CN1644794A - Completely biological degradable polylactic coating materials - Google Patents
Completely biological degradable polylactic coating materials Download PDFInfo
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- CN1644794A CN1644794A CN 200410011366 CN200410011366A CN1644794A CN 1644794 A CN1644794 A CN 1644794A CN 200410011366 CN200410011366 CN 200410011366 CN 200410011366 A CN200410011366 A CN 200410011366A CN 1644794 A CN1644794 A CN 1644794A
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Abstract
A fully biodegradable polylactic acid coating material for the coated paper consisting of paper substrate and coated plasticizing polylactic acid composition is disclosed. Said plasticizing polylactic acid composition contains proportionally polylactic acid, composite plasticizer chosen from polyethandiol, glucoside triacetate, triethyl citrate, tributyl citrate, triethyl acetylacetate, etc, lipoamide and inorganic filler. The coated paper features high resistance to water, oil and high temp, air tight, and antibacterial effect.
Description
Technical field
The invention belongs to the preparation method of completely biological degradation polylactic acid coating material.
Background technology
Macromolecular material based on petrochemicals is used widely in national defence and civil area with film, sheet material, tubing, fiber, foams and other forms.These macromolecular materials all become discarded object and natural environment are caused certain influence after use.Though a large amount of research and industrialization effort have been done to the regeneration of high molecular waste material in countries in the world, it is unsatisfactory to produce effects, and can not fundamentally solve the pollution problem of high molecular waste material to natural environment.In order to overcome this problem, countries in the world give increasing attention to the complete biodegradable macromolecular material.
PLA is a kind of macromolecular material of complete biodegradable, and the enzyme effect by microorganisms in natural environment finally is degraded into inorganic substances such as water and carbon dioxide.In degradable thermoplastic macromolecule material, PLA has the highest fusing point, and therefore the highest glass transition temperature and mechanical strength have better heat-resisting.But there are shortcomings such as poor toughness, processing temperature scope are narrower, cost of raw material height in PLA, is restricted in Application for Field such as Application Areas that requires pliability such as flexible packages.By improving the toughness of PLA to a great extent, especially help processing and reduce cost with the plasticizer blend.Can be with extruding through the PLA of plasticising, injection moulding, curtain coating, blowing, spinning, multiple mode such as biaxial stretch-formed is processed.Can expect that this completely biological degradation polylactic acid coating material will be widely used in the disposable packaging field.
Chinese patent ZL 99125782.0, ZL 99252343.5 and ZL 00263400.7 relate to the composite material for package of food of paper composite construction, and its skin is polylactic acid layers or copolymer of poly lactic acid layer.In these three patents, do not relate to plasticized poly lactic acid, so its workability and low cost are restricted.Chinese patent ZL 00112783.7 relates to a kind of plasticized poly lactic acid material that is applied to medical anti-adhesive film, and used plasticizer comprises water-soluble plasticizer such as polyethylene glycol and oil-soluble plasticizer such as oleic acid, stearic acid, capric acid, ethyl oleate in this material.Chinese patent ZL 02123145.1 relates to a kind of biodegradable plastics product of the 5-50% of containing weight portion polyglycereol acetic acid esters plasticized poly lactic acid.Chinese patent ZL 03117482.5 relates to the poly (lactic acid) composition film of the medical plasticizer of a kind of 2-15% of containing, and used plasticizer is polyethylene glycol, ATBC, tributyl 2-acetylcitrate, lactic acid oligomer.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of completely biological degradation polylactic acid coating material.
Since the nontoxic polyol ester class that can be used for packaging for foodstuff, citric acid ester type, and the polyesters plasticizer respectively has pluses and minuses to the plasticization effect of PLA at aspects such as heat resistance, resistance to migration, compatibilities, and result of use can not be satisfactory separately.If adopt the composite plasticizer that comprises more than two classes or two classes then can improve the comprehensive serviceability of PLA, the present invention is based on this understanding and obtains.
Paper that the ply of paper material therefor is made by string among the present invention or cardboard or the nonwoven fabric of making by acid fiber by polylactic, the coating material therefor is that the used composite plasticizer of the composition of composite plasticizer and PLA is selected from polyethylene glycol, glycerol triacetate, triethyl citrate, ATBC, acetyl triethyl citrate, one or two or more kinds that tributyl 2-acetylcitrate or polyesters plasticizer adipic acid kind polyester and decanedioic acid kind polyester are interim, consumption is the 5-115 weight portion with respect to the PLA of 100 weight portions, is preferably the 20-80 weight portion; According to purposes, can add slipping agent, inorganic filler in the poly (lactic acid) composition, the slipping agent of selecting for use is aliphatic amide, oleamide or erucyl amide, its addition is 0.05～1 part with respect to the PLA of 100 weight portions, the inorganic filler of selecting for use is silica, titanium dioxide, diatomite, carbon black, calcium carbonate or talcum powder, and its addition is 1～20 part with respect to the PLA of 100 weight portions; Used PLA can be selected crystalline polylactic acid or amorphism PLA for use.
The preparation method of completely biological degradation polylactic acid coating material, employing melt extrudes coating process or the solution coat method realizes, the solution coat method comprises coating processes commonly used such as transfer coated, dip-coating, blade coating, and wherein solvent is selected acetone, chloroform or both mixed solvents for use.
The preparation method who melt extrudes coating at first mixes the PLA of 100 weight portions with 5～120 parts of composite plasticizer in proportion by mechanical agitation, melt extrude through double screw extruder and utilize the extrusion coated equipment of being furnished with T pattern head to be extruded into plasticized poly lactic acid membranaceous after granulation obtains plasticized poly lactic acid or sheet is pressed on and forms the completely biological degradation polylactic acid coating material on the ply of paper;
The preparation method of solution coat be at first the PLA of 100 weight portions and 5～120 parts of composite plasticizer and 500～1000 parts by weight solvent are mixed in proportion obtain plasticized poly lactic acid solution after, utilize transfer coated, dip-coating or blade coating, with coating apparatus plasticized poly lactic acid is coated on the ply of paper with film or sheet form, dry out solvent forms the completely biological degradation polylactic acid coating material.
Description of drawings
Accompanying drawing 1 is the completely biological degradation polylactic acid coating material
(1) is ply of paper among the figure, and (2) are coating
The present invention 1 is described below in conjunction with the accompanying drawings: the completely biological degradation polylactic acid coating material comprises the coating (2) on ply of paper (1) and the ply of paper.The coated paper that possesses this structure is convenient to suitability for industrialized production, and has the complete biodegradable characteristic, and this coated paper can have functions such as waterproof, choke, grease resistance, antibiotic, colored printing, heat-resisting, heat-sealing.Coated paper with this kind structure can be applied to make dixie cup, cutlery box, disposable packaging etc.
The specific embodiment
Embodiment 1:
The amorphism PLA that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 5 weight portions, the oleamide of 0.1 weight portion.Composite plasticizer contains 2 parts of polyethylene glycol and 3 parts of triethyl citrates.The PLA of above-mentioned composition, composite plasticizer and additive are mixed by mechanical agitation, melt extrude granulation through double screw extruder and obtain plastification polylactic acid composition, utilize the extrusion coated equipment be furnished with T pattern head to be extruded into plastification polylactic acid composition membranaceous or sheet is pressed on and forms the completely biological degradation polylactic acid coating material on the ply of paper.
Embodiment 2:
The amorphism PLA that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 30 weight portions.Composite plasticizer contains 20 parts of glycerol triacetates and 10 parts of poly-decanedioic acid 1,3-butanediol ester, and preparation methods is with embodiment 1.
Embodiment 3:
The crystalline polylactic acid that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 70 weight portions, 5 weight portion diatomite.Composite plasticizer contain 20 parts of glycerol triacetates, 20 parts of poly-adipic acid 1,3 butylene glycol esters and 30 parts of acetyl triethyl citrate, preparation methods is with embodiment 1.
Embodiment 4:
The amorphism PLA that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 120 weight portions, the oleamide of 0.5 weight portion, 20 weight portion calcium carbonate.The composition of composite plasticizer contains 40 parts of glycerol triacetates, 60 parts of poly-decanedioic acid 1,3-butanediol ester and 20 parts of tributyl 2-acetylcitrates, and preparation methods is with embodiment 1.
Embodiment 5:
The amorphism PLA that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 60 weight portions, the oleamide of 0.1 weight portion, 3 weight portion titanium dioxides.The composition of composite plasticizer contains 20 parts of ATBCs and 40 parts of PPA, the chloroform that adopts 800 weight portions be solvent and PLA and plasticizer mix obtain plasticized poly lactic acid solution after, utilize transfer coated equipment that plasticized poly lactic acid is coated on the ply of paper with film or sheet form, dry out solvent forms the completely biological degradation polylactic acid coating material.
Embodiment 6:
The crystalline polylactic acid that comprises 100 weight portions in the composition of coating material, the composite plasticizer of 100 weight portions, the oleamide of 0.2 weight portion, 1 weight portion talcum powder.The composition of composite plasticizer contains 40 parts of glycerol triacetates, 30 parts of tributyl 2-acetylcitrates and 30 parts of poly-adipic acids 1, the 3-butanediol ester, the acetone that adopts the chloroform of 500 weight portions and 100 weight portions be solvent and PLA and plasticizer mix obtain plasticized poly lactic acid solution after, utilization is scraped automatic doubler surface glouer plasticized poly lactic acid is coated on the ply of paper with film or sheet form, and dry out solvent forms the completely biological degradation polylactic acid coating material.
Claims (6)
1, a kind of preparation method of completely biological degradation polylactic acid coating material, it is characterized in that coating material is made up of the plastification polylactic acid composition on ply of paper and the ply of paper, the ply of paper material therefor is paper, cardboard of being made by string or the nonwoven fabric of being made by acid fiber by polylactic.
2, the preparation method of completely biological degradation polylactic acid coating material as claimed in claim 1, it is characterized in that described plastification polylactic acid composition calculates by weight percentage, composition contains 100 parts PLA, 5～120 parts of composite plasticizer, 0～1 part of aliphatic amide slipping agent, 0～20 part of inorganic filler.
3, the preparation method of completely biological degradation polylactic acid coating material as claimed in claim 1 is characterized in that used PLA is crystalline polylactic acid or amorphism PLA.
4, the preparation method of claim 1 and 2 described completely biological degradation polylactic acid coating materials, it is characterized in that used composite plasticizer is selected from polyethylene glycol, glycerol triacetate, triethyl citrate, ATBC, acetyl triethyl citrate, tributyl 2-acetylcitrate or polyesters plasticizer adipic acid kind polyester and wherein one or two or more kinds of decanedioic acid kind polyester, consumption is the 5-120 weight portion with respect to the PLA of 100 weight portions, is preferably the 20-80 weight portion.
5, the preparation method of claim 1 and 2 described completely biological degradation polylactic acid coating materials is characterized in that described aliphatic amide slipping agent is oleamide or erucyl amide.
6, the preparation method of claim 1 and 2 described completely biological degradation polylactic acid coating materials is characterized in that described inorganic filler is silica, titanium dioxide, diatomite, carbon black, calcium carbonate or talcum powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011366 CN1644794A (en) | 2004-12-17 | 2004-12-17 | Completely biological degradable polylactic coating materials |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011366 CN1644794A (en) | 2004-12-17 | 2004-12-17 | Completely biological degradable polylactic coating materials |
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| CN1644794A true CN1644794A (en) | 2005-07-27 |
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| CN 200410011366 Pending CN1644794A (en) | 2004-12-17 | 2004-12-17 | Completely biological degradable polylactic coating materials |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304471C (en) * | 2005-04-15 | 2007-03-14 | 浙江工业大学 | Polylactic acid resin composition |
| CN101148536B (en) * | 2006-09-22 | 2011-04-20 | 华东理工大学 | Polyhydroxyl carboxylic acid modified material capable of completely biodegrading |
| CN102040814A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Special black master batch for polylactic acid based degradable plastics and preparation method thereof |
| CN102444056A (en) * | 2010-10-12 | 2012-05-09 | 龙盟环保纸（集团）有限公司 | Five-layer resolvable or degradable environmental friendly paper and production method thereof |
| WO2013023329A1 (en) * | 2011-08-12 | 2013-02-21 | 浙江凯恩特种材料有限公司 | Filter-paper for filter bag, filter bag for tea and bag tea |
| CN101824212B (en) * | 2010-02-02 | 2013-06-05 | 广东上九生物降解塑料有限公司 | Preparation method of polylactic acid degradable material |
| WO2013166744A1 (en) * | 2012-05-08 | 2013-11-14 | Wang Lei | Rewritable paper product |
| CN103429503A (en) * | 2011-03-07 | 2013-12-04 | 斯塔诺阿埃索澳吉有限公司 | Heat sealable biodegradable packaging material, its manufacturing method and a product package made therefrom |
| US8637126B2 (en) | 2006-02-06 | 2014-01-28 | International Paper Co. | Biodegradable paper-based laminate with oxygen and moisture barrier properties and method for making biodegradable paper-based laminate |
| CN105536063A (en) * | 2015-12-17 | 2016-05-04 | 大博医疗科技股份有限公司 | Polylactic acid-based antibacterial slow-release composite coating and preparation method thereof |
| CN106049185A (en) * | 2016-05-19 | 2016-10-26 | 苏州倍力特物流设备有限公司 | Polylactic-acid composite paperboard film material and preparation method therefor |
| CN106087584A (en) * | 2016-06-08 | 2016-11-09 | 铜陵方正塑业科技有限公司 | Waterproof and oilproof paper substrate complex pocket and preparation method thereof |
| CN103429503B (en) * | 2011-03-07 | 2016-11-30 | 斯塔诺阿埃索澳吉有限公司 | Heat-sealable biodegradable packaging material, its manufacture method and the product packaging being produced from |
| CN106801363A (en) * | 2016-12-30 | 2017-06-06 | 李宗飞 | A kind of compound degradable waterproof paper of PLA enhanced film waterproof heat resistant performance |
| CN107955346A (en) * | 2016-10-16 | 2018-04-24 | 长春工业大学 | A kind of polylactic acid plasticizing compound preparation method |
| CN108003760A (en) * | 2017-11-10 | 2018-05-08 | 夏新发 | A kind of coating liquid for vinyl house |
| CN109914038A (en) * | 2019-04-08 | 2019-06-21 | 山东彩汇包装科技有限公司 | A kind of preparation process of degradable nonwoven fabrics packaging |
| CN110878488A (en) * | 2019-11-20 | 2020-03-13 | 民丰特种纸股份有限公司 | Novel leather release paper |
| CN113478903A (en) * | 2021-07-28 | 2021-10-08 | 上海丹麒包装材料有限公司 | Compression-resistant color box processing technology |
| CN113605140A (en) * | 2021-07-13 | 2021-11-05 | 美盈森集团股份有限公司 | Polylactic acid waterproof coating material, preparation method and paper pulp molding |
-
2004
- 2004-12-17 CN CN 200410011366 patent/CN1644794A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304471C (en) * | 2005-04-15 | 2007-03-14 | 浙江工业大学 | Polylactic acid resin composition |
| US8637126B2 (en) | 2006-02-06 | 2014-01-28 | International Paper Co. | Biodegradable paper-based laminate with oxygen and moisture barrier properties and method for making biodegradable paper-based laminate |
| CN101148536B (en) * | 2006-09-22 | 2011-04-20 | 华东理工大学 | Polyhydroxyl carboxylic acid modified material capable of completely biodegrading |
| CN101824212B (en) * | 2010-02-02 | 2013-06-05 | 广东上九生物降解塑料有限公司 | Preparation method of polylactic acid degradable material |
| CN102444056A (en) * | 2010-10-12 | 2012-05-09 | 龙盟环保纸（集团）有限公司 | Five-layer resolvable or degradable environmental friendly paper and production method thereof |
| CN102444056B (en) * | 2010-10-12 | 2016-08-10 | 龙盟环保纸（集团）有限公司 | Five layers of decomposable asymmetric choice net or the environment protecting paper of degraded and manufacture method thereof |
| CN102040814B (en) * | 2010-12-29 | 2012-06-27 | 深圳市科聚新材料有限公司 | Special black master batch for polylactic acid based degradable plastics and preparation method thereof |
| CN102040814A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Special black master batch for polylactic acid based degradable plastics and preparation method thereof |
| CN103429503B (en) * | 2011-03-07 | 2016-11-30 | 斯塔诺阿埃索澳吉有限公司 | Heat-sealable biodegradable packaging material, its manufacture method and the product packaging being produced from |
| CN103429503A (en) * | 2011-03-07 | 2013-12-04 | 斯塔诺阿埃索澳吉有限公司 | Heat sealable biodegradable packaging material, its manufacturing method and a product package made therefrom |
| WO2013023329A1 (en) * | 2011-08-12 | 2013-02-21 | 浙江凯恩特种材料有限公司 | Filter-paper for filter bag, filter bag for tea and bag tea |
| WO2013166744A1 (en) * | 2012-05-08 | 2013-11-14 | Wang Lei | Rewritable paper product |
| CN105536063A (en) * | 2015-12-17 | 2016-05-04 | 大博医疗科技股份有限公司 | Polylactic acid-based antibacterial slow-release composite coating and preparation method thereof |
| CN106049185A (en) * | 2016-05-19 | 2016-10-26 | 苏州倍力特物流设备有限公司 | Polylactic-acid composite paperboard film material and preparation method therefor |
| CN106087584A (en) * | 2016-06-08 | 2016-11-09 | 铜陵方正塑业科技有限公司 | Waterproof and oilproof paper substrate complex pocket and preparation method thereof |
| CN107955346A (en) * | 2016-10-16 | 2018-04-24 | 长春工业大学 | A kind of polylactic acid plasticizing compound preparation method |
| CN107955346B (en) * | 2016-10-16 | 2020-02-11 | 长春工业大学 | Preparation method of polylactic acid plasticized compound |
| CN106801363A (en) * | 2016-12-30 | 2017-06-06 | 李宗飞 | A kind of compound degradable waterproof paper of PLA enhanced film waterproof heat resistant performance |
| CN108003760A (en) * | 2017-11-10 | 2018-05-08 | 夏新发 | A kind of coating liquid for vinyl house |
| CN108003760B (en) * | 2017-11-10 | 2020-04-07 | 安徽新源农业科技有限公司 | Film coating liquid for plastic greenhouse |
| CN109914038A (en) * | 2019-04-08 | 2019-06-21 | 山东彩汇包装科技有限公司 | A kind of preparation process of degradable nonwoven fabrics packaging |
| CN110878488A (en) * | 2019-11-20 | 2020-03-13 | 民丰特种纸股份有限公司 | Novel leather release paper |
| CN113605140A (en) * | 2021-07-13 | 2021-11-05 | 美盈森集团股份有限公司 | Polylactic acid waterproof coating material, preparation method and paper pulp molding |
| CN113478903A (en) * | 2021-07-28 | 2021-10-08 | 上海丹麒包装材料有限公司 | Compression-resistant color box processing technology |
| CN113478903B (en) * | 2021-07-28 | 2023-02-28 | 上海丹麒包装材料有限公司 | Compression-resistant color box processing technology |
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