CN102440979A - Cellulose derivative composite membrane and preparation method thereof - Google Patents
Cellulose derivative composite membrane and preparation method thereof Download PDFInfo
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- CN102440979A CN102440979A CN2010102978881A CN201010297888A CN102440979A CN 102440979 A CN102440979 A CN 102440979A CN 2010102978881 A CN2010102978881 A CN 2010102978881A CN 201010297888 A CN201010297888 A CN 201010297888A CN 102440979 A CN102440979 A CN 102440979A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 61
- 239000001913 cellulose Substances 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 64
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 64
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims abstract description 15
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims abstract description 15
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims abstract description 15
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 12
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 12
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 12
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007766 curtain coating Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 6
- AXTGDCSMTYGJND-UHFFFAOYSA-N 1-dodecylazepan-2-one Chemical compound CCCCCCCCCCCCN1CCCCCC1=O AXTGDCSMTYGJND-UHFFFAOYSA-N 0.000 claims description 6
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 6
- 229940041616 menthol Drugs 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
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- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000003814 drug Substances 0.000 description 6
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- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 2
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- PVHUJELLJLJGLN-INIZCTEOSA-N (S)-nitrendipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OC)[C@@H]1C1=CC=CC([N+]([O-])=O)=C1 PVHUJELLJLJGLN-INIZCTEOSA-N 0.000 description 1
- TWBNMYSKRDRHAT-RCWTXCDDSA-N (S)-timolol hemihydrate Chemical compound O.CC(C)(C)NC[C@H](O)COC1=NSN=C1N1CCOCC1.CC(C)(C)NC[C@H](O)COC1=NSN=C1N1CCOCC1 TWBNMYSKRDRHAT-RCWTXCDDSA-N 0.000 description 1
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
- GJSURZIOUXUGAL-UHFFFAOYSA-N Clonidine Chemical compound ClC1=CC=CC(Cl)=C1NC1=NCCN1 GJSURZIOUXUGAL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
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- 229960002896 clonidine Drugs 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
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- 229960005309 estradiol Drugs 0.000 description 1
- 229930182833 estradiol Natural products 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- PJMPHNIQZUBGLI-UHFFFAOYSA-N fentanyl Chemical compound C=1C=CC=CC=1N(C(=O)CC)C(CC1)CCN1CCC1=CC=CC=C1 PJMPHNIQZUBGLI-UHFFFAOYSA-N 0.000 description 1
- 229960002428 fentanyl Drugs 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960005425 nitrendipine Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229960002646 scopolamine Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008337 systemic blood flow Effects 0.000 description 1
- 229960003604 testosterone Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229960004605 timolol Drugs 0.000 description 1
- 238000013271 transdermal drug delivery Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a cellulose derivative composite membrane which is mainly prepared from the following raw materials in parts by weight: 1-10 parts of cellulose hydrophilic derivative and 1-10 parts of polyvinyl alcohol, wherein the cellulose hydrophilic derivative is carboxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, and the polyvinyl alcohol is PVA05-88, PVA17-88 or a mixture of PVA05-88 and PVA 17-88. The invention has wide applicability to raw materials, and all cellulose derivatives having hydrophilic substituent groups can be applied to the invention. Therefore, the raw materials of the invention have wide sources. The cellulose derivative composite membrane has good light transmittance, swelling property and permeability. The invention has no irritation to skin, no sensitization or intradermal reaction, namely has good biocompatibility and safety, and the preparation method has the advantages of simple and convenient operation, stable process and low manufacturing cost.
Description
Technical field
The invention belongs to macromolecular material and learn field, particularly a kind of cellulose derivative transdermal composite membrane.
Background technology
Transdermal drug delivery system or transdermal formulation (being called for short TTS) refer to stick the mode medication through skin, and medicine gets into the systemic blood circulation by skin absorbs and reaches one type of preparation of effective blood drug concentration, realization disease treatment or prevention.Since first TTS-Scopolamine Patch is gone on the market in the U.S. in 1981, existing at present multiple transdermal absorption formulation, as: TTS such as nitroglycerin, estradiol, fentanyl, clonidine, testosterone, nitrendipine, timolol are applied to clinical being well received.China medicine scholar early has understanding to percutaneous dosing, in the medical science ancient books and records of China, has collected a large amount of plaster prescriptions local and the treatment internal disease that is used for.Internal diseases such as various forms of in recent years Chinese medicine external curing respiratory systems, cardiovascular system, gastrointestinal tract have been obtained certain achievement.And the key of Percutaneously administrable prepn is good carrier material and drug-supplying system.
Membrane has been because advantage such as easy to use has at present become a kind of important transdermal administration carrier, be widely used in oral, suck, Sublingual or mucosal drug delivery and the surperficial covering of skin trauma, burn or inflammation.The macromolecular polysaccharide that cellulose is made up of glucose, water insoluble and common organic solvents is a kind of polysaccharide that occurring in nature distributes the most extensively, content is maximum.Cellulose derivative is with the product behind the hydroxyl in the cellulose macromolecule and chemical reagent generation esterification or the etherification reaction.Through replacing the selection and the technological design of reagent; Make the cellulose derivative product can be water-soluble, dilute alkaline soln or organic solvent; Or have performances such as thermoplasticity; The cellulose soluble derivative has good dispersive property, emulsifying, thickening, bonding, film forming, water-retaining property; Have simultaneously and performance such as dissolve in superior water solublity, surface activity, stability, the organic solvent and excellent biological compatibility is widely used in life science and pharmaceutical field, many at present binding agent, wetting agent and disintegrating agents as medicament, and also be in the exploratory stage in the application of transdermal membrane.
Summary of the invention
The object of the present invention is to provide a kind of cellulose derivative composite membrane.
The technical scheme that the present invention adopts is following: a kind of cellulose derivative composite membrane; It is mainly processed by the raw material of following parts by weight: cellulose hydrophilic derivatives 1～10, polyvinyl alcohol 1～10; Said cellulose hydrophilic derivatives is carboxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methylcellulose, and said polyvinyl alcohol is the mixture of PVA05-88, PVA17-88 or PVA05-88 and PVA17-88.
The method for preparing of cellulose derivative composite membrane, its step is following:
(1) preparation quality concentration is 1～10% cellulose hydrophilic derivatives solution;
(2) preparation quality concentration is 1～10% poly-vinyl alcohol solution;
(3) the cellulose hydrophilic derivatives solution with 10～100 weight portions joins in the poly-vinyl alcohol solution of 10～100 weight portions, leaves standstill aerofluxus, treats that bubble drains, and solution coat or curtain coating are paved, and drying is processed the cellulose derivative composite membrane.
The substep The tape casting prepares the method for cellulose derivative composite membrane, and its step is following:
(1) preparation quality concentration is 1～10% cellulose hydrophilic derivatives solution, leaves standstill aerofluxus;
(2) preparation quality concentration is 1～10% poly-vinyl alcohol solution, leaves standstill aerofluxus;
(3) the cellulose hydrophilic derivatives solution with 10～100 weight portions prolongs coating film forming, dry, and curtain coating 10～100 weight account polyethylene alcoholic solutions on cellulose hydrophilic derivatives film again, drying is processed the cellulose derivative composite membrane.
The azone or the menthol that add 1～10 weight portion in the cellulose hydrophilic derivatives solution of said step (1).
The glycerol, sorbitol or the propylene glycol that add 1～10 weight portion in the poly-vinyl alcohol solution of said step (2).
The poly-vinyl alcohol solution of the cellulose hydrophilic derivatives solution of said step (1) and step (2) prepares under 2000～5000 rev/mins the condition at 25～60 ℃.
Beneficial effect of the present invention: the present invention has extensive applicability to raw material, and the cellulose derivative of all possess hydrophilic property substituted radicals all goes for the present invention.Therefore, raw material sources of the present invention very extensively.Cellulose derivative composite membrane of the present invention has good light transmittance, swellability and permeability.The present invention promptly has excellent biological compatibility and safety to skin nonirritant, no sensitization or intradermoreaction, and method for preparing has easy and simple to handle, process stabilizing, advantage cheap for manufacturing cost.
Performance test of the present invention can be known by Fig. 1 that shown in Fig. 1～3 composite membrane of different proportion carboxymethyl cellulose and polyvinyl alcohol preparation has transmittance preferably in visible wavelength, show that the compound cellulose film has good transparency, and outward appearance is good.Can know that by Fig. 2 the composite membrane of different proportion hydroxypropyl methylcellulose and polyvinyl alcohol preparation has good swellbility (minimum swellbility reaches more than 300%), shows that compound cellulose film water absorption is good, has resistance to water preferably, and is easy to use.Can know that by Fig. 3 the composite membrane of different proportion carboxymethyl cellulose and polyvinyl alcohol preparation shows that along with the prolongation of time has good transmitance the compound cellulose film has good permeability, helps the healing of trauma skin.
Description of drawings
Fig. 1 is the light transmittance (■: carboxymethyl cellulose: polyvinyl alcohol=1/9 of cellulose derivative composite membrane at different wave length; ◆: carboxymethyl cellulose: polyvinyl alcohol=3/7);
Fig. 2 is the water absorption (■: hydroxypropyl methylcellulose: polyvinyl alcohol=1/9 of cellulose derivative composite membrane; ◆: hydroxypropyl methylcellulose: polyvinyl alcohol=7/3);
Fig. 3 is the transmitance (■s: carboxymethyl cellulose: polyvinyl alcohol=1/9 of the different films of cellulose derivative composite membrane to xylenol orange; ◆: carboxymethyl cellulose: polyvinyl alcohol=3/7).
The specific embodiment
Embodiment 1
With the 1.0g carboxymethyl cellulose, the 2g azone adds in the 50g deionized water, and preparation quality concentration is 2% cmc soln, with the stirring of 3000rpm speed, 50 ℃ of heating for dissolving; With 2.5g polyvinyl alcohol (PVA05-88), 2g glycerol adds in the 50g water, and preparation quality concentration is 5% poly-vinyl alcohol solution, fully stirring and dissolving; Cmc soln is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, plane curtain coating coating film forming is drying to obtain the cellulose derivative composite membrane.
Embodiment 2
With the 3.0g hydroxypropyl cellulose, the 5g azone adds in the 60g deionized water, and preparation quality concentration is 5% hydroxypropyl cellulose solution, under the room temperature with 2000rpm speed stirring and dissolving; With 0.8g polyvinyl alcohol (PVA17-88), the 3g propylene glycol adds in the 40g water, and preparation quality concentration is 2% poly-vinyl alcohol solution, fully stirring and dissolving; Hydroxypropyl cellulose solution is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, curtain coating coating film forming on the plane is drying to obtain the cellulose derivative composite membrane.
Embodiment 3
With the 4.0g hydroxypropyl methylcellulose, the 5g menthol adds in the 40g deionized water, makes mass concentration and be 10% hydroxypropyl methylcellulose solution, under 25 ℃, with 4500rpm speed stirring and dissolving; With the 1.8g polyvinyl alcohol (PVA05-88: PVA17-88=1: 1, g/g) add in the 60g water, preparation quality concentration is 3% poly-vinyl alcohol solution, adds sorbitol 0.5g, fully stirring and dissolving; Hydroxypropyl methylcellulose solution is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, the curtain coating coating film forming is drying to obtain the cellulose derivative composite membrane in the plane.
Embodiment 4
With the 2.5g hydroxypropyl cellulose, the 4g menthol adds in the 50g deionized water, makes mass concentration and be 5% hydroxypropyl cellulose solution, with 3500rpm speed stirring and dissolving, leaves standstill aerofluxus; With the 2g polyvinyl alcohol (PVA05-88: PVA17-88=1: 2, g/g) add in the 50g water, preparation quality concentration is 4% poly-vinyl alcohol solution, fully stirring and dissolving leaves standstill aerofluxus; Adopt the substep The tape casting to prepare composite membrane, get hydroxypropyl cellulose solution casting film-forming on flat board of 5%, room temperature is air-dry, and the painting polyethylene alcoholic solution is drying to obtain the cellulose derivative double-layered compound film above that.
Embodiment 5
With the 5.0g carboxymethyl cellulose, the 5g azone adds in the 50g deionized water, and preparation quality concentration is 10% cmc soln, with the stirring of 3000rpm speed, 30 ℃ of heating for dissolving; With 5.0g polyvinyl alcohol (PVA05-88), 2g glycerol adds in the deionized water, and preparation quality concentration is 10% poly-vinyl alcohol solution, fully stirring and dissolving; Cmc soln is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, plane curtain coating coating film forming is drying to obtain the cellulose derivative composite membrane.
Embodiment 6
With the 3.0g hydroxypropyl cellulose, the 5g azone adds in the 60g deionized water, and preparation quality concentration is 5% hydroxypropyl cellulose solution, under the room temperature with 2000rpm speed stirring and dissolving; With 2g polyvinyl alcohol (PVA 17-88), the 3g propylene glycol adds in the 40g deionized water, abundant stirring and dissolving, and preparation quality concentration is 5% poly-vinyl alcohol solution; Hydroxypropyl cellulose solution is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, curtain coating coating film forming on the plane is drying to obtain the cellulose derivative composite membrane.
Embodiment 7
With the 0.4g hydroxypropyl methylcellulose, the 5g menthol adds in the 40g deionized water, makes mass concentration and be 10% hydroxypropyl methylcellulose solution, under 25 ℃, with 4500rpm speed stirring and dissolving; With the 6g polyvinyl alcohol (PVA05-88: PVA17-88=1: 1, g/g) add in the 60g water, preparation quality concentration is 10% poly-vinyl alcohol solution, adds sorbitol 0.5g, fully stirring and dissolving; Hydroxypropyl methylcellulose solution is slowly added poly-vinyl alcohol solution, stirring and evenly mixing; Leave standstill aerofluxus, treat that bubble drains, the curtain coating coating film forming is drying to obtain the cellulose derivative composite membrane in the plane.
Embodiment 8
With the 0.5g hydroxypropyl cellulose, the 4g menthol makes mass concentration and is 1% hydroxypropyl cellulose solution, with 3500rpm speed stirring and dissolving, leaves standstill aerofluxus; With the 0.5g polyvinyl alcohol (PVA05-88: PVA17-88=1: 2, g/g), 3g glycerol adds in the 50g deionized water, makes mass concentration and be 1% poly-vinyl alcohol solution, fully stirring and dissolving leaves standstill aerofluxus; Adopt the substep The tape casting to prepare composite membrane, get hydroxypropyl cellulose solution casting film-forming on flat board, room temperature is air-dry, and the painting polyethylene alcoholic solution is drying to obtain the cellulose derivative double-layered compound film above that.
Claims (6)
1. cellulose derivative composite membrane; It is characterized in that: it is mainly processed by the raw material of following parts by weight: cellulose hydrophilic derivatives 1～10, polyvinyl alcohol 1～10; Said cellulose hydrophilic derivatives is carboxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methylcellulose, and said polyvinyl alcohol is the mixture of PVA05-88, PVA17-88 or PVA05-88 and PVA17-88.
2. the method for preparing of cellulose derivative composite membrane as claimed in claim 1 is characterized in that: its step is following:
(1) preparation quality concentration is 1～10% cellulose hydrophilic derivatives solution;
(2) preparation quality concentration is 1～10% poly-vinyl alcohol solution;
(3) the cellulose hydrophilic derivatives solution with 10～100 weight portions joins in the poly-vinyl alcohol solution of 10～100 weight portions, leaves standstill aerofluxus, treats that bubble drains, and solution coat or curtain coating are paved, and drying is processed the cellulose derivative composite membrane.
3. the method for preparing of cellulose derivative composite membrane as claimed in claim 1 is characterized in that: its step is following:
(1) preparation quality concentration is 1～10% cellulose hydrophilic derivatives solution, leaves standstill aerofluxus;
(2) preparation quality concentration is 1～10% poly-vinyl alcohol solution, leaves standstill aerofluxus;
(3) the cellulose hydrophilic derivatives solution with 10～100 weight portions prolongs coating film forming, dry, and curtain coating 10～100 weight account polyethylene alcoholic solutions on cellulose hydrophilic derivatives film again, drying is processed the cellulose derivative composite membrane.
4. according to the method for preparing of claim 2 or 3 described cellulose derivative composite membranes, it is characterized in that: the azone or the menthol that add 1～10 weight portion in the cellulose hydrophilic derivatives solution of said step (1).
5. according to the method for preparing of claim 2 or 3 described cellulose derivative composite membranes, it is characterized in that: the glycerol, sorbitol or the propylene glycol that add 1～10 weight portion in the poly-vinyl alcohol solution of said step (2).
6. according to the method for preparing of claim 2 or 3 described cellulose derivative composite membranes; It is characterized in that: the poly-vinyl alcohol solution of the cellulose hydrophilic derivatives solution of said step (1) and step (2) prepares under 2000～5000 rev/mins the condition at 25～60 ℃.
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| CN102827441A (en) * | 2012-06-30 | 2012-12-19 | 安徽安生生物化工科技有限责任公司 | Cooling gel sheet |
| CN103172886A (en) * | 2013-03-14 | 2013-06-26 | 南京林业大学 | Method for quickly preparing colorful nanocrystalline cellulose film |
| CN105037760A (en) * | 2013-04-27 | 2015-11-11 | 湖州展望天明药业有限公司 | Preparation method of cellulose nanofiber flexible transparent films |
| CN107090150A (en) * | 2017-03-22 | 2017-08-25 | 汪家秀 | The rice-straw fibre doping preservative film and its preparation technology of a kind of gelatin coatings |
| CN108244155A (en) * | 2018-01-11 | 2018-07-06 | 日照职业技术学院 | A kind of antiseptic and antibiotic packaging material prepared based on microbial method |
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