CN202492626U - Textile fiber - Google Patents
Textile fiber Download PDFInfo
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- CN202492626U CN202492626U CN2011203700680U CN201120370068U CN202492626U CN 202492626 U CN202492626 U CN 202492626U CN 2011203700680 U CN2011203700680 U CN 2011203700680U CN 201120370068 U CN201120370068 U CN 201120370068U CN 202492626 U CN202492626 U CN 202492626U
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Abstract
The utility model relates to a textile, and particularly relates to a textile fiber with inlaid heat storing microcapsules inside the fiber and/or on the fiber surface. The textile fiber has a heat storing function, is suitable for use in textile fibers of various fabrics, can not only ensure inherent characteristics of the fabric fibers, but also have thermal insulation and heat storing functions.
Description
Technical field
The utility model relates to textile fabrics, specifically a kind of textile fabric.
Background technology
Now, the textile fabrics in the society is of a great variety, and the lining that adopts more and more especially, can satisfy all kinds of crowds' needs; But, to reduce a lot relatively for the kind of insulation textile fabrics, and have multiple lining not have heat insulation function, so just limited its application, can not satisfy people for many-sided requirements such as comfort level, cost, durability.
The utility model content
The utility model provides a kind of textile fabric with heat accumulation function.In the textile fabric applicable to multiple lining, can guarantee the characteristic of face liber itself, have the thermal isolation and heat storage function simultaneously again.
For realizing above-mentioned purpose, the technical scheme that the utility model adopts is:
A kind of textile fabric is inlaid with the accumulation of heat microcapsules at fibrous inside and/or fiber surface.
Said microcapsules are for being shell material with synthesized polymer material or natural macromolecular material; Can accomplish a kind of in the lyophobic dust of solid-liquid phase transformation during with variations in temperature between-50 to 100 ℃ or be mixed into core more than two kinds, core and shell material mass ratio are 100: the accumulation of heat microcapsules of 5-50.
Fibre diameter is the 6-15 micron, and the microcapsules particle diameter is at the 1-5 micron.
Said microcapsules are for being shell material with synthesized polymer material or natural macromolecular material, can accomplish a kind of in the lyophobic dust of solid-liquid phase transformation during with variations in temperature between-50 to 100 ℃ or be mixed into core more than two kinds; Core and shell material mass ratio are 100: the accumulation of heat microcapsules of 5-50.
Said synthesized polymer material is: the weight average molecular weight of monomer polymerization is polystyrene, nylon or the Polyurethane of 6000-300000; Weight average molecular weight in prepolymer or the polymer is phenolic resins, epoxy resin or the aminoplast of 6000-300000;
Said natural macromolecular material is that weight average molecular weight is gelatin or the shitosan of 1000-100000;
Core is a carbon number at the alkane of 5-36, carbon number higher aliphatic, chlorocarbon, animal oil or the vegetable oil at 4-36.
The outer shell material of said microcapsules is a 2-8 layer shell material layer, and the shell material that 2-8 layer shell material layer is adopted can be identical or different.
The production method of said heat-storing material microencapsulation: adopt method of emulsion polymerization, in agitated reactor, with crosslinking agent and/or emulsifiers dissolve in water; Make system temperature be raised to the core fusing point to the condition that is higher than 30 ℃ of core fusing points, add core and the raw material that generates shell material, the volume ratio of water and core is 1: 0.5-0.95; Wherein core is 100 with the mass ratio that generates the shell material raw material: 5-50, carry out emulsification pretreatment, and examine under a microscope the particle diameter 0.5-15 micron of core; Be that emulsification is accomplished; Add curing agent or initator, add the reaction temperature that is warming up to the shell material stock yard after finishing and be incubated 0.5-5 hour, get product.
Said shell material is a nylon, it adopts acyl chloride material and carboxylated compound to make the crosslinking agent prepared in reaction; Acyl chloride material and carboxylated compound mass ratio 1: 0.5-20; Said acyl chloride material is adipyl chlorine, terephthalyl chloride, uncle's diacid chloride, sebacoyl chloride, azelaoyl chloride, o-phthaloyl chloride, acyl chlorides dimer or acyl chlorides trimer; Carboxylated compound is an amino acid; Make initator with benzoyl peroxide, addition is the 3%-10% of acyl chloride quality of materials;
Said shell material is a polyurethane, and it adopts the macromolecule crosslink agent of multi-functional isocyanates and hydroxyl and/or macromolecule emulsifier is the raw material reaction preparation; The macromolecule crosslink agent of multi-functional isocyanates and hydroxyl and/or macromolecule emulsifier mass ratio 1: 5-20; Said multi-functional isocyanates is toluene di-isocyanate(TDI) or oneself two cyanates; The macromolecule crosslink agent of hydroxyl and/or macromolecule emulsifier are polyvinyl alcohol, methylcellulose, HES or hydroxypropul starch; The employing initator is an ethylenediamine, and its addition is the 0.5-5% of crosslinking agent and/or emulsifying agent gross mass;
Said shell material is an epoxy resin, and it adopts polyamine is the curing agent prepared in reaction; Epoxide and polyamine mass ratio 100: 5-40; Said polyamine is ethylenediamine, hexamethylene diamine, dicyandiamide, triethylene tetramine, diethylaminopropylamine or trimethyl hexamethylene diamine phenolic resins; Adopting the trade mark is that 1799 polyvinyl alcohol is made emulsifying agent and coalescents, and its addition is the 1-20% of shell material raw materials quality;
Said shell material is a phenolic resins, and it adopts phenol and aldehyde is the raw material reaction preparation, and the mol ratio of phenol and aldehyde is 1: between the 1.1-3; Said phenol is oil-soluble alkyl phenol or water-soluble polyhydroxy phenol; Aldehyde be formaldehyde, glyoxal, glutaraldehyde or furfural, adopting the trade mark is that 1799 polyvinyl alcohol is made emulsifying agent and coalescents, its addition is the 1-20% of shell material raw materials quality; Adopting inorganic acid or organic acid is initator, regulation system PH0.5-6;
Said shell material is an aminoplast; It adopts weight average molecular weight is 3000-150000 Lauxite, melamine resin, be raw material through Lauxite that contains methylol behind the etherification reaction or the melamine resin that behind etherification reaction, contains methylol, and contain carboxyl or sulfonic compound and do the crosslinking agent reaction and generate aminoplast; Containing carboxyl or sulfonic compound is dodecyl sodium sulfate, lauryl sodium sulfate, ethylene methacrylic-Ma Lai acid anhydride copolymer, isobutene-styrene-Ma Lai acid anhydride copolymer, styrene-Ma Lai acid anhydride copolymer, Sodium Polyacrylate or sodium polymethacrylate; Its addition is the 10-50% of shell material raw materials quality; Adopting inorganic acid or organic acid is initator, regulation system PH4-6;
Said shell material is a polystyrene, and it adopts styrene and contains carboxyl or sulfonic compound is made crosslinking agent and/or emulsifying agent prepared in reaction; Styrene with contain carboxyl or sulfonic compound mass ratio 1: 5-20; Containing carboxyl or sulfonic compound is dodecyl sodium sulfate, lauryl sodium sulfate, ethylene methacrylic-Ma Lai acid anhydride copolymer, isobutene-styrene-Ma Lai acid anhydride copolymer, styrene-Ma Lai acid anhydride copolymer, Sodium Polyacrylate or sodium polymethacrylate; The employing initator is potassium peroxydisulfate, ammonium persulfate or benzoyl peroxide, and its addition is the 0.5-5% of crosslinking agent and/or emulsifying agent gross mass.
Emulsion process is through stirring high-shear emulsifying under high-shear emulsion machine on-line velocity >=20 meter per second conditions; During linear velocity 20-40 meter per second, can obtain＞microcapsules of 1-20 micron grain size; During linear velocity＞40-60 meter per second, can obtain the microcapsules of 500 nanometers-1 micron grain size.
Said fiber is synthetic fiber or regenerated fiber; Synthetic fiber are acrylic fibers, polyvinyl, terylene, polyamide fibre, spandex or polypropylene fibre, and regenerated fiber is claimed regeneration again
CelluloseFiber, it is a viscose.
Having the heat accumulation function textile fabric, to prepare process following: the accumulation of heat microcapsules that in the spinning solution of preparation synthetic fiber or regenerated fiber, are added with the particle diameter 1-5 micron of fibrous raw material quality 4-8%; Spinning solution is extruded or is sprayed from the spinneret orifice of spinning machine; Solidificating fiber is enclosed with the accumulation of heat microcapsules or is bonded with the accumulation of heat microcapsules at fiber surface at fibrous inside.
The process of preparation synthetic fiber or regenerated fiber adopts melt spinning, wet spinning or dry spinning.
The utility model product can through knitting or woven, process the textile fabrics that is used for satisfying demands such as people's health is warming, dress ornament, home decoration.The heat insulating products cost is high in order to solve, expensive problem, and lining can be various simultaneously, can enrich the kind of textile fabrics, both kept the various special performances of existing fibre, can embody the good characteristics of thermal isolation and heat storage again.Thereby make fabric not only greatly reduce product cost, improved wearability, and further expanded the application space of fiber product.
Description of drawings
Fig. 1 is the utility model structural representation, and 1 is the accumulation of heat microcapsules among the figure, and 2 is fiber.
The specific embodiment
The process that the utility model prepares regenerated fiber adopts wet spinning; With the bamboo fibre in the native cellulose, cotton fiber, xylon, flax fibre, Chinese alpine rush fiber, cellulose fibre is a kind of or be raw material more than two kinds, processes soluble cellulose through alkalization, aging, sulfonation operation
Sulphonic acid ester, be dissolved in sig water again and process viscose glue, warp
Wet spinningAnd process.
Be specially:
The raw material of producing viscose is a kind of in bamboo fibre, cotton fiber, xylon, flax fibre, Chinese alpine rush fiber or the cellulose fibre or more than two kinds.
Fibrous raw material is dropped in the container, is to soak 1-3 hour in the NaOH liquid of 10%-50% in mass concentration, and soaking temperature is 20 ℃-99 ℃.Drop into pulverizer then and be ground into slurry; After sulfonation is handled, carrying out homogeneous again disperses, grinds; Sulfonation liquid is made up of carbon disulfide and NaOH; The quality of carbon disulfide accounts for the 5%-10% of total sulfonated liquid quality, and the quality of NaOH accounts for the 0.1%-5% of gross mass, and remainder is a deionized water.The temperature of sulfonation liquid is 20 ℃-55 ℃, and the sulfonation time is 2-4 hour; With viscose in proportion input, viscose and the mass ratio that spins liquid in advance be 1: 1.5-2.5; Fully mix; Viscose is composite by NaOH and the deionized water of the cellulose of mass content 7%-10% and mass content 2-7%; Use 2000 orders-5000 purpose screen filtration again, remove thick component not up to standard and promptly get viscose and spin liquid in advance.
This is spun liquid in advance drops in the spinning container; The 4%-8% that presses the fibrous raw material quality drop into particle diameter the 0.5-5 micron, accumulation of heat microcapsules powder or solid content at the liquid heat storage microcapsules 35% or more, just when dropping into body accumulation of heat at night microcapsules, should stir by the mass range interpolation of contained oven-dry weight; Left standstill 20-40 minute; The bubble in the liquid is spun in cancellation in advance, under 40 ℃-99 ℃, 0.2-3Kpa pressure, carries out viscose glue accumulation of heat fibre spinning then, and spun silk carries out the typing of first road through coagulating bath to be handled; Coagulating bath is composite by the sulfuric acid and the deionized water of the chemical pure level of every liter of 100-150 gram; The temperature of coagulating bath is 40 ℃-60 ℃, and traction is carried out the typing of second road after twining receipts again, and the coagulating bath of second road typing is composite by every liter of 100-400 gram chemical pure agent sulfuric acid and deionized water; The temperature of coagulating bath is 40 ℃-70 ℃, and promptly getting diameter is the viscose glue accumulation of heat fiber first product of 6-15 micron.Through pickling, desulfurization, washing, bleaching, shredding, oven dry, promptly get required viscose glue accumulation of heat fibrous finished product again.
Embodiment 1
The preparation of accumulation of heat microcapsules: with nylon is the shell material, and n-dodecanol is the accumulation of heat microcapsules production method of core.
1, at 1M
3Agitated reactor in 400 kilograms of cores are added, be heated to 24-30 ℃, after making it to melt fully, this coils 20 5 kilograms to add surfactant, 50 kilograms of adipyl chlorine mix.
2, at 2M
3Agitated reactor in add 400 kilograms of deionized waters, lysine salt fully stirs for 8 kilograms, regulation system PH is warmed up to 25-30 ℃ between 8-9.In will 1. adding 2.; Open high-shear emulsion machine core is carried out emulsification, after examining under a microscope particle diameter and reaching the 2-4 micron, add 10 kilograms of (hexamethylene diamines: water=1: 1) be warmed up between 40-80 ℃ of the hexamethylene diamine aqueous solution; Be incubated 1-5 hour, promptly get required product.
Preparation with textile fabric of heat accumulation function:
1) raw material of production viscose is a bamboo fibre:
Fibrous raw material is dropped in the container, is to soak 2 hours in 30% the NaOH liquid in mass concentration, and soaking temperature is 60 ℃.Drop into pulverizer then and be ground into slurry; After sulfonation is handled, carry out homogeneous again and disperse, grind, sulfonation liquid is made up of carbon disulfide and NaOH, and the quality of carbon disulfide accounts for 8% of total sulfonated liquid quality; The quality of NaOH accounts for 2% of gross mass, and remainder is a deionized water.The temperature of sulfonation liquid is 40 ℃, and the sulfonation time is 3 hours; Input, viscose and the mass ratio that spins liquid in advance are 1: 2 in proportion with viscose; Fully mix; Viscose is composite by the NaOH and the deionized water of the cellulose of mass content 8% and mass content 5%; Use 4000 purpose screen filtrations again, remove thick component not up to standard and promptly get viscose and spin liquid in advance.
This is spun liquid in advance drop in the spinning container, press 6% of fibrous raw material quality and drop into the accumulation of heat microcapsules powder of particle diameter, stir in the preparation of 0.5-2 micron, moisture 6%; Left standstill 30 minutes; The bubble in the liquid is spun in cancellation in advance, under 50 ℃, 1Kpa pressure, carries out viscose glue accumulation of heat fibre spinning then, and spun silk carries out the typing of first road through coagulating bath to be handled; Coagulating bath is composite by the sulfuric acid and the deionized water of the chemical pure level of every liter 120 gram; The temperature of coagulating bath is 50 ℃, and traction twines carries out the typing of second road after the receipts again, and the coagulating bath of second road typing is composite by every liter 300 gram chemical pure agent sulfuric acid and deionized water; The temperature of coagulating bath is 60 ℃, and promptly getting diameter is the viscose glue accumulation of heat fiber first product of 9-12 micron.Through pickling, desulfurization, washing, bleaching, shredding, oven dry, promptly get required viscose glue accumulation of heat fibrous finished product again.
Be with embodiment 1 difference:
The preparation of accumulation of heat microcapsules: with the polystyrene is the shell material, and modified paraffin is done the accumulation of heat microcapsules production method of core.
(1), at 1M
3Agitated reactor in to add phase transition temperature be 35 ℃ 300 kilograms of modified paraffins, be warmed up to 35 ℃-40 ℃, after making it fully to dissolve, add 30 kilograms of styrene monomers, 6 kilograms of hydroxy propyl methacrylates, benzoyl peroxide fully stirs for 3 kilograms.
(2), at 2M
3Add 240 kilograms of deionized waters, 80 kilograms of content in the agitated reactor and be sodium salt solution, 10 kilograms of sodium polymethacrylates, 1 kilogram of lauryl sodium sulfate of 8% styrene-maleic anhydride copolymer, be warmed up to 45-65 ℃, will 1. add 2.; Start high-shear emulsion machine and carry out emulsification; After examining under a microscope average grain diameter and reaching 4 microns, be warmed up to 74-80 ℃, drip ammonium persulfate aqueous solution 20-30 kilogram with 1: 0.5 dilution proportion; Be incubated 4-15 hour, promptly get required product.
Preparation with textile fabric of heat accumulation function: the raw material of producing viscose is a cotton fiber, presses 5% of fibrous raw material quality and drops into the accumulation of heat microcapsules powder of particle diameter in the preparation of 2-5 micron, moisture 10%.
The accumulation of heat microcapsules are used for the embodiment of melt spinning:
One, melt prepares equipment: single screw rod or twin-screw ((multiscrew) extruder.
Two, melt spinning material:
A, this technology are applicable to fusing point at the melt spinning of 340 degree with interior all material, and the most frequently used has: polyester (terylene thread), polyamide (nylon yarn) or polypropylene (polypropylene fibre) etc.
B, moisture are not more than 2/1000ths powder accumulation of heat microcapsules.
(1) at 1M
3The epoxy resin E-51 that adds 20 kilograms in the agitated reactor slowly adds 500 kilograms of the positive hexadecanols of core after being heated to 50 ℃, and the HLB value stirs 5 kilograms of the non-ionic surface active agents below 4.
(2) at 2M
3Add 400 kg of water in the agitated reactor, contain 260 kilograms of the aqueous solution of 7% methylcellulose, make the system pH value between 2-4, temperature between 45-55 ℃, 10 kilograms of TX-10 of adding under stirring condition.After (1) material is joined in (2) material, under stirring condition, open high-shear emulsion machine and make linear velocity reach 35 meter per seconds, core is carried out emulsification; Examine under a microscope after average grain diameter reaches 2 microns; Slowly add the hexamethylene diamine 4-8 kilogram that diluted with 1: 1 deionized water, under 75-90 ℃ of condition, be incubated 0.5-2 hour, then system temperature is dropped to below 60 ℃; 200 kilograms of sodium salt solutions that under stirring condition, in system, add the styrene-maleic anhydride copolymer of solid content 7%; Solid content is 60 kilograms in 50% amino resins, and the regulation system pH value is warmed up to 70-95 ℃ between 4-5; Be incubated 1-3 hour, promptly being able to epoxy resin is the microcapsule product of shell for inner casing amino resins.
Implementing process (this implementing process is melt material with the polyester):
1, earlier with the oven dry of melt material polyester, removes moisture content.Dry the back that also should clean up that the ash content of coal is high;
2, the melt material with oven dry gets into screw extruder through tremie pipe, under 290 ℃ of-298 ℃ of conditions, carries out fusion and forms spinning melt, gets into spinning manifold through the melt pipeline again.The mode that adds powder accumulation of heat microcapsules has three kinds: can add tremie pipe (adopting this kind mode at this) with melt material, also can after forming spinning melt, add in the melt pipeline or directly add and lean on the mixing arrangement of special preparation that powder accumulation of heat microcapsules and spinning melt are mixed in the spinning manifold.The addition of powder accumulation of heat microcapsules is the 4%-15% (is 8% at this) of spinning melt quality.
3, the spinning melt that contains powder accumulation of heat microcapsules is stable, even, quantitative from the spinnerets even tow of ejection formation downwards thread continuously under the speed with per minute 500-4000 (is 3000 at this) rice under the pressure of 6-15 (is 9 at this) KPa through spinning pump.
4, from the tow thread of spinnerets ejection crosswind wind speed 0.3-0.8 (is 0.6 at this) rice/minute, the crosswind wind-warm syndrome is 20-40 ℃ (is 30 ℃ at this), crosswind rheumatism is solidified into the fibre bundle that contains heat storage performance under the condition of 40%-75% (is 60% at this).
5, the fibre bundle that forms; Guiding through positioning disk; At the heat-stretching roller drafting multiple is 2.5-4.5 (is 3 times at this) times; Drawing temperature is 35 ℃-75 ℃ (are 50 ℃ at this), and heat setting temperature is that drafting forming promptly gets the accumulation of heat fiber filament that diameter is the 6-15 micron under the condition of 80 ℃-100 ℃ (are 90 ℃ at this).
The accumulation of heat microcapsules are used for the embodiment of solvent spinning
One, fiber production equipment: spinning machine is by measuring pump, duplex heater, spinning shaft, compositions such as traction feeding machine, spinning nitrogen circulation air flow system.
Two, solvent spinning material: spinning solution is provided by raw materials producers.
Three, use solid content be not less than 35% liquid heat storage microcapsules or powder accumulation of heat microcapsules all can, its addition is for amounting to into after the accumulation of heat microcapsules oven-dry weight 4%-15% by high polymer in the spinning solution (forming the material of acrylic fiber) solid content.
At 2M
3Add 300 kg of water in the agitated reactor, being warmed up to and dropping into phase transition temperature after 30 ℃ successively is 24 ℃ 500 kilograms of core fatty acid monomers, 150 kilograms in the amino resins of solid content 50%; 200 kilograms of the phenylethylene-maleic anhydride salting liquids of solid content 10%, 5 kilograms of the neopelexes of solid content 1% make system remain on 30-60 ℃; Fully opening high-shear emulsion machine under the stirring condition, linear velocity is examined under a microscope after the core average grain diameter reaches 3 microns more than 30 meter per seconds; The pH value of regulation system is between 4-5; System is warmed up between 70-95 ℃, is incubated 2-5 hour, add the material to remove free formaldehyde such as urea, Jiao (Asia) phosphate, sulphite etc. then; 70-95 ℃ of insulation 25 minutes, promptly get required product.
Implementing process (this implementing process produced acrylic fiber spinning solution be the main material of solvent spinning)
1. in head tank, drop into spinning solution; The final high polymer solid content (is 32% at this) between 30%-36% that forms acrylic fiber in this stoste; Drop into solid content again and be not less than 35% liquid (is 36% at this) accumulation of heat microcapsules or accumulation of heat powder microcapsules; Drop into quality and amount to into oven-dry weight and calculate, should be in spinning solution (is 10% at this) between the 4%-15% of high polymer quality, mix, be the spinning solution that contains the accumulation of heat microcapsules.(annotate: dry spinning is identical with the adding method of accumulation of heat microcapsules in the wet spinning)
2. the spinning solution for preparing leaves standstill through 20-40 minute (is 30 minutes at this), to eliminate wherein bubble.Again through booster pump entering spinning machine under the pressure of 0.5-2KPa (is 1KPa at this).Synergy through measuring pump and duplex heater; Spinning solution is remained on evenly extrude from spinnerets continuously under 75 ℃-95 ℃, the pressure (is 85 ℃, 1KPa at this) of 0.5-2KPa and form the stoste thread; Get into spinning shaft; It is that the high temperature nitrogen of 350 ℃-420 ℃ (are 400 ℃ at this) makes solvent and water evaporates in the stoste thread that temperature is arranged in the path; Cause the superpolymer concentration in the stoste thread to increase, reach critical when solidifying concentration, the stoste thread just is cured as strand, and to form the diameter with heat storage performance be the nascent acrylic fiber of 6-15 micron.
3. the washing hauling machine guiding of outlet gets into spray, cooling, washing procedure to this as-spun fibre through the path again, gets product---accumulation of heat acrylic fiber long filament.
Claims (2)
1. a textile fabric is characterized in that: be inlaid with the accumulation of heat microcapsules at fibrous inside and/or fiber surface.
2. according to the said textile fabric of claim 1, it is characterized in that:
Fibre diameter is the 6-15 micron, and the microcapsules particle diameter is at the 1-5 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011203700680U CN202492626U (en) | 2011-09-29 | 2011-09-29 | Textile fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011203700680U CN202492626U (en) | 2011-09-29 | 2011-09-29 | Textile fiber |
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| Publication Number | Publication Date |
|---|---|
| CN202492626U true CN202492626U (en) | 2012-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011203700680U Expired - Fee Related CN202492626U (en) | 2011-09-29 | 2011-09-29 | Textile fiber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696096A (en) * | 2015-07-03 | 2016-06-22 | 怀宁县宝友工贸有限公司 | Temperature adjustable fabric |
| CN108499497A (en) * | 2018-04-18 | 2018-09-07 | 济南圣泉集团股份有限公司 | A kind of graphene microcapsules, intelligent temperature adjusting fiber and preparation method thereof |
| CN109805479A (en) * | 2017-11-21 | 2019-05-28 | 唐山宇慈生物科技有限公司 | Wearable edible biological polyoses fiber cotton material and preparation method thereof |
| CN114941196A (en) * | 2022-03-30 | 2022-08-26 | 绍兴市劲松针纺有限公司 | Fragrant fabric production process |
-
2011
- 2011-09-29 CN CN2011203700680U patent/CN202492626U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696096A (en) * | 2015-07-03 | 2016-06-22 | 怀宁县宝友工贸有限公司 | Temperature adjustable fabric |
| CN109805479A (en) * | 2017-11-21 | 2019-05-28 | 唐山宇慈生物科技有限公司 | Wearable edible biological polyoses fiber cotton material and preparation method thereof |
| CN108499497A (en) * | 2018-04-18 | 2018-09-07 | 济南圣泉集团股份有限公司 | A kind of graphene microcapsules, intelligent temperature adjusting fiber and preparation method thereof |
| CN114941196A (en) * | 2022-03-30 | 2022-08-26 | 绍兴市劲松针纺有限公司 | Fragrant fabric production process |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121017 Termination date: 20150929 |
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| EXPY | Termination of patent right or utility model |