CN100410323C - Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof - Google Patents
Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof Download PDFInfo
- Publication number
- CN100410323C CN100410323C CNB2006101163340A CN200610116334A CN100410323C CN 100410323 C CN100410323 C CN 100410323C CN B2006101163340 A CNB2006101163340 A CN B2006101163340A CN 200610116334 A CN200610116334 A CN 200610116334A CN 100410323 C CN100410323 C CN 100410323C
- Authority
- CN
- China
- Prior art keywords
- foam plastic
- polylactic acid
- masterbatch
- acid foam
- proof
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses an antibiotic fungus-proof decomposalbe polylactic foam plastic and preparing method, which comprises the following parts: 100wt% polylactic resin, 1-5wt% antibiotic fungus-proof additive, 0.5-2wt% crosslinking agent, 0.5-5wt% nucleation agent, 0.5-2.5wt% foaming agent, 0.5-3wt% plasticizer and 0.5-1wt% anti-oxidant. The manufacturing method comprises the following steps: squeezing the composite material without foaming agent to prepare antibiotic fungus-proof mother material directly; adding foaming agent in the mother material; squeezing directly; moulding; flatting; drawing; coiling; packing.
Description
Technical field
The invention belongs to the engineering plastics technical field, be specifically related to a kind of polylactic acid foam plastic and preparation method thereof.
Background technology
Along with the development of country, the progressively raising of living standards of the people, the people's health perception and the consciousness of environment protection strengthened day by day.Create comfortable, cleaning, antibacterial and mouldproof, life, study and the Working environment of propagating that ward off disease be the pursuit that people make earnest efforts.But the degraded of product abandonment thing automated biological, free from environmental pollution also is an urgent demand of present international environmental protection cause.Regrettably, follow people when improving own living environment, also created favourable condition for the breeding growth of microorganism, bacterium.White pollution serious day by day, also the environment of depending on for existence to us causes huge pressure.
Bacterium and mould are two kinds of main types of microorganism, have characteristics of a great variety, that distributed pole is wide, vitality is vigorous.When envrionment conditions be relative 65%, temperature between 20-30 ℃, pH value is under the slightly acidic condition, will absorb the growth of nourishing and generating rapidly, cause material to go mouldy and destroy.The mycelium that forms during mould-growth is a conductor, and material insulation property is descended.The metabolite of mould-growth institute performance contains organic acid and mycin, can make that being clamminess appears in product surface, variable color, phenomenon such as become fragile, and can make that also the people of long-term these mould curd products of contact goes down with.
The goods that adopt general-purpose plastics to make at will abandon after the use, can cause white pollution.Because the general-purpose plastics molecular weight is big, molecular arrangement is tight, is not easy degraded.The agricultural mulching that for example uses materials such as PP, PVC to make can remain in the soil, causes the soil anoxic, makes farming for being choked to death; The disposable lunch box that use PP expanded plastic is made is the important source of white pollution especially.Therefore, control and elimination unwanted bacteria, mould, the protection human health is eliminated white pollution, has been the major subjects that current scientific and technological circle face jointly, is subjected to extensive concern day by day.
This does not exist poly(lactic acid) (PLA) in nature.It is to obtain through polycondensation by the lactic acid that obtains behind the amylofermentation.Poly(lactic acid) has the favorable biological degradability energy, and degraded product is carbonic acid gas and water, can not produce any detrimentally affect to environment.Poly(lactic acid) is with a wide range of applications, as fields such as food product pack, fibrous woven, daily plastics.In addition, poly(lactic acid) also has excellent biological compatibility and Bioabsorbable, has been considered to the most promising degradable high polymer material in medical field.But because the too high restriction of poly(lactic acid) production cost, it is started late as using with degradative plastics, in recent years, because the shortage of environmental requirement and petroleum resources makes people extraordinarily pay attention to poly(lactic acid), has begun the exploration exploitation of poly-lactic acid products.Though the price of PLA resin along with a large amount of manpower financial capacities' input, will make the poly(lactic acid) industry make a breakthrough also than higher at present.
In U.S. Pat Patent576309 (1998), people such as Kameoka adopt and to sneak into the method that chemical foaming agent and pneumatogen directly extrude and prepare polylactic acid foam plastic.The domestic relevant report that making expanded polylactic acid plastics are also arranged.But adopt direct extrusion molding to make still blank of antibacterial mould-proof-type polylactic acid foam plastic field.The present invention draws main thought of the present invention according to the related characteristics of prior art (for example CN1294145A), the fungi-proofing technology of nanometer and the biodegradable material of relevant antibacterial mildew inhibitor manufacture method.
Summary of the invention
The purpose of this invention is to provide a kind of good mechanical properties, antibacterial and mouldproof superior performance, biodegradable polylactic acid foam plastic and preparation method thereof.
The polylactic acid foam plastic of the anti-bacterium mildew-proof biodegradable that the present invention proposes, by various raw material blend directly extrude masterbatch, add whipping agent then and directly extrude and obtain, its feed composition prescription by weight is as follows:
Polylactic resin 100,
Antibacterial and mouldproof masterbatch 1-5,
Linking agent 0.5-2,
Nucleator 0.5-5,
Whipping agent 0.5-2.5,
Softening agent 0.5-3,
Oxidation inhibitor 0.5-1.
Among the present invention, described polylactic resin is left-handed rotation or racemization photosensitiveness polylactic resin, and number-average molecular weight is 18-20W, and molecular weight distribution is 1.8-2.2, and degree of crystallinity is 25-35%.
Among the present invention, described antibacterial and mouldproof masterbatch is with Ag+, Zn2+, Cu2+, nano-TiO
2A kind of or wherein multiple mixture as antiseptic-germicide, with a kind of or wherein multiple mixture of thiabendazole, m-tetrachlorophthalodinitrile, No. 75 industrial fungicides, derosal as mould inhibitor.
Among the present invention, described linking agent is a kind or several mixture in butyleneglycol, tolylene diisocyanate, xylylene diisocyanate, the diphenylmethanediisocyanate (MDI).
Among the present invention, described nucleator is polynite or talcum powder.
Among the present invention, described whipping agent is the AC whipping agent, and decomposition temperature is between 140 ℃-190 ℃.
Among the present invention, described softening agent is a dioctyl phthalate (DOP), a kind or 2 kinds of mixtures in the polyoxyethylene glycol.
Among the present invention, described oxidation inhibitor is a kind or 2 kinds of mixtures in pyrocatechol and the Resorcinol.
The preparation method of the anti-bacterium mildew-proof biodegradable polylactic acid foam plastic that the present invention proposes, concrete steps are as follows:
(1) by metering polylactic resin, nucleator, antibacterial and mouldproof masterbatch, oxidation inhibitor are mixed, extrude with forcing machine and make masterbatch;
(2) by measuring, use the forcing machine extrusion foaming, add linking agent and softening agent to forcing machine in the extrusion masterbatch, whipping agent uniform mixing; The temperature of extruding agent is controlled between 140-210 ℃;
(3) typing, cutting flattens, and traction is batched, packing.
The high foaming of antibacterial and mouldproof performance of the present invention poly(lactic acid) plastics have closed pore formula foamy structure, by being prepared from after the direct extrusion foaming typing of forcing machine.The discarded back of this kind antibacterial and mouldproof poly(lactic acid) is biodegradable, and degraded product is environmentally friendly, its production technique advanced person, product performance are good, and by the poly(lactic acid) that corn fermentation makes, raw material sources are extensive, overcome the restriction of oil shortage, the cost performance height is widely used in various wrapping material.
Embodiment
Below will come further detailed explanation the present invention by embodiment.In an embodiment, mark and per-cent is all by weight except as otherwise noted.But be not limited to these examples.The person skilled in the art of this area can do some unsubstantialities to the present invention according to foregoing and improve and adjust.
Embodiment 1
Polylactic resin (U.S. Natrueworks will be arranged, 4042D) 100 weight parts and antibacterial and mouldproof masterbatch 3 weight parts, polynite (DK4 type) 2 weight parts, the raw material of forming mixes, join in the forcing machine and extrude, extruder temperature is 160-210 ℃, engine speed is 850rpm, and the rotating speed of screw rod is 30rpm, makes the masterbatch cooling and dicing.Masterbatch, whipping agent 0.3 weight part uniform mixing joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add tolylene diisocyanate 0.5 weight part, dioctyl phthalate (DOP) 0.5 weight part by volume pump in extruding.Extrude foam, cooling, flattens, batches after the traction at typing, cutting.Pulling speed is 28rpm, and the products obtained therefrom specification is: thickness 3mm, and width 1200mm, cell diameter are 0.145mm, cell density is 1.8 * 10
5Individual/cm
3Cell density is a product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds; Fungicidal properties is 0 grade.
Embodiment 2
Identical among the amount of polylactic resin and antibacterial and mouldproof and the embodiment 1 in the compound, polynite (DK4) 3 weight parts, the raw material that pyrocatechol 0.5 weight part is formed mixes, join in the forcing machine and extrude, extruder temperature is between 150-230 ℃, engine speed is 800rpm, and screw speed is 30rpm, makes the masterbatch cooling and dicing.Masterbatch, whipping agent 0.6 weight part evenly joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add tolylene diisocyanate 0.5 weight part, dioctyl phthalate (DOP) 1 weight part by volume pump in extruding.Extrude foam, cooling, flattens, batches after the traction at typing, cutting.Pulling speed is 30rpm, and the products obtained therefrom specification is: thickness 2.9mm, width are 1200mm,, cell diameter is 0.121mm, cell density is 3.1 * 10
5Individual/cm
3Abscess product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds: fungicidal properties is 0 grade.
Embodiment 3
Polylactic resin (U.S. Natrueworks will be arranged, 4042D) 100 weight parts and antibacterial and mouldproof masterbatch 4 weight parts, pyrocatechol 0.5 weight part and Resorcinol 0.5 weight part, polynite (DK4 type) 3.5 weight parts, the raw material of forming mixes, join in the forcing machine and extrude, extruder temperature is 170-240 ℃, engine speed is 850rpm, and the rotating speed of screw rod is 30rpm, makes the masterbatch cooling and dicing.Masterbatch, whipping agent 1.0 weight part uniform mixing are joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add tolylene diisocyanate 0.5 weight part by volume pump in extruding, xylylene diisocyanate 0.5 weight part, dioctyl phthalate (DOP) 2 weight parts.Extrude foam, cooling, flattens, batches after the traction at typing, cutting.Pulling speed is 30rpm, and the products obtained therefrom specification is: thickness 3.0mm, and width 1200mm, cell diameter are 0.125mm, cell density is 3.3 * 10
5Individual/cm
3Cell density is a product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds; Fungicidal properties is 0 grade.
Embodiment 4
Polylactic resin (U.S. Natrueworks will be arranged, 4042D) 100 weight parts and antibacterial and mouldproof masterbatch 3 weight parts, talcum powder (DK4 type) 3 weight parts, the raw material that Resorcinol 1 weight part is formed mixes, join in the forcing machine and extrude, extruder temperature is 160-230 ℃, engine speed is 850rpm, and the rotating speed of screw rod is 30rpm, makes the masterbatch cooling and dicing.Masterbatch, whipping agent 1.3 weight part uniform mixing are joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add xylylene diisocyanate 0.5 weight part, diphenylmethanediisocyanate 0.5 weight part, dioctyl phthalate (DOP) 1 weight part by volume pump in extruding.Extrude foam, cooling, flattens, batches after the traction at typing, cutting.Pulling speed is 30rpm, and the products obtained therefrom specification is: thickness 3.1mm, and width 1200mm, cell diameter are 0.113mm, cell density is 3.5 * 10
5Individual/cm
3Cell density is a product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds; Fungicidal properties is 0 grade.
Embodiment 5
Polylactic resin (U.S. Natrueworks will be arranged, 4042D) 100 weight parts and antibacterial and mouldproof masterbatch 3.5 weight parts, polynite 5 (DK4 type) weight part, the raw material that Resorcinol 1.0 weight parts are formed mixes, join in the forcing machine and extrude, extruder temperature is 140-200 ℃, engine speed is 900rpm, and the rotating speed of screw rod is 30rpm, makes the masterbatch cooling and dicing.Masterbatch, whipping agent 2.5 weight part uniform mixing are joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add tolylene diisocyanate 1 weight part by volume pump in extruding, diphenylmethanediisocyanate 1 weight part, dioctyl phthalate (DOP) 0.5 weight part, ethylene glycol 0.5 weight part.Extrude to such an extent that foam batches after cooling, typing, cutting, flattening, traction.Pulling speed is 30rpm, and the products obtained therefrom specification is: thickness 2.6mm, and width 1200mm, cell diameter are 0.078mm, cell density is 3.6 * 10
5Individual/cm
3Cell density is a product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds; Fungicidal properties is 0 grade.
Embodiment 6
Polylactic resin (U.S. Natrueworks will be arranged, 6400D) 100 weight parts and antibacterial and mouldproof masterbatch 4 weight parts, polynite (DK4 type, 5 weight parts, the raw material that Resorcinol 1.0 weight parts are formed mixes, join in the forcing machine and extrude, extruder temperature is 170-240 ℃, and engine speed is 800rpm, the rotating speed of screw rod is 30rpm, makes the masterbatch cooling and dicing.Masterbatch 100 weight parts, whipping agent 0.7 weight part uniform mixing joined carry out extrusion foaming in the forcing machine, extrusion temperature and engine speed, screw speed are the same, add diphenylmethanediisocyanate 1 weight part, dioctyl phthalate (DOP) 0.5 weight part by volume pump in extruding.Extrude foam, cooling, flattens, batches after the traction at typing, cutting.Pulling speed is 28rpm, and the products obtained therefrom specification is: thickness 3.2mm, and width 1200mm, cell diameter are 0.157mm, cell density is 1.6 * 10
5Individual/cm
3Cell density is a product antibacterial and mouldproof performance: to large intestine Ai Xishi bacterium and streptococcus aureus: 24H antibiotic rate＞99%; Aspergillus niger, terreus etc. are mixed mould for 8 kinds; Fungicidal properties is 0 grade.
Claims (8)
1. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic, it is characterized in that by various raw material blend directly extrude masterbatch, add whipping agent then and directly extrude and obtain, its feed composition prescription by weight is as follows:
Polylactic resin 100,
Antibacterial and mouldproof masterbatch 1-5,
Linking agent 0.5-2,
Nucleator 0.5-5,
Whipping agent 0.5-2.5,
Softening agent 0.5-3,
Oxidation inhibitor 0.5-1;
Wherein, described antibacterial and mouldproof masterbatch is with Ag
+, Zn
2+, Cu
2+, nano-TiO
2A kind of or wherein multiple mixture as antiseptic-germicide, the matrix material of forming as mould inhibitor with a kind of or wherein multiple mixture of thiabendazole, m-tetrachlorophthalodinitrile, No. 75 industrial fungicides, derosal.
2. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1, it is characterized in that described resin is left-handed rotation or racemization photosensitiveness polylactic resin, number-average molecular weight is 10-25W, and molecular weight distribution is 1.8-2.2, and degree of crystallinity is 25-35%.
3. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that described linking agent is a kind or several mixture in butyleneglycol, tolylene diisocyanate, xylylene diisocyanate, the diphenylmethanediisocyanate.
4. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that described nucleator is polynite or talcum powder.
5. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that described whipping agent is the AC whipping agent, and decomposition temperature is between 140 ℃-190 ℃.
6. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that described softening agent is a dioctyl phthalate (DOP), a kind or 2 kinds of mixtures in the polyoxyethylene glycol.
7. anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that described oxidation inhibitor is a kind or 2 kinds of mixtures in pyrocatechol and the Resorcinol.
8. the preparation method of anti-bacterium mildew-proof biodegradable polylactic acid foam plastic according to claim 1 is characterized in that concrete steps are as follows:
(1) by metering poly(lactic acid), nucleator, antibacterial and mouldproof masterbatch, oxidation inhibitor are mixed, extrude with forcing machine and make masterbatch, cooling and dicing;
(2) by measuring masterbatch, whipping agent uniform mixing, use the forcing machine extrusion foaming, add linking agent and softening agent in the extrusion in forcing machine, the temperature of forcing machine is controlled between 140-240 ℃;
(3) typing, cutting flattens, and traction is batched, packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101163340A CN100410323C (en) | 2006-09-21 | 2006-09-21 | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101163340A CN100410323C (en) | 2006-09-21 | 2006-09-21 | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1923891A CN1923891A (en) | 2007-03-07 |
| CN100410323C true CN100410323C (en) | 2008-08-13 |
Family
ID=37816728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101163340A Expired - Fee Related CN100410323C (en) | 2006-09-21 | 2006-09-21 | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100410323C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245175B (en) * | 2007-05-21 | 2010-09-08 | 肖望东 | Biodegradation expanded plastic |
| CN101891941B (en) * | 2010-07-23 | 2012-07-18 | 西安工程大学 | Biodegradable composite foamed plastic and preparation method |
| CN102086299B (en) * | 2011-01-14 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | Transparent crystallization polylactic acid plastic and preparation method thereof |
| CN102212896A (en) * | 2011-05-27 | 2011-10-12 | 东华大学 | High-efficiency antibacterial mildew-proof PLA (poly lactic acid) fiber with skin-core structure and preparation method thereof |
| KR101393811B1 (en) | 2011-12-13 | 2014-05-13 | (주)엘지하우시스 | Foam sheet using cross-linked pla and manufacturing method of thereof |
| CN102604343A (en) * | 2012-02-23 | 2012-07-25 | 江南大学 | Food antimicrobial packaging material with slow release performance and preparation method of food antimicrobial packaging material |
| CN104804361A (en) * | 2014-01-28 | 2015-07-29 | 深圳齐心集团股份有限公司 | Antibacterial resin composite material and preparation method thereof |
| CN107006593B (en) * | 2017-03-10 | 2021-01-05 | 浙江省农业科学院 | Antibacterial and shock-absorbing foam for fruits and vegetables |
| CN108912627A (en) * | 2018-05-30 | 2018-11-30 | 苏州汉德瑞生物工程有限公司 | A kind of degradable controlled release antibiotic food packaging and preparation method |
| CN111607207B (en) * | 2020-06-29 | 2022-04-19 | 无锡会通轻质材料股份有限公司 | Expandable biodegradable particles and biodegradable foaming beads with antibacterial function |
| CN114350005A (en) * | 2022-01-10 | 2022-04-15 | 珠海市四唯包装材料有限公司 | Preparation method of green environment-friendly biodegradable PLA (polylactic acid) foaming material |
| CN115058107B (en) * | 2022-06-25 | 2023-07-04 | 扬州工业职业技术学院 | Antibacterial mildew-proof biodegradable polylactic acid plastic and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302424A (en) * | 1998-04-27 | 1999-11-02 | Mitsui Chem Inc | Biodegradable foamed sheet |
| JP2000328422A (en) * | 1999-05-26 | 2000-11-28 | Toyobo Co Ltd | Antibacterial and antifungal polylactic acid structure and its production |
| JP2004256795A (en) * | 2003-02-07 | 2004-09-16 | Toray Ind Inc | Polylactic acid film and laminate using it |
| JP2006111839A (en) * | 2004-10-18 | 2006-04-27 | Yasuhara Chemical Co Ltd | Antibacterial polylactic acid resin composition |
-
2006
- 2006-09-21 CN CNB2006101163340A patent/CN100410323C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302424A (en) * | 1998-04-27 | 1999-11-02 | Mitsui Chem Inc | Biodegradable foamed sheet |
| JP2000328422A (en) * | 1999-05-26 | 2000-11-28 | Toyobo Co Ltd | Antibacterial and antifungal polylactic acid structure and its production |
| JP2004256795A (en) * | 2003-02-07 | 2004-09-16 | Toray Ind Inc | Polylactic acid film and laminate using it |
| JP2006111839A (en) * | 2004-10-18 | 2006-04-27 | Yasuhara Chemical Co Ltd | Antibacterial polylactic acid resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1923891A (en) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100410323C (en) | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof | |
| CN102850626B (en) | Degradable mulch film and preparation method thereof | |
| CN101735636B (en) | Biodegradation time controlled plastic film and preparation method thereof | |
| CN106496672B (en) | A kind of preparation process based on quaternary ammonium salt antibacterial antiplaque agent natural latex products | |
| CN101250299B (en) | Method for preparing antibiotic fresh-keeping linear low density polyethylene film master batch | |
| CN104448476B (en) | High polymer quaternary ammonium salt antibacterial tube and preparation method thereof | |
| CN111742748B (en) | Biodegradable nutrition pot for boron-nitrogen-phosphorus slow-release compound fertilizer and preparation method and application thereof | |
| CN109485998A (en) | A kind of composite plastic of novel degradable and preparation method thereof | |
| CN104725709A (en) | Degradable fresh-keeping packaging material for vegetables and fruits and method for manufacturing degradable fresh-keeping packaging material | |
| CN110696318A (en) | Preparation method and application of biodegradable composite tubular material | |
| CN102702577A (en) | Degradable rubber and plastic film with plant peel and shell, fiber, plant powder as raw materials and preparation method thereof | |
| CN113583422B (en) | Biodegradable preservative film with antibacterial function and preparation method thereof | |
| JP2015532334A (en) | A polymer composition derived from the leaf sheath of a tree belonging to the palm family that has been melt-treated | |
| CN1958668A (en) | Plastic foam sheet material of poly lactic acid as suction plastic, and preparation method | |
| KR20110014001A (en) | Antibacterial and antifungal plastic, its product and its manufacturing method | |
| US9017587B2 (en) | Manufacturing method of biodegradable net-shaped articles | |
| CN103159983A (en) | Novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and method for preparing same | |
| KR101946143B1 (en) | Antiboitic biomass sheet and method of preparing the same | |
| CN105199490A (en) | Antibacterial coating masterbatch, antibacterial coating woven bag and production method of antibacterial coating masterbatch | |
| CN104175579A (en) | Double-layer hollow high thermal insulation greenhouse film and preparation method thereof | |
| CN102140185A (en) | Biodegradable mulching film and preparation method thereof | |
| CN107722449A (en) | Degradable composite material, production technology and mulch film | |
| CN102167845A (en) | Method for preparing degradable biomass material and straw | |
| KR100964570B1 (en) | Eco-friendly artificial wood and its manufacturing method | |
| CN103739940B (en) | A kind of method of medical waste infusion bag of carrying out a biological disposal upon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080813 Termination date: 20130921 |