴계 섬유는 섬유 구조 중 아크릴로니트릴의 함량이 35% 이상인 합성 섬유를 말하며, 아크릴로니트릴의 함량이 85% 이상인 아크릴 섬유와 아크릴로니트릴의 함량이 35~85%인 모다크릴 섬유로 분류한다. 아크릴계 섬유의 아크릴로니트릴은 구조 중 니트릴기를 포함한다. 이러한 아크릴계 섬유를 수산화나트륨 등과 같은 알칼리로 고온에서 처리하면 가수분해반응에 의해 니트릴기가 강한 친수성기인 카르복시기로 변환되므로 결과적으로 아크릴계 섬유는 강한 수분 흡수성을 띠게 되어 아크릴계 섬유에 흡습발열 기능을 부여할 수 있게 된다.Acrylic fibers refer to synthetic fibers having an acrylonitrile content of at least 35% in the fiber structure, and are classified into acrylic fibers having an acrylonitrile content of at least 85% and modacryl fibers having an acrylonitrile content of 35 to 85%. Acrylonitrile of acrylic fibers includes nitrile groups in the structure. When the acrylic fiber is treated with an alkali such as sodium hydroxide at a high temperature, the nitrile group is converted into a carboxyl group, which is a strong hydrophilic group, by hydrolysis reaction, and as a result, the acrylic fiber has a strong water absorbency, which can give a hygroscopic heat generation function to the acrylic fiber. do.
한편 구리는 높은 전도성을 가진 금속으로, 금속 상태로 존재하면 산화에 의한 변색이 발생하고, 피부에 접촉 시 문제를 일으키므로 금속 구리를 그대로 의복 등 섬유제품에 적용하기 곤란한 점이 있다. 이러한 구리는 이온 상태로 존재할 수도 있으며, 구리 이외의 다른 원소와 결합하여 구리 화합물 형태로 존재할 수 있다. 특히 황과 결합하여 황화구리 화합물을 형성하면 전기가 통하는 전도성을 가지게 되고, 비교적 안정되므로 섬유와 결합시키면 금속 구리 형태와 비교해 안전한 전도성 섬유의 제조가 가능하여 의복 등의 섬유제품에 적용하기에 적합하며, 배터리 등에 의해 전기를 공급해주면 저항에 의해 열이 발생하는 전기발열 기능의 부여가 가능하다. On the other hand, copper is a metal with high conductivity, and when present in a metallic state, discoloration occurs due to oxidation, and it causes problems when contacted with the skin, which makes it difficult to apply metallic copper to textile products such as clothes. Such copper may be present in an ionic state and may be present in the form of a copper compound in combination with other elements than copper. In particular, when combined with sulfur to form a copper sulfide compound, it has electrical conductivity, and is relatively stable. Therefore, when combined with fiber, it is possible to manufacture safe conductive fibers in comparison with metallic copper forms, and is suitable for application to textile products such as garments. If electricity is supplied by a battery or the like, it is possible to give an electric heat generating function that generates heat by resistance.
본 발명의 발열섬유의 제조 방법은, 아크릴계 섬유를 가교제로 처리하는 가교반응 단계 및 알칼리로 가수분해하여 카르복시기를 섬유에 도입하는 가수분해반응 단계를 포함하는 제1처리 공정, 및 상기 제1처리 공정을 거친 아크릴계 섬유를 구리 화합물로 처리하는 구리이온 결합 단계 및 황을 포함하는 환원제로 처리하여 섬유 내부에 다량의 황화구리 화합물이 형성되도록 하는 환원반응 단계를 포함하는 제2처리 공정을 포함한다. 아래에서 본 발명의 발열섬유 제조 방법에 관하여 각 공정별로 상세하게 설명한다.
The method for producing a pyrogenic fiber of the present invention includes a first treatment step including a crosslinking reaction step of treating acrylic fibers with a crosslinking agent and a hydrolysis reaction step of hydrolyzing with alkali to introduce carboxyl groups into the fiber, and the first treatment step. And a second treatment process including a copper ion bonding step of treating the acrylic fiber through the copper compound with a copper compound, and a reduction reaction step of forming a large amount of copper sulfide compound in the fiber by treating with a reducing agent including sulfur. Hereinafter, the heating fiber manufacturing method of the present invention will be described in detail for each process.
제1처리 공정1st process
먼저 섬유에 흡습발열 기능을 부여하기 위한 제1처리 공정은 가교제가 포함된 수용액으로 아크릴계 섬유를 가교처리하는 가교반응 단계 및 알칼리 수용액으로 가수분해하여 카르복시기를 섬유에 도입하는 가수분해반응 단계를 포함한다.First, a first treatment process for imparting a hygroscopic heating function to the fiber includes a crosslinking step of crosslinking acrylic fibers with an aqueous solution containing a crosslinking agent and a hydrolysis reaction step of hydrolyzing with an aqueous alkali solution to introduce carboxyl groups into the fiber. .
아크릴계 섬유는 알칼리로 가수분해하면 니트릴기가 카르복시기로 변환됨에 따라 섬유가 물에 용해되려는 성질인 수용성이 증가하여 섬유의 형태를 유지하기 어렵게 된다. 따라서 제1처리 공정에서 가수분해에 따른 섬유의 수용성화를 방지하여 섬유제품으로 사용하기 적합한 섬유를 제조하기 위해, 아크릴계 섬유를 가교제로 처리하여 분자간 가교결합을 도입하는 가교반응 단계를 실시한다. When the acrylic fiber is hydrolyzed with alkali, the nitrile group is converted into a carboxyl group, so that the water solubility of the fiber is soluble in water, so that it is difficult to maintain the form of the fiber. Therefore, in order to prepare a fiber suitable for use as a fiber product by preventing the water solubilization of the fiber due to hydrolysis in the first treatment process, a crosslinking reaction step of introducing an intermolecular crosslinking by treating the acrylic fiber with a crosslinking agent.
본 발명의 발열섬유 제조 방법은, 이러한 점을 고려하여 제1처리 공정의 가수분해반응 단계 이전에 가교반응을 수행하는 것이 바람직하다.In consideration of this point, in the method of manufacturing the exothermic fiber of the present invention, it is preferable to perform the crosslinking reaction before the hydrolysis step of the first treatment process.
상기 가교반응 단계는 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 구아니딘, 구아니딘카보네이트, 구아니딘나이트레이트, 구아니딘하이드로클로라이드, 구아니딘포스페이트 중 선택된 1종 이상의 가교제를 섬유 중량에 대해 10 내지 100중량% 포함하는 수용액을 사용하며, 더욱 바람직하게는 가교제를 섬유 중량에 대하여 40~90중량% 포함하는 수용액을 사용하여 아크릴계 섬유를 80 내지 120℃에서 30분 내지 3시간 처리하는 것을 특징으로 한다. 또한 상기 처리하는 가교제 수용액의 욕비는 1:5~30으로 하는 것이 바람직하다. 상기한 욕비의 범위 내에서는 균일하고 경제적인 처리가 가능하나, 욕비가 1:5 미만일 경우에는 매우 불균일하게 처리되며, 1:30을 초과하는 경우에는 생산성 저하 등의 문제가 발생하므로 바람직하지 않다. The crosslinking step includes 10 to 100% by weight of at least one crosslinking agent selected from ethylenediamine, diethylenetriamine, triethylenetetramine, guanidine, guanidine carbonate, guanidine nitrate, guanidine hydrochloride, and guanidine phosphate. An aqueous solution is used, and more preferably, acrylic fibers are treated at 80 to 120 ° C. for 30 minutes to 3 hours using an aqueous solution containing 40 to 90% by weight of the crosslinking agent. Moreover, it is preferable that the bath ratio of the crosslinking agent aqueous solution to process is set to 1: 5-30. Although uniform and economical treatment is possible within the range of the above bath ratio, if the bath ratio is less than 1: 5, it is very unevenly processed, and if it exceeds 1:30, it is not preferable because problems such as productivity decrease occur.
또한 상기 가교제 수용액에 알칼리 화합물을 섬유 중량에 대하여 10 내지 30중량%를 추가로 포함시켜서 가교제 수용액을 제조할 수도 있다. 일반적으로 아크릴계 섬유는 내부구조가 치밀하여 화학 약제의 침투가 어려우며, 가교제 역시 효과적으로 섬유 내부에 침투하기가 쉽지 않아 충분한 가교결합을 형성하기 위해서는 많은 양의 가교제를 필요로 한다. 따라서 가교제를 사용한 가교반응 시 알칼리 화합물을 같이 사용하면 섬유 분자의 구조가 느슨해지는 효과가 있어 가교반응을 촉진하게 되어 보다 적은 양의 가교제를 사용할 수 있는 효과가 있다. 상기 알칼리 화합물로는 수산화나트륨, 수산화칼륨, 탄산나트륨 중 선택된 1종 이상의 화합물을 사용할 수 있다. In addition, the aqueous solution of the crosslinking agent may be prepared by further including 10 to 30% by weight of the alkali compound in the crosslinking agent aqueous solution. In general, acrylic fibers have a dense internal structure, making it difficult to penetrate chemical agents, and crosslinking agents also need a large amount of crosslinking agents to form sufficient crosslinks because they are difficult to penetrate effectively into the fibers. Therefore, when the alkali compound is used together in the crosslinking reaction using the crosslinking agent, the structure of the fiber molecules is loosened, thereby promoting the crosslinking reaction, and thus, a smaller amount of the crosslinking agent can be used. As the alkali compound, at least one compound selected from sodium hydroxide, potassium hydroxide and sodium carbonate may be used.
아크릴계 섬유를 가수분해반응시킬 때 사용되는 알칼리 화합물의 종류와 사용량 및 처리 온도와 처리 조건 등에 따라 카르복시기로 변환되는 정도를 조절할 수 있는데 그 중 가장 영향이 큰 것은 알칼리 화합물의 사용량이다. 즉, 많은 양의 알칼리로 가수분해반응을 시키면 카르복시기의 양이 늘어나게 되어 수분 흡수성이 증가하므로 높은 흡습발열성을 기대할 수 있지만, 너무 많은 카르복시기가 부여되면 섬유가 물에 용해되어버리므로 의복 등 섬유제품으로 사용하기 부적합해진다. 따라서 적절한 농도를 사용해야 한다. 본 발명의 발열섬유 제조 방법은, 이러한 점을 고려하여 제1처리 공정의 가수분해반응 단계에서 알칼리 화합물을 섬유 중량에 대해 10 내지 100중량% 포함하는 알칼리 수용액을 사용하며, 더욱 바람직하게는 알칼리 화합물을 섬유 중량에 대하여 20~70중량% 포함하는 수용액을 사용하여 80 내지 120℃에서 30분 내지 3시간 처리하는 것을 특징으로 한다. 또한 상기 처리하는 알칼리 수용액의 욕비는 1:5~30으로 하는 것이 바람직하다. 상기한 욕비의 범위 내에서는 균일하고 경제적인 처리가 가능하나, 욕비가 1:5 미만일 경우에는 매우 불균일하게 처리되며, 1:30을 초과하는 경우에는 생산성 저하 등의 문제가 발생하므로 바람직하지 않다. 본 발명에서 욕비란 처리할 섬유 중량에 대한 처리용액의 부피비를 의미한다.The degree of conversion to carboxyl groups can be controlled according to the type and amount of alkali compound used when hydrolyzing acrylic fibers and the treatment temperature and treatment conditions. In other words, if the hydrolysis reaction is carried out with a large amount of alkali, the amount of carboxyl groups is increased and the water absorption is increased. Therefore, high hygroscopic heat generation can be expected. However, if too much carboxyl groups are given, the fibers are dissolved in water, so textile products such as clothing It becomes unsuitable for use. Therefore, proper concentration should be used. In consideration of this point, the method for producing a heating fiber of the present invention uses an aqueous alkali solution containing 10 to 100% by weight of the alkali compound based on the weight of the fiber in the hydrolysis reaction step of the first treatment step, more preferably the alkali compound. It characterized in that the treatment for 30 minutes to 3 hours at 80 to 120 ℃ using an aqueous solution containing 20 to 70% by weight relative to the weight of the fiber. Moreover, it is preferable that the bath ratio of the alkali aqueous solution to process is set to 1: 5-30. Although uniform and economical treatment is possible within the range of the above bath ratio, if the bath ratio is less than 1: 5, it is very unevenly processed, and if it exceeds 1:30, it is not preferable because problems such as productivity decrease occur. In the present invention, the bath ratio means the volume ratio of the treatment solution to the weight of the fiber to be treated.
또한 상기 가수분해용 수용액에 추가로 가교제를 섬유 중량에 대하여 10~60중량% 포함하는 것도 바람직하다. 가수분해 시 가교제를 함께 사용함으로써 가교반응과 가수분해반응이 동시에 일어나도록 하여 두 가지 반응이 경쟁함으로써 급격한 가수분해를 방지하여 보다 균일한 처리가 가능해지는 이점이 있고, 섬유의 수용성화를 더욱 방지해주는 효과가 있다.Furthermore, it is also preferable to contain 10-60 weight% of crosslinking agents with respect to a fiber weight further to the said hydrolysis aqueous solution. By using a crosslinking agent in the case of hydrolysis, the crosslinking reaction and the hydrolysis reaction occur at the same time, so that the two reactions compete to prevent rapid hydrolysis, thereby allowing more uniform treatment, and further preventing water solubility of the fiber. It works.
상기 알칼리 화합물로는 수산화나트륨, 수산화칼륨, 탄산나트륨 중 선택된 1종 이상의 화합물을 사용할 수 있으며, 가교제로는 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 구아니딘, 구아니딘카보네이트, 구아니딘나이트레이트, 구아니딘하이드로클로라이드, 구아니딘포스페이트 중 선택된 1종 이상을 사용할 수 있다.
As the alkali compound, at least one compound selected from sodium hydroxide, potassium hydroxide and sodium carbonate may be used, and as a crosslinking agent, ethylenediamine, diethylenetriamine, triethylenetetramine, guanidine, guanidine carbonate, guanidine nitrate and guanidine hydro One or more selected from chloride and guanidine phosphate may be used.
제2처리 공정2nd treatment process
섬유에 전기발열 기능을 부여하는 제2처리 공정은 섬유에 구리이온을 결합시키는 구리이온 결합 단계 및 환원반응 단계를 포함한다.The second treatment process of imparting the heat generating function to the fiber includes a copper ion bonding step and a reduction reaction step of bonding copper ions to the fiber.
먼저 구리이온 결합 단계는 제1처리 공정을 거친 아크릴계 섬유에 대해 황산제2구리, 아세트산제2구리, 염화제2구리 중 선택된 1종 이상을 섬유 중량 대비 10 내지 50중량% 포함하는 구리 화합물 수용액으로 아크릴계 섬유를 80 내지 100℃에서 10분 내지 2시간 처리하여 아크릴계 섬유의 카르복실기에 구리이온을 결합시킨다. 또한 상기 처리하는 구리 화합물 수용액의 욕비는 1:5~30으로 하는 것이 바람직하다. 상기한 욕비의 범위 내에서는 균일하고 경제적인 처리가 가능하나, 욕비가 1:5 미만일 경우에는 매우 불균일하게 처리되며, 1:30을 초과하는 경우에는 생산성 저하 등의 문제가 발생하므로 바람직하지 않다. First, the copper ion bonding step is a copper compound solution containing 10 to 50% by weight relative to the fiber weight of at least one selected from cupric sulfate, cupric acetate, and cupric chloride with respect to the acrylic fiber after the first treatment step. The acrylic fiber is treated at 80 to 100 ° C. for 10 minutes to 2 hours to bond copper ions to the carboxyl group of the acrylic fiber. Moreover, it is preferable that the bath ratio of the copper compound aqueous solution to process is set to 1: 5-30. Although uniform and economical treatment is possible within the range of the above bath ratio, if the bath ratio is less than 1: 5, it is very unevenly processed, and if it exceeds 1:30, it is not preferable because problems such as productivity decrease occur.
다음으로 상기에서 구리이온을 결합시킨 아크릴계 섬유에 대해 티오아세트아마이드, 티오우레아, 황화나트륨, 티오황산나트륨, 아황산수소나트륨, 차아황산나트륨, 포름알데히드설폭실산나트륨 중 선택된 1종 이상의 화합물을 섬유 중량에 대해 10 내지 50중량% 포함하는 환원제 수용액으로 아크릴계 섬유를 60 내지 100℃에서 30분 내지 5시간 처리하는 환원반응 단계를 포함한다. 또한 상기 처리하는 환원제 수용액의 욕비는 1:5~30으로 하는 것이 바람직하다. 상기한 욕비의 범위 내에서는 균일하고 경제적인 처리가 가능하나, 욕비가 1:5 미만일 경우에는 매우 불균일하게 처리되며, 1:30을 초과하는 경우에는 생산성 저하 등의 문제가 발생하므로 바람직하지 않다. Next, at least one compound selected from thioacetamide, thiourea, sodium sulfide, sodium thiosulfate, sodium bisulfite, sodium hyposulfite, and sodium formaldehyde sulfoxylate was used for the acrylic fiber bonded copper ions. It comprises a reduction reaction step of treating the acrylic fiber at 60 to 100 ℃ 30 minutes to 5 hours with an aqueous reducing agent containing from 50% by weight. Moreover, it is preferable that the bath ratio of the reducing agent aqueous solution to process is set to 1: 5-30. Although uniform and economical treatment is possible within the range of the above bath ratio, if the bath ratio is less than 1: 5, it is very unevenly processed, and if it exceeds 1:30, it is not preferable because problems such as productivity decrease occur.
황화구리는 불용성이기 때문에 섬유에 직접 결합하기는 어렵다. 상기 제1처리 공정을 거쳐 다량의 카르복시기가 부여된 아크릴계 섬유는 수용성 구리 화합물로 처리하면 음이온인 카르복시기와 양이온인 구리 이온의 정전기적인 인력에 의해 구리 이온이 아크릴계 섬유에 흡착되어 구리 이온과 카르복시기간에 강한 배위결합을 형성하게 된다. Because copper sulfide is insoluble, it is difficult to bond directly to fibers. When the acrylic fiber imparted with a large amount of carboxyl group through the first treatment process is treated with a water-soluble copper compound, copper ions are adsorbed to the acrylic fiber by electrostatic attraction of anion carboxyl groups and cationically copper ions, which is resistant to copper ions and carboxy periods. Coordination bonds are formed.
이렇게 해서 구리 이온을 아크릴계 섬유 내부에 강하게 결합시킨 후 황을 포함하는 환원제를 사용하여 아크릴계 섬유를 처리하면 환원반응에 의해 황이 구리와 결합하여 섬유 내부에 황화구리 화합물이 형성되고, 결과적으로 섬유는 전도성을 띠게 되어 배터리 등에 의해 전기를 공급해주면 저항에 의해 열이 발생하게 되는 전기발열 기능이 부여된다.In this way, copper ions are strongly bound to the inside of the acrylic fiber and the acrylic fiber is treated using a reducing agent containing sulfur. Thus, sulfur is combined with copper by a reduction reaction to form a copper sulfide compound inside the fiber. When the electricity is supplied by a battery or the like, an electric heat generating function is generated in which heat is generated by a resistance.
아래에서 본 발명은 실시예를 기초로 하여 상세하게 설명한다. 제시된 실시예는 예시적인 것으로 본 발명의 범위를 제한하기 위한 것은 아니다.
In the following the present invention will be described in detail on the basis of examples. The examples presented are exemplary and are not intended to limit the scope of the invention.
실시예 1Example 1
아크릴 섬유(아크릴로니트릴 함량 85% 이상) 100g을 수산화나트륨 20g 및 구아니딘하이드로클로라이드 60g을 포함하는 수용액으로, 욕비 1:15로 하여 110℃에서 2시간 처리하여 가교반응시키고, 이 섬유를 다시 수산화나트륨 60g 및 구아니딘하이드로클로라이드 30g을 포함하는 수용액으로, 욕비 1: 15로 하여 100℃에서 2시간 처리하여 가수분해 반응시키는 제1처리 공정을 거쳤다. 이 섬유를 다시 황산제2구리 30g을 포함하는 수용액으로, 욕비 1:15로 하여 100℃에서 30분간 처리하여 구리이온을 흡착시키고, 다시 티오황산나트륨 30g 및 황산 6g을 포함하는 수용액으로, 욕비 1:15로 하여 90℃에서 2시간 처리하여 실시예 1의 섬유를 얻었다.
100 g of acrylic fiber (acrylonitrile content of 85% or more) is an aqueous solution containing 20 g of sodium hydroxide and 60 g of guanidine hydrochloride, crosslinked by treatment at 110 ° C. for 2 hours at a bath ratio of 1:15, and the fiber is again subjected to sodium hydroxide. An aqueous solution containing 60 g and 30 g of guanidine hydrochloride was subjected to a first treatment step of performing a hydrolysis reaction at 100 ° C. for 2 hours at a bath ratio of 1:15. The fiber was again treated with an aqueous solution containing 30 g of cupric sulfate, treated with a bath ratio of 1:15 at 100 ° C. for 30 minutes to adsorb copper ions, and again with an aqueous solution containing 30 g of sodium thiosulfate and 6 g of sulfuric acid. The fiber of Example 1 was obtained by making it into 15 and processing at 90 degreeC for 2 hours.
실시예 1의 섬유는 다음의 방법에 의해 웹 상태로 제조하여 흡습발열 성능과 전기발열 성능을 측정하였다.
The fiber of Example 1 was manufactured in the web state by the following method, and the hygroscopic and exothermic performance was measured.
<섬유웹 시료의 제조 방법> <Method for producing fiber web sample>
실시예 1에서 제조된 섬유를 개개의 섬유로 분리하여 물에 분산한 후, 여과지에 이를 통과시켜 물만 빠져나가도록 한 후 여과지 채로 건조하고 여과지 위에 형성된 섬유웹을 채취한다.
The fibers prepared in Example 1 are separated into individual fibers, dispersed in water, and passed through the filter paper so that only the water is drained, dried with filter paper, and the fibrous web formed on the filter paper is collected.
<흡습발열 성능 측정 방법> <Method for measuring hygroscopic heat generation performance>
상기 섬유웹 시료를 가로 2.5cm, 세로 5cm의 크기로 2개 절단하여 겹치고, 반으로 접은 후 가운데에 온도 센서를 부착하여 온도 34℃, 습도 10%RH의 저습 환경에 2시간 이상 방치한다. 다시 온도 34℃, 습도 90%RH의 고습 환경에 노출시켜 시간에 따른 섬유의 표면 온도를 측정하여 최대 온도와 초기 온도와의 차이를 흡습발열 성능으로 나타내었다.
The fibrous web samples are cut into two pieces of 2.5 cm long and 5 cm long, overlapped, folded in half, and then attached with a temperature sensor in the center, and left in a low humidity environment of 34 ° C. and a humidity of 10% RH for 2 hours or more. In addition, the surface temperature of the fiber was measured by exposing it to a high humidity environment having a temperature of 34 ° C. and a humidity of 90% RH, and the difference between the maximum temperature and the initial temperature was expressed as a hygroscopic heat generation performance.
<전기발열 성능 측정 방법> <Method of measuring heat generation performance>
20℃, 65%RH의 환경에서 상기 섬유웹 시료 표면에 온도 센서를 부착하고, 섬유웹에 전극을 연결하여 9V의 전기를 흘려주어 최대 표면 온도를 측정하여 초기 온도와의 차이를 전기발열 성능으로 나타내었다.
The temperature sensor is attached to the surface of the fibrous web sample at 20 ° C. and 65% RH, and an electrode is connected to the fibrous web to supply 9V of electricity to measure the maximum surface temperature. Indicated.
상기 방법으로 실시예 1의 섬유웹의 발열성능을 측정한 결과, 흡습발열 성능은 9.2℃였고, 전기발열 성능은 23.4℃ 였다. 따라서 이러한 결과를 통해 본 발명에 의해 제조된 발열섬유는 흡습발열 기능과 전기발열 기능을 동시에 가지고 있다는 것을 확인하였고, 두 가지 기술의 단점을 보완하고, 장점을 극대화할 수 있는 고효율 하이브리드 발열섬유의 제조가 가능하였다. The exothermic performance of the fibrous web of Example 1 was measured by the above method. As a result, the hygroscopic heat generation performance was 9.2 ° C, and the electric heat generation performance was 23.4 ° C. Therefore, through these results, it was confirmed that the exothermic fiber produced by the present invention has a hygroscopic heat generating function and an electric heat generating function at the same time, to manufacture the high efficiency hybrid heating fiber which can complement the disadvantages of the two technologies and maximize the advantages. Was possible.
Claims (7)
상기 제1처리 공정을 거친 아크릴계 섬유를 구리 화합물로 처리하는 구리이온 결합 단계 및 황을 포함하는 환원제로 처리하여 섬유 내부에 황화구리 화합물이 형성되도록 하는 환원반응 단계를 포함하는 제2처리 공정을 포함하는 흡습발열 기능과 전기발열 기능을 동시에 가진 발열 섬유의 제조 방법.A first treatment step including a crosslinking step of treating the acrylic fiber with a crosslinking agent and a hydrolysis step of hydrolyzing with an alkali to introduce a carboxyl group into the fiber; And
And a second treatment step including a copper ion bonding step of treating the acrylic fiber having undergone the first treatment step with a copper compound, and a reduction reaction step of forming a copper sulfide compound in the fiber by treating with a reducing agent including sulfur. Method for producing a heating fiber having a moisture-absorbing heat generating function and an electric heat generating function at the same time.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200057359A (en) | 2018-11-16 | 2020-05-26 | 주식회사 오라 | Electrical Heating Textile with Graphene/PVDF-HFP Composite by Various Circuit Pattering Conditions |
| KR102700637B1 (en) | 2023-06-13 | 2024-08-29 | 남용희 | Heat-generating Fiber And Method for Manufacturing the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100556711B1 (en) | 2004-11-17 | 2006-03-10 | 동일방직주식회사 | Acrylic hygroscopic heat-generating fiber product with excellent dyeability |
| KR100772056B1 (en) | 2006-11-28 | 2007-10-31 | 최환철 | Conductive acrylic fiber containing amide oxime group and its manufacturing method |
| KR100794086B1 (en) | 2001-01-26 | 2008-01-10 | 니혼 엑스란 고교 (주) | High-density hygroscopic fiber and method for producing such fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100794086B1 (en) | 2001-01-26 | 2008-01-10 | 니혼 엑스란 고교 (주) | High-density hygroscopic fiber and method for producing such fiber |
| KR100556711B1 (en) | 2004-11-17 | 2006-03-10 | 동일방직주식회사 | Acrylic hygroscopic heat-generating fiber product with excellent dyeability |
| KR100772056B1 (en) | 2006-11-28 | 2007-10-31 | 최환철 | Conductive acrylic fiber containing amide oxime group and its manufacturing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200057359A (en) | 2018-11-16 | 2020-05-26 | 주식회사 오라 | Electrical Heating Textile with Graphene/PVDF-HFP Composite by Various Circuit Pattering Conditions |
| KR102700637B1 (en) | 2023-06-13 | 2024-08-29 | 남용희 | Heat-generating Fiber And Method for Manufacturing the Same |
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