CN110863264B - Preparation method of degradable superfine fiber based tea packaging material - Google Patents

Preparation method of degradable superfine fiber based tea packaging material Download PDF

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CN110863264B
CN110863264B CN201910970533.5A CN201910970533A CN110863264B CN 110863264 B CN110863264 B CN 110863264B CN 201910970533 A CN201910970533 A CN 201910970533A CN 110863264 B CN110863264 B CN 110863264B
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solution
fiber
potato starch
preparation
spinning
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CN110863264A (en
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李祥龙
杨斌
侯腾
许丹
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Zhejiang Sci Tech University ZSTU
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Zhejiang Sci Tech University ZSTU
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/123—Polyaldehydes; Polyketones
    • 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
    • D06M13/10—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 oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a micro-nano material preparation technology, and aims to provide a preparation method of a degradable superfine fiber based tea packaging material. The method comprises the following steps: respectively preparing a potato starch solution and a polyvinyl alcohol aqueous solution, and continuously adding a plasticizer after mixing; continuously stirring the mixed solution for 2 hours under the condition of 50 ℃ water bath to obtain spinning solution; preparing a fiber membrane by a centrifugal spinning method; crosslinking the fiber membrane with a crosslinking agent at 130 ℃; and moving the fiber to a hot rolling mill for hot rolling treatment to obtain the degradable fiber-based packaging material. The invention uses starch and polyvinyl alcohol as spinning raw materials, the preparation method is simple and easy, the process conditions are easy to realize, and the starch is used as the main component, so the cost is low, and the invention is an ideal material for replacing filter paper type tea bags with large energy consumption and complex production process. The prepared superfine fiber has good degradability and biocompatibility, and is an ideal material for replacing most of the existing non-woven tea bags prepared from non-degradable synthetic polymers.

Description

Preparation method of degradable superfine fiber based tea packaging material
Technical Field
The invention relates to a micro-nano material preparation technology, in particular to a preparation method of a degradable superfine fiber based tea packaging material.
Background
Throughout history, tea is always the mainstream drink in many countries and regions, and is popular and loved by consumers at home and abroad. In recent years, tea consumption is newly developed in many countries, the consumption field is continuously expanded, and the consumption mode and the consumption group are increasingly diversified. Today, with the greatly improved living standard of people, the selection of tea products in different age groups is quite different. For example, young populations tend toward tea beverages, while middle aged and elderly populations tend toward tea products of fashion, premium, and health preserving types.
The tea packaging material is vital to the development of tea products, and the main packaging forms of the tea packaging material are metal can packaging, carton packaging, plastic forming container packaging, paper bag packaging and the like. Paper bag packaging is favored in the market due to its advantages of being lightweight and portable, quick to brew, clean and sanitary, and convenient to remove residue. At present, tea packaging bags used at home and abroad mainly comprise filter paper and non-woven fabrics, have the defects of complicated production process, serious pollution, no degradability, biocompatibility and the like, and have the danger of harming human health. On the other hand, with the gradual improvement of living standard, people's demand for tea bags is further expanded, and further green and edible new requirements are also provided for the tea bags. Therefore, the development of a novel green and environment-friendly teabag is a necessary way for further meeting the needs of people.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a degradable superfine fiber based tea packaging material.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the degradable superfine fiber based tea packaging material comprises the following steps:
(1) preparation of the spinning dope
Respectively preparing a potato starch solution with the mass percentage concentration of 12% and a polyvinyl alcohol aqueous solution with the mass percentage concentration of 8%, and then mixing the two solutions according to the weight ratio of 3-1: 1-1;
continuously adding a plasticizer into the mixed solution, and controlling the adding amount of the plasticizer to be 30% of the mass of the starch in the mixed solution; continuously stirring the mixed solution for 2 hours under the condition of 50 ℃ water bath to obtain spinning solution;
(2) preparation of centrifugal spinning superfine fiber membrane
Adding the spinning solution into a spinning device of a centrifugal spinning device, and preparing a fiber membrane by a centrifugal spinning method;
(3) cross-linking treatment of fibrous membranes
Placing the fiber membrane and a cross-linking agent in an oven (for example, placing the fiber membrane side by side), and carrying out cross-linking treatment at 130 ℃;
(4) hot rolling treatment of fibrous membranes
And (3) transferring the fiber membrane subjected to crosslinking treatment to a hot rolling mill for hot rolling treatment to obtain the degradable fiber-based packaging material.
In the step (1), the potato starch is natural potato starch or cross-linked potato starch, the polyvinyl alcohol is 1799 type polyvinyl alcohol, and the plasticizer is glycerol.
In the step (1), the preparation method of the potato starch solution comprises the following steps: dissolving sodium hydroxide in distilled water to prepare a solution with the mass concentration of 2%, and magnetically stirring for 0.5h at 25 ℃; continuously adding potato starch, and magnetically stirring at 25 deg.C for 10 hr to obtain potato starch solution, wherein the mass concentration of potato starch in the solution is controlled to 12%.
In the step (2), the operation parameters of the centrifugal spinning device are as follows: the diameter of the nozzle is 0.3-0.5 mm, and the rotation speed is 1200-2000 rpm.
In the step (3), the cross-linking agent is a mixed solution composed of ethanol, formic acid and glutaraldehyde according to the volume ratio of 20: 2: 1; the crosslinking treatment time in the oven was 3 h.
In the step (4), the temperature of the hot rolling treatment is 100-140 ℃.
Description of the inventive principles:
the invention utilizes the mixing of natural degradable material potato starch and synthetic degradable material polyvinyl alcohol to obtain spinning solution, and prepares high-quality micro-nano fiber material by regulating and controlling the rotating speed and the nozzle diameter of a centrifugal spinning device. Subsequently, the fiber is subjected to cross-linking treatment and hot rolling treatment to obtain the tea packaging base material. The preparation process flow is simple, the cost is low, the production process is environment-friendly, the obtained fiber is used for tea packaging and is harmless to human bodies, no pollution is generated to the environment after the fiber is used, and the green and sustainable development direction in China is met.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses starch and polyvinyl alcohol as spinning raw materials, the preparation method is simple and easy to implement, the process conditions are easy to realize, and the starch is used as a main component, so the cost is low. Is an ideal material for replacing filter paper tea bags with large energy consumption and complex production process.
2. The superfine fiber prepared by the invention has good degradability and biocompatibility, and is an ideal material for replacing most of the existing non-degradable synthetic polymers to prepare non-woven tea bags.
3. The fiber membrane prepared by the invention can be used for tea packaging materials, and has wide application prospects in the fields of food packaging, drug sustained release, biological scaffolds and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a fiber prepared in example 3 of the present invention;
FIG. 2 is an SEM photograph of the fiber obtained in example 3 of the present invention after soaking in hot water (90. + -. 5 ℃) for 30 min.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
(1) Weighing a certain amount of natural potato starch and polyvinyl alcohol, respectively preparing solutions with mass percentage concentrations of 12% (w/w) and 8% (w/w), mixing the two solutions according to a mass ratio of 3/1, adding 30% (w/w) glycerol according to the amount of starch in the mixed solution, and continuously stirring for 2 hours at 50 ℃ to obtain the spinning solution.
The preparation method of the potato starch solution comprises the following steps: dissolving sodium hydroxide in distilled water to prepare a solution with the mass concentration of 2%, and magnetically stirring for 0.5h at 25 ℃; the addition of potato starch was continued and magnetic stirring was carried out at 25 ℃ for 10h to obtain a potato starch solution in which the mass concentration of potato starch was controlled at 12% (the following examples are all carried out in this way and will not be described again).
(2) Preparation of centrifugal spinning fiber membrane:
the centrifugal spinning device of the present invention can be selected from conventional devices in the prior art, such as the centrifugal spinning device disclosed in the chinese utility model patent ZL201520785596.0 (the following embodiments are the same and will not be repeated). A nozzle having a diameter of 0.3mm was selected, and 2mL of the spinning solution was injected into a spinneret by a syringe to carry out centrifugal spinning, wherein the rotational speed was set at 2000 rpm.
(3) The prepared fiber is put into an oven with the temperature of 130 ℃, and crosslinking treatment is carried out on the fiber by using ethanol/formic acid/glutaraldehyde mixed solution with the volume ratio of 20/2/1, and the crosslinking time is 3 hours.
(4) And hot rolling the treated fiber on a hot rolling mill at the temperature of 100 ℃ to obtain the fiber film.
Example 2
(1) Weighing a certain amount of natural potato starch and polyvinyl alcohol, respectively preparing solutions with mass percentage concentrations of 12% and 8% (w/w), mixing the two solutions according to a mass ratio of 1/1, adding 30% (w/w) glycerol according to the amount of starch in the mixed solution, and continuously stirring for 2 hours at 50 ℃ to obtain the spinning solution.
(2) Preparing a centrifugal spinning fiber membrane: a nozzle having a diameter of 0.5mm was selected, and 2mL of the spinning solution was injected into a spinneret by a syringe to carry out centrifugal spinning, wherein the rotational speed was set at 1200 rpm.
(3) The prepared fiber is put into an oven with the temperature of 130 ℃, and crosslinking treatment is carried out on the fiber by using ethanol/formic acid/glutaraldehyde mixed solution with the volume ratio of 20/2/1, and the crosslinking time is 3 hours.
(4) And hot rolling the treated fiber on a hot rolling mill at the temperature of 140 ℃ to obtain a fiber film.
Example 3
(1) Weighing a certain amount of cross-linked potato starch and polyvinyl alcohol, respectively preparing solutions with mass percentage concentrations of 12% and 8% (w/w), mixing the two solutions according to a mass ratio of 1/1, adding 30% (w/w) glycerol according to the amount of starch in the mixed solution, and continuously stirring for 2h at 50 ℃ to obtain the spinning solution.
(2) Preparation of centrifugal spinning fiber membrane: a nozzle having a diameter of 0.3mm was selected, and 2mL of the spinning solution was injected into a spinneret by a syringe to carry out centrifugal spinning, wherein the rotational speed was set at 2000 rpm.
(3) The prepared fiber is put into an oven with the temperature of 130 ℃, and crosslinking treatment is carried out on the fiber by using ethanol/formic acid/glutaraldehyde mixed solution with the volume ratio of 20/2/1, and the crosslinking time is 3 hours.
(4) And hot rolling the treated fiber on a hot rolling mill at the temperature of 140 ℃ to obtain a fiber film.
Example 4
(1) Weighing a certain amount of cross-linked potato starch and polyvinyl alcohol, respectively preparing solutions with mass percentage concentrations of 12% and 8% (w/w), mixing the two solutions according to a mass ratio of 2/1, adding 30% (w/w) glycerol according to the amount of starch in the mixed solution, and continuously stirring for 2h at 50 ℃ to obtain the spinning solution.
(2) Preparation of centrifugal spinning fiber membrane: a nozzle having a diameter of 0.4mm was selected, and 2mL of the spinning solution was injected into a spinneret by a syringe to carry out centrifugal spinning, wherein the rotation speed was set to 1600 rpm.
(3) The prepared fiber is put into an oven with the temperature of 130 ℃, and crosslinking treatment is carried out on the fiber by using ethanol/formic acid/glutaraldehyde mixed solution with the volume ratio of 20/2/1, and the crosslinking time is 3 hours.
(4) And hot rolling the treated fiber on a hot rolling mill at the temperature of 120 ℃ to obtain a fiber film.
The micro-nanofiber raw material starch and PVA are hydrophilic materials, and have more excellent exudation performance when being used as a tea packaging material. Meanwhile, as can be seen from fig. 2, the fibers in the fiber membrane only undergo a swelling phenomenon in hot water, indicating that it has good durability in hot water. In addition, starch, as a natural polymer rich in nature, has self-evident degradation properties; PVA can be biodegraded by bacteria to ultimately form carbon dioxide and water. Therefore, the tea packaging material provided by the invention is a completely degradable green and environment-friendly material.
The above description is only a specific example of the present invention. It is obvious that the invention is not limited to the above examples of embodiment, but that many materials are possible. Other polymeric materials that can be derived or suggested directly from the disclosure herein by one of ordinary skill in the art are considered to be within the scope of the present invention.

Claims (5)

1. A preparation method of a degradable superfine fiber based tea packaging material is characterized by comprising the following steps:
(1) preparation of the spinning dope
Dissolving sodium hydroxide in distilled water to prepare a solution with the mass concentration of 2%, and magnetically stirring for 0.5h at 25 ℃; continuously adding potato starch, and magnetically stirring for 10h at 25 ℃ to obtain a potato starch solution, wherein the mass concentration of the potato starch in the solution is controlled to be 12%;
mixing a potato starch solution with the mass percentage concentration of 12% and a polyvinyl alcohol aqueous solution with the mass percentage concentration of 8% according to the weight ratio of 3-1: 1-1;
continuously adding a plasticizer into the mixed solution, and controlling the adding amount of the plasticizer to be 30% of the mass of the starch in the mixed solution; continuously stirring the mixed solution for 2 hours under the condition of 50 ℃ water bath to obtain spinning solution;
(2) preparation of centrifugal spinning fiber membrane
Adding the spinning solution into a spinning device of a centrifugal spinning device, and preparing a fiber membrane by a centrifugal spinning method;
(3) cross-linking treatment of fibrous membranes
Putting the fiber membrane and a cross-linking agent into an oven, and carrying out cross-linking treatment at 130 ℃;
(4) hot rolling treatment of fibrous membranes
And (3) transferring the fiber membrane subjected to crosslinking treatment to a hot rolling mill for hot rolling treatment to obtain the degradable fiber-based packaging material.
2. The method of claim 1, wherein in step (1), the potato starch is native potato starch or cross-linked potato starch, the polyvinyl alcohol is 1799 type polyvinyl alcohol, and the plasticizer is glycerol.
3. The method according to claim 1, wherein in the step (2), the operating parameters of the centrifugal spinning device are as follows: the diameter of the nozzle is 0.3-0.5 mm, and the rotation speed is 1200-2000 rpm.
4. The method according to claim 1, wherein in the step (3), the crosslinking agent is a mixed solution of ethanol, formic acid and glutaraldehyde in a volume ratio of 20: 2: 1; the crosslinking treatment time in the oven was 3 h.
5. The method according to claim 1, wherein the temperature of the hot rolling treatment in the step (4) is 100 to 140 ℃.
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Publication number Priority date Publication date Assignee Title
CN115537947A (en) * 2022-09-29 2022-12-30 浙江理工大学桐乡研究院有限公司 Superfine fiber-based fiber membrane airflow centrifugal spinning device and preparation method

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JPH08296121A (en) * 1995-04-25 1996-11-12 Kuraray Co Ltd Production of fibril comprising polyvinyl alcohol and starch
CN1807713A (en) * 2005-01-21 2006-07-26 李官奇 Fiber spinning dope containing protein and manufacturing method thereof
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CN103242561A (en) * 2013-05-27 2013-08-14 新疆师范大学 Method for preparing degradable mulching film by taking potato starch as raw material
CN104862827A (en) * 2015-05-29 2015-08-26 浙江理工大学 Method for preparing high amylopectin starch fiber
CN104894685A (en) * 2015-07-02 2015-09-09 上海全宇生物科技遂平有限公司 Modified starch/polyvinyl alcohol composite fiber and preparation method thereof
CN106492272A (en) * 2015-11-27 2017-03-15 广州迈普再生医学科技有限公司 Tissue repair fibrous membrane and its preparation method and application and tissue repair product
CN108699742A (en) * 2015-12-03 2018-10-23 纳幕尔杜邦公司 Fiber body structure and relative method
CN108715744A (en) * 2018-06-11 2018-10-30 佛山皖阳生物科技有限公司 A kind of preparation method of Starch Based Wood Adhesives
CN109881369A (en) * 2019-02-27 2019-06-14 浙江工业大学 A kind of preparation method for reinforcing antibacterial vapor-permeable type composite fibre static spinning membrane
CN110129917A (en) * 2019-05-05 2019-08-16 苏州回蓝环保科技有限公司 A kind of antibacterial starch base melt spinning resin and its application

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GB888276A (en) * 1958-05-26 1962-01-31 Kurashiki Rayon Kk Polyvinyl alcohol fibre production
US3044974A (en) * 1958-05-26 1962-07-17 Kurashiki Rayon Co Method of preparing polyvinyl alcohol filaments containing starch or derivatives thereof
US3922463A (en) * 1972-07-22 1975-11-25 Kanzaki Paper Mfg Co Ltd Paper material for pressure sensitive recording system
JPH04100913A (en) * 1990-08-20 1992-04-02 Toray Ind Inc Biodegradable fiber, biodegradable film and its production
JPH08296121A (en) * 1995-04-25 1996-11-12 Kuraray Co Ltd Production of fibril comprising polyvinyl alcohol and starch
CN1894447A (en) * 2003-12-18 2007-01-10 宝洁公司 Rotary spinning processes for forming hydroxyl polymer-containing fibers
CN1807713A (en) * 2005-01-21 2006-07-26 李官奇 Fiber spinning dope containing protein and manufacturing method thereof
CN103242561A (en) * 2013-05-27 2013-08-14 新疆师范大学 Method for preparing degradable mulching film by taking potato starch as raw material
CN104862827A (en) * 2015-05-29 2015-08-26 浙江理工大学 Method for preparing high amylopectin starch fiber
CN104894685A (en) * 2015-07-02 2015-09-09 上海全宇生物科技遂平有限公司 Modified starch/polyvinyl alcohol composite fiber and preparation method thereof
CN106492272A (en) * 2015-11-27 2017-03-15 广州迈普再生医学科技有限公司 Tissue repair fibrous membrane and its preparation method and application and tissue repair product
CN108699742A (en) * 2015-12-03 2018-10-23 纳幕尔杜邦公司 Fiber body structure and relative method
CN108715744A (en) * 2018-06-11 2018-10-30 佛山皖阳生物科技有限公司 A kind of preparation method of Starch Based Wood Adhesives
CN109881369A (en) * 2019-02-27 2019-06-14 浙江工业大学 A kind of preparation method for reinforcing antibacterial vapor-permeable type composite fibre static spinning membrane
CN110129917A (en) * 2019-05-05 2019-08-16 苏州回蓝环保科技有限公司 A kind of antibacterial starch base melt spinning resin and its application

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