CN102924890A - Fully-biodegradable heat shrinkage film and preparation method thereof - Google Patents
Fully-biodegradable heat shrinkage film and preparation method thereof Download PDFInfo
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- CN102924890A CN102924890A CN2012103796432A CN201210379643A CN102924890A CN 102924890 A CN102924890 A CN 102924890A CN 2012103796432 A CN2012103796432 A CN 2012103796432A CN 201210379643 A CN201210379643 A CN 201210379643A CN 102924890 A CN102924890 A CN 102924890A
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Abstract
The invention discloses a fully-biodegradable heat shrinkage film. A substrate resin material is any one or a mixed material of polyhydroxyalkanoate, poly-butylenes succinate, polylactic acid, polycaprolactone, polyesteramide and polypropylene carbonate. The heat shrinkage film is prepared from a fully-biodegradable material, has superior physical and mechanical properties, can be used for replacing the conventional heat shrinkage film, can be biodegraded fully after being discarded, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of heat-shrinkable film, particularly a kind of fully biodegradable heat-shrinkable film and preparation method thereof.
Background technology
Heat-shrinkable film is mainly used in the sale of product and the transportation product being packed, and heat-shrinkable film has good puncture resistance and string stress, and its Main Function is to stablize preferably and to protect product.
The heat-shrinkable film packing is compared other technologies of the package, and its principal feature is: good looking appearance, be close to commodity, suitable various difform commodity packagings; Moistureproof and waterproof is good; The transparency is good; Protectiveness is good; Keeping a public place clean property is good, especially is fit to precision instrument, high-grade, precision and advanced packing electronic component; Various article can be packaging together with a large shrink film, good economy performance and can avoid losing; Good stability, commodity can be not dilapidated in packing film, avoid damaging.
In view of heat-shrinkable film has above-mentioned good function, development is rapid in packaging industry in recent years.But mostly heat-shrinkable film is to utilize the conventional plastic material to make, such as polyvinyl chloride (PVC), polyvinylidene dichloride (PVDC), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyester (PET), polyolefine (PO) etc.Above-mentioned conventional plastic material does not have biodegradability, and because heat-shrinkable film is thin-film material, be very easy in the use damage, lose recycling and be worth, can cause severe contamination to environment after abandoning in a large number, the product that urgent need can substitute traditional heat-shrinkable film occurs.
Summary of the invention
For overcoming above-mentioned technological deficiency, the invention discloses a kind of heat-shrinkable film of fully biodegradable.
Fully biodegradable heat-shrinkable film disclosed by the invention, its matrix resin material are any one or a few mixing material in PHA, poly butylene succinate, poly(lactic acid), polycaprolactone, polyesteramide, the poly (propylene carbonate).
Preferably contain at least PHA in the matrix resin material of described heat-shrinkable film, the heat-shrinkable film performance of its preparation is more excellent.Especially, more preferably contain PHA and poly(lactic acid) in the matrix resin material of described heat-shrinkable film.
The poly (hydroxyalkanoate) ester content is 60%-100% in the described matrix resin material.
In the fully biodegradable heat-shrinkable film, also contain softening agent, lubricant, oxidation inhibitor.By mass, described matrix resin material is 100 parts, and described softening agent is 0.05-10 part, and described lubricant is 0.05-10 part, and described oxidation inhibitor is 0.05-10 part.
Further, by mass, described matrix resin material is 100 parts, and described softening agent is 0.5-5 part, and described lubricant is 0.5-5 part, and described oxidation inhibitor is 0.05-5 part.
The invention also discloses the preparation method of above-mentioned fully biodegradable heat-shrinkable film, it is characterized in that comprising the steps:
(1) batch mixing granulation: each component is mixed granulation;
(2) blown films: the pellet of step (1) is carried out blown film or extrusion sheet, cooling and shaping;
(3) radiation crosslinking: film or sheet material to step (2) cooling and shaping carry out radiation crosslinking, and the radiation crosslinking metering is preferably the kilogray (kGy) into 5-30;
(4) secondary blown film: to film or the sheet material preheating behind step (3) radiation crosslinking, carry out secondary and propel the price of typing, preheating temperature is preferably 100-200 ℃;
(5) rolling warehouse-in.
The problem that exists for solving existing heat-shrinkable film, the present invention utilizes completely biodegradable material successfully to prepare heat-shrinkable film as the matrix resin material, not only can replace traditional heat-shrinkable film to use, and also has biological degradation function.Particularly utilize PHA (PHA) as material of main part, the performance of its heat-shrinkable film has preferably heat sealability and ventilation property, also possesses very excellent physical and mechanical properties simultaneously as having excellent percent thermal shrinkage, tear strength, anti-puncture ability etc.This invention product can successfully have been realized alternative traditional heat-shrinkable film, can realize biological degradation when reaching the product service requirements, not to environment.
Embodiment
The below will the present invention is described in detail by specific embodiment.
Embodiment 1:
Take by weighing poly 3-hydroxy butyrate-4 hydroxybutyric acid ester P3HB4HB100 part, 1.5 parts of citrates, 1.0 parts in paraffin, oxidation inhibitor 2,0.5 part of 6-di-tert-butyl-4-methy phenol is put into the high mixer mixing and is taken out, and then passes through granulation, water-cooled slitting, produces the pellet for the preparation of heat-shrinkable film; Then pellet is added in the inflation film manufacturing machine, blows out the film that wall thickness is 100 μ m, through cooling and shaping, then carry out cross-linking radiation, wherein the cross-linking radiation metering is 5 kilogray (kGy)s; The film material is drawn preheating after the irradiation, its preheating temperature is 150 degrees centigrade, and through the typing of secondary inflation, can blow out wall thickness is 8-30 μ m film, through flattening, detect qualified after, the product rolling is put in storage.
Embodiment 2:
Take by weighing PHBV PHBV80 part, 20 parts of poly(lactic acid), 3 parts of citrates, 2 parts in paraffin, 1.5 parts of oxidation inhibitor 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate are put into the high mixer mixing and are taken out, then pass through granulation, water-cooled slitting, produce the pellet for the preparation of heat-shrinkable film; Then pellet is added in the inflation film manufacturing machine, blows out the film that wall thickness is 100 μ m, through cooling and shaping, traction, flattening, rolling; Then the film material of extruding is carried out cross-linking radiation, wherein the cross-linking radiation metering is 10 kilogray (kGy)s; Film material material is drawn after the irradiation, preheating, its temperature is asked 170 degrees centigrade, through the typing of secondary inflation, qualified after testing after, the product rolling is put in storage.
Embodiment 3:
Take by weighing poly--3-hydroxybutyrate ester-common-3-hydroxycaproic ester PHBH70 part, 30 parts of polycaprolactones, 5 parts of citrates, 1.0 parts in paraffin, oxidation inhibitor 2,2 parts of 6-di-tert-butyl-4-methy phenols are put into the high mixer mixing and are taken out, and then pass through granulation, water-cooled slitting, produce the pellet for the preparation of heat-shrinkable film; Then pellet is added in the casting machine, its wall thickness of extrusion sheet is 200 μ m, through cooling and shaping, upper dish; Then the sheet material of extruding is carried out cross-linking radiation, wherein the cross-linking radiation metering is 12 kilogray (kGy)s; Sheet material is drawn preheating after the irradiation, its temperature is 120 degrees centigrade, through longitudinal stretching, cross directional stretch, cooling and shaping, qualified after testing after, the product rolling is put in storage.
Embodiment 4:
Take by weighing 100 parts of poly(lactic acid), 8 parts of sorbyl alcohols, 6 parts of stearic acid, 8 parts of oxidation inhibitor 2,6 di tert butyl 4 methyl phenols are put into the high mixer mixing and are taken out, and then pass through granulation, water-cooled slitting, produce the pellet for the preparation of heat-shrinkable film; Then pellet is added in the inflation film manufacturing machine, blows out the film that wall thickness is 100 μ m, through cooling and shaping, then carry out cross-linking radiation, wherein the cross-linking radiation metering is 5 kilogray (kGy)s; The film material is drawn preheating after the irradiation, its preheating temperature is 150 degrees centigrade, and through the typing of secondary inflation, can blow out wall thickness is 8-30 μ m film, through flattening, detect qualified after, the product rolling is put in storage.
Embodiment 5:
Take by weighing 80 parts of poly-succinic fourth diester, 20 parts of poly(lactic acid), 2.5 parts of citrates, 1.0 parts in paraffin, 1.5 parts of oxidation inhibitor 2,6 di tert butyl 4 methyl phenols are put into the high mixer mixing and are taken out, then pass through granulation, water-cooled slitting, produce the pellet for the preparation of heat-shrinkable film; Then pellet is added in the inflation film manufacturing machine, blows out the film that wall thickness is 100 μ m, through cooling and shaping, traction, flattening, rolling; Then the film material of extruding is carried out cross-linking radiation, wherein the cross-linking radiation metering is 10 kilogray (kGy)s; Film material material is drawn after the irradiation, preheating, its temperature is asked 170 degrees centigrade, through the typing of secondary inflation, qualified after testing after, the product rolling is put in storage.
Embodiment 6:
Take by weighing 30 parts of polyesteramides, 50 parts of poly (propylene carbonate)s, 20 parts of polycaprolactones, 3.5 parts of citrates, 1.0 parts in paraffin, oxidation inhibitor 2,0.5 part of 6-di-tert-butyl-4-methy phenol is put into the high mixer mixing and is taken out, and then passes through granulation, water-cooled slitting, produces the pellet for the preparation of heat-shrinkable film; Then pellet is added in the casting machine, its wall thickness of extrusion sheet is 200 μ m, through cooling and shaping, upper dish; Then the sheet material of extruding is carried out cross-linking radiation, wherein the cross-linking radiation metering is 30 kilogray (kGy)s; Sheet material is drawn preheating after the irradiation, its temperature is 180 degrees centigrade, through longitudinal stretching, cross directional stretch, cooling and shaping, qualified after testing after, the product rolling is put in storage.
The heat-shrinkable film for preparing among above-described embodiment 1-6, its main performance index is as described below:
(1) tensile strength (MPa): vertically 〉=70, laterally 〉=70;
(2) elongation at break (%): vertically 〉=15, laterally 〉=15;
(3) tear strength (N/mm): vertically 〉=65, laterally 〉=65;
(4) percent thermal shrinkage (%): vertically 〉=100, laterally 〉=100.
Therefore, the fully biodegradable heat-shrinkable film of the present invention's preparation, its excellent combination property, can substitute the heat-shrinkable film by the traditional material preparation fully, and abandon rear fully biodegradable outside using, can not pollute environment, have larger economic worth and social value.
In sum; although the specific embodiment of the present invention is described in detail the present invention; but persons skilled in the art should be understood that; above-described embodiment only is the description to the preferred embodiments of the present invention; but not limiting the scope of the invention; persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily is all within protection scope of the present invention.
Claims (10)
1. fully biodegradable heat-shrinkable film, it is characterized in that: the matrix resin material of described heat-shrinkable film is any one or a few mixing material in PHA, poly butylene succinate, poly(lactic acid), polycaprolactone, polyesteramide, the poly (propylene carbonate).
2. fully biodegradable heat-shrinkable film as claimed in claim 1 is characterized in that: contain PHA in the matrix resin material of described heat-shrinkable film.
3. fully biodegradable heat-shrinkable film as claimed in claim 2, it is characterized in that: the matrix resin material of described heat-shrinkable film contains PHA and poly(lactic acid).
4. fully biodegradable heat-shrinkable film as claimed in claim 2, it is characterized in that: the poly (hydroxyalkanoate) ester content is 60%-100% in the described matrix resin material.
5. fully biodegradable heat-shrinkable film as claimed in claim 1 is characterized in that: also contain softening agent, lubricant, oxidation inhibitor.
6. fully biodegradable heat-shrinkable film as claimed in claim 5, it is characterized in that: by mass, described matrix resin material is 100 parts, and described softening agent is 0.05-10 part, and described lubricant is 0.05-10 part, and described oxidation inhibitor is 0.05-10 part.
7. fully biodegradable heat-shrinkable film as claimed in claim 6, it is characterized in that: by mass, described matrix resin material is 100 parts, and described softening agent is 0.5-5 part, and described lubricant is 0.5-5 part, and described oxidation inhibitor is 0.05-5 part.
8. such as the preparation method of the described fully biodegradable heat-shrinkable film of claim 1-7 any one, it is characterized in that comprising the steps:
(1) batch mixing granulation: each component is mixed granulation;
(2) blown films: the pellet of step (1) is carried out blown film or extrusion sheet, cooling and shaping;
(3) radiation crosslinking: film or sheet material to step (2) cooling and shaping carry out radiation crosslinking;
(4) secondary blown film: to film or the sheet material preheating behind step (3) radiation crosslinking, carry out secondary and propel the price of typing;
(5) rolling warehouse-in.
9. preparation method as claimed in claim 8 is characterized in that: the radiation crosslinking metering in the described step (3) is the 5-30 kilogray (kGy).
10. preparation method as claimed in claim 8, it is characterized in that: the preheating temperature in the described step (4) is 100-200 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147230A (en) * | 2013-03-20 | 2013-06-12 | 武汉纺织大学 | Fully-degradable bird-repelling agricultural non-woven fabric and preparation method for same |
| CN103483789A (en) * | 2013-09-29 | 2014-01-01 | 太仓市鸿运包装材料有限公司 | Biodegradable thermal shrinkage film and preparation method thereof |
| CN105802159A (en) * | 2014-12-29 | 2016-07-27 | 江苏华信新材料股份有限公司 | Degradable PHA/PLA mixture film and preparation method thereof |
| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water body degradation material with adjustable degradation period and preparation method thereof |
| CN111846327A (en) * | 2020-07-22 | 2020-10-30 | 山东野迈塑胶有限公司 | Full-degradable PE heat shrinkable film |
| WO2021026993A1 (en) * | 2019-08-09 | 2021-02-18 | 广东安德力新材料有限公司 | Heat shrink film and preparation method therefor |
| CN112920436A (en) * | 2021-01-26 | 2021-06-08 | 安徽农业大学 | Application of polyesteramide as high-temperature-resistant heat-shrinkable film |
| CN112940245A (en) * | 2021-04-09 | 2021-06-11 | 湖州汇盎生物降解塑料制品有限公司 | Biodegradable shrink film and preparation method thereof |
| CN115785636A (en) * | 2023-01-03 | 2023-03-14 | 中化泉州能源科技有限责任公司 | Degradable heat shrinkable film and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198714A (en) * | 1995-08-01 | 1998-11-11 | 奥托里夫发展有限公司 | Safety-belt retractor mechanism |
| JP2005007610A (en) * | 2003-06-16 | 2005-01-13 | Asahi Kasei Life & Living Corp | Biodegradable multilayered heat-shrinkable film and package |
| JP2005035238A (en) * | 2003-07-18 | 2005-02-10 | Fuji Seal International Inc | Heat shrinkable film and package |
| CN1643060A (en) * | 2002-04-02 | 2005-07-20 | 三菱树脂株式会社 | Heat-shrinkable polylactic acid film |
| CN100999587A (en) * | 2006-12-25 | 2007-07-18 | 刘津平 | Biological whole degrading film and mfg. process of its material |
| CN101205356A (en) * | 2006-12-22 | 2008-06-25 | 深圳市奥贝尔科技有限公司 | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid |
| CN101500805A (en) * | 2006-08-18 | 2009-08-05 | Skc株式会社 | Multilayered aliphatic polyester film |
| CN101775199A (en) * | 2008-11-18 | 2010-07-14 | 深圳市意可曼生物科技有限公司 | High-rigidity PHAs/PLA blending alloy and preparation method thereof |
| WO2012067388A2 (en) * | 2010-11-15 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly heat-shrinkable film |
| WO2012067472A2 (en) * | 2010-11-19 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly heat-shrinkable film |
-
2012
- 2012-10-09 CN CN2012103796432A patent/CN102924890A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198714A (en) * | 1995-08-01 | 1998-11-11 | 奥托里夫发展有限公司 | Safety-belt retractor mechanism |
| CN1643060A (en) * | 2002-04-02 | 2005-07-20 | 三菱树脂株式会社 | Heat-shrinkable polylactic acid film |
| JP2005007610A (en) * | 2003-06-16 | 2005-01-13 | Asahi Kasei Life & Living Corp | Biodegradable multilayered heat-shrinkable film and package |
| JP2005035238A (en) * | 2003-07-18 | 2005-02-10 | Fuji Seal International Inc | Heat shrinkable film and package |
| CN101500805A (en) * | 2006-08-18 | 2009-08-05 | Skc株式会社 | Multilayered aliphatic polyester film |
| CN101205356A (en) * | 2006-12-22 | 2008-06-25 | 深圳市奥贝尔科技有限公司 | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid |
| CN100999587A (en) * | 2006-12-25 | 2007-07-18 | 刘津平 | Biological whole degrading film and mfg. process of its material |
| CN101775199A (en) * | 2008-11-18 | 2010-07-14 | 深圳市意可曼生物科技有限公司 | High-rigidity PHAs/PLA blending alloy and preparation method thereof |
| WO2012067388A2 (en) * | 2010-11-15 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly heat-shrinkable film |
| WO2012067472A2 (en) * | 2010-11-19 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly heat-shrinkable film |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147230A (en) * | 2013-03-20 | 2013-06-12 | 武汉纺织大学 | Fully-degradable bird-repelling agricultural non-woven fabric and preparation method for same |
| CN103483789A (en) * | 2013-09-29 | 2014-01-01 | 太仓市鸿运包装材料有限公司 | Biodegradable thermal shrinkage film and preparation method thereof |
| CN105802159A (en) * | 2014-12-29 | 2016-07-27 | 江苏华信新材料股份有限公司 | Degradable PHA/PLA mixture film and preparation method thereof |
| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water body degradation material with adjustable degradation period and preparation method thereof |
| WO2021026993A1 (en) * | 2019-08-09 | 2021-02-18 | 广东安德力新材料有限公司 | Heat shrink film and preparation method therefor |
| CN111846327A (en) * | 2020-07-22 | 2020-10-30 | 山东野迈塑胶有限公司 | Full-degradable PE heat shrinkable film |
| CN112920436A (en) * | 2021-01-26 | 2021-06-08 | 安徽农业大学 | Application of polyesteramide as high-temperature-resistant heat-shrinkable film |
| CN112940245A (en) * | 2021-04-09 | 2021-06-11 | 湖州汇盎生物降解塑料制品有限公司 | Biodegradable shrink film and preparation method thereof |
| CN112940245B (en) * | 2021-04-09 | 2021-12-14 | 浙江汇盎新材料科技有限公司 | Biodegradable shrink film and preparation method thereof |
| CN115785636A (en) * | 2023-01-03 | 2023-03-14 | 中化泉州能源科技有限责任公司 | Degradable heat shrinkable film and preparation method thereof |
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Application publication date: 20130213 |