CN104650549A - PLA (polylactic acid) degradable color master batch and preparation method thereof - Google Patents
PLA (polylactic acid) degradable color master batch and preparation method thereof Download PDFInfo
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- CN104650549A CN104650549A CN201510070027.2A CN201510070027A CN104650549A CN 104650549 A CN104650549 A CN 104650549A CN 201510070027 A CN201510070027 A CN 201510070027A CN 104650549 A CN104650549 A CN 104650549A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004626 polylactic acid Substances 0.000 title abstract 9
- 239000004595 color masterbatch Substances 0.000 title abstract 5
- 229920003023 plastic Polymers 0.000 claims abstract description 56
- 239000004033 plastic Substances 0.000 claims abstract description 56
- 239000000049 pigment Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 59
- 238000007670 refining Methods 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 26
- -1 poly(lactic acid) Polymers 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000004040 coloring Methods 0.000 abstract description 6
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000071 blow moulding Methods 0.000 abstract 1
- 238000010096 film blowing Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of plastic coloring, and provides a PLA (polylactic acid) degradable color master batch and a preparation method thereof. The PLA degradable color master batch is prepared from the following raw materials in percentage by weight: 66-74% of PLA plastic, 19-25% of refined pigment and 7-9% of assistant. The preparation method comprises the following steps: weighing the components according to percentage by weight, uniformly mixing the components to obtain a mixture, adding the obtained mixture into a double screw extruder, and carrying out melt extrusion to obtain the PLA degradable color master batch. The PLA degradable color master batch has the advantages of uniform coloring, low cost, controllable processing technique and the like on the premise of not changing the advantages of environment friendliness and degradability of the PLA plastic, and is widely used in the traditional plastic processing techniques, such as injection molding, blow molding, film blowing, sheet making and the like.
Description
Technical field
The invention belongs to field of plastic coloring, particularly relate to a kind of PLA degraded Masterbatch and preparation method thereof.
Background technology
Masterbatch also claims pigment preparation matter, by pigment, vector resin and additive composition, Masterbatch is by special method, pigment high density is scattered in equably the efficient tinting material of one formed in specific resin, therefore be also called condensed pigment, one seat has been occupied in the world rapidly since plastics occur, the problem simultaneously also causing white pollution is easily being brought for productive life, simultaneously due to the continuous minimizing of petroleum resources, take oil as the conventional plastic industry cost increase of raw material, biodegradable plastic substitutes conventional plastic will become a kind of trend, wherein, PLA plastics (poly(lactic acid)) are more important one, because PLA plastics have excellent biocompatibility, biodegradability, final degraded product is carbonic acid gas and water, can not to environment, it is a kind of desirable environment-friendly material, be widely used in the fields such as bio-medical material, PLA plastics have higher tensile strength simultaneously, modulus of compression, but matter is hard, toughness is poor, lack flexible and elasticity, these shortcomings all limit its application, in order to overcome the shortcoming that PLA plastics exist in the application, PLA Masterbatch in the market, major part is all processed into PLA Masterbatch to PLA plastics do modification, all add other resin copolymerization, and the resin copolymerization added to account for PLA Masterbatch ratio quite high, thus environmental protection aspect and the degradation property of PLA Masterbatch is affected, lose the advantage of PLA plastic material itself.
In sum, how can produce the PLA degraded Masterbatch that outward appearance is beautiful, colour fastness is high, mobility is strong in the performance basis not changing PLA plastics is problem demanding prompt solution.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of PLA degraded Masterbatch and preparation method thereof is provided, be intended to solve in prior art to overcome the shortcoming that PLA plastics exist in the application, modification processing is done to PLA plastics, thus affects the environmental protection aspect of PLA Masterbatch and the problem of degradation property.
The present invention is achieved in that on the one hand, provides the PLA degraded Masterbatch that a kind of outward appearance is beautiful, colour fastness is high, mobility is strong, comprises the component of following weight percent:
PLA plastics 66-74%
Refining pigment 19-25%
Auxiliary agent 7-9%.
Particularly, described refining pigment is obtained by Banbury mixer processing banburying.
Particularly, described refining pigment is pigment dyestuff or mineral dye.
Particularly, the fusing point of described PLA plastics is 175 ~ 185 DEG C, and density is 1.20-1.30kg/L, and intrinsic viscosity IV is 0.2 ~ 8dl/g.
Particularly, the weight-average molecular weight of described PLA plastics is 40000-200000.
Particularly, described poly(lactic acid) is L-type poly(lactic acid) or D type poly(lactic acid), and its melting index under 190 DEG C/2.16kg condition is 5-30g/10min.
On the other hand, provide a kind of PLA degraded Masterbatch preparation method, comprise the following steps:
(1) recipe ingredient is taken
Described PLA plastics, refining pigment and auxiliary agent is taken respectively according to the formula of PLA degraded Masterbatch described in claim 1;
(2) mixture is prepared
The described PLA plastics taken in step (1), refining pigment and auxiliary agent are added in blender, mixes, obtain mixture;
(3) melt extrude
The described mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Particularly, in step (2), the rotating speed of described blender is 800-1200 rev/min, and mixing time is 5-20 minute.
Particularly, in step (3), the shape of described PLA degraded Masterbatch can be column, pearl, square piece shape or former sheet.
Beneficial effect of the present invention is: PLA degraded Masterbatch of the present invention, adopt based on PLA plastics, add refining pigment and auxiliary agent, extrude through twin screw extruder, obtain PLA degraded Masterbatch, this PLA degraded Masterbatch can reach under the prerequisite not changing PLA plastics environment protecting degraded advantage, has uniform coloring, cost is low, complete processing is easy to the advantages such as control, is widely used in conventional plastic complete processing as injection moulding, blowing, blown film, sheet material etc.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in embodiment below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the PLA degraded Masterbatch preparation method schema that the embodiment of the present invention provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.
The embodiment of the present invention provides a kind of PLA degraded Masterbatch, comprises the component of following weight percent:
PLA plastics 66-74%
Refining pigment 19-25%
Auxiliary agent 7-9%.
Particularly, above-mentioned PLA plastics are refined by maize cereal to form, matter is hard, intensity and rigidity high, surface-brightening, smooth degree is fine, processing odorlessness, can natural degradation, do not circumnutate during printing, not alice, meet U.S. FDA certification, its fusing point is 175 ~ 185 DEG C, density is 1.20-1.30kg/L, intrinsic viscosity IV is 0.2 ~ 8dl/g, as preferred embodiment, PLA can purchase in U.S. Nature Works company PLA degradative plastics, in a particular embodiment, the mass percentage of these PLA plastics can be 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, concrete component such as 74% grade.
The weight-average molecular weight of above-mentioned PLA plastics (poly(lactic acid)) is 40000-200000.
Above-mentioned poly(lactic acid) is L-type poly(lactic acid) or D type poly(lactic acid), and its melting index under 190 DEG C/2.16kg condition is 5-30g/10min, and concrete melting index can according to ASTM D1238 standard.
Above-mentioned refining pigment refines pigment by the FDA food grade that Banbury mixer processing banburying is obtained, this pigment is pigment dyestuff or mineral dye, wherein, pigment dyestuff has: phthalocyanine is red, phthalocyanine blue, phthalocyanine green, everbright fast red, macromole is red, macromole is yellow, Deng, conventional mineral dye has: titanium dioxide, carbon black, titan yellow and ultramarine etc., by adding a certain amount of different pigment, the color of the PLA degraded Masterbatch made is made to have bright red, orange, yellow, green, sky blue, purple, grey, black, white, PLA primary colors, pink, join Pantone look, and this PLA degrades, Masterbatch color distribution is even, bright in colour, colour fastness is high, be suitable for what injection moulding, blown film, blowing, the machine-shapings such as extrusion moulding, can be applicable to food container, toy, medical treatment product, the industries such as sheet material, in a particular embodiment, the mass percentage of this pigment can be 19%, 20%, 21%, 22%, 23%, 24%, concrete component such as 25% grade.
Above-mentioned auxiliary agent plays lubrication and increases heatproof and hardness effect, and in a particular embodiment, the mass percentage of this auxiliary agent can be the concrete component such as 7%, 8%, 9%.
Correspondingly, the embodiment of the present invention provides a kind of PLA degraded Masterbatch preparation method, and as shown in Figure 1, this preparation method comprises the steps: this preparation method's schema
S01 takes recipe ingredient
Described PLA plastics, refining pigment and auxiliary agent is taken respectively according to the formula of above-mentioned PLA degraded Masterbatch;
S02 prepares mixture
The described PLA plastics taken in step S01, refining pigment and auxiliary agent are added in blender, mixes, obtain mixture;
S03 melt extrudes
The described mixture obtained in step S02 is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm, is extruded into PLA Masterbatch through twin screw extruder, the PLA raw material of every 25 kilograms adds PLA Masterbatch and is about 2-4%, so the finished product made can not change environmental protection and the natural degradation of PLA plastics.
Particularly, in above-mentioned steps S02, the rotating speed of blender is 800-1200 rev/min, and mixing time is 5-20 minute.
Particularly, in above-mentioned steps S03, the shape of PLA degraded Masterbatch can be column, pearl, square piece shape or former sheet.
PLA degraded Masterbatch of the present invention, adopt based on PLA plastics, add refining pigment and auxiliary agent, extrude through twin screw extruder, obtain PLA degraded Masterbatch, this PLA degraded Masterbatch can reach under the prerequisite not changing PLA plastics environment protecting degraded advantage, has uniform coloring, lovely luster, colour fastness is high, cost is low, complete processing is easy to the advantages such as control, is widely used in conventional plastic complete processing as injection moulding, blowing, blown film, sheet material etc.
Below in conjunction with specific embodiment, one detailed elaboration is done to the present invention.
Embodiment 1
This embodiment PLA degrades Masterbatch, by weight percentage, composed of the following components:
PLA plastics 70%, refining pigment 22%, auxiliary agent 8%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Embodiment 2
The PLA degraded Masterbatch of this embodiment, by weight percentage, composed of the following components:
PLA plastics 66%, refining pigment 25%, auxiliary agent 9%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Embodiment 3
The PLA degraded Masterbatch of this embodiment, by weight percentage, composed of the following components:
PLA plastics 74%, refining pigment 19%, auxiliary agent 7%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Embodiment 4
The PLA degraded Masterbatch of this embodiment, by weight percentage, composed of the following components:
PLA plastics 68%, refining pigment 25%, auxiliary agent 7%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Embodiment 5
The PLA degraded Masterbatch of this embodiment, by weight percentage, composed of the following components:
PLA plastics 72%, refining pigment 9%, auxiliary agent 19%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Embodiment 6
The PLA degraded Masterbatch of this embodiment, by weight percentage, composed of the following components:
PLA plastics 73%, refining pigment 20%, auxiliary agent 7%.
Its preparation method is as follows:
(1) each component is taken by above-mentioned weight percent;
(2) the PLA plastics taken in step (1), refining pigment, auxiliary agent are put into blender, mix, obtain mixture;
(3) mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
Can find that this PLA degrades Masterbatch employing based on PLA plastics by above embodiment, add refining pigment and auxiliary agent, extrude through twin screw extruder, obtain PLA degraded Masterbatch, this PLA degraded Masterbatch can reach under the prerequisite not changing PLA plastics environment protecting degraded advantage, have uniform coloring, lovely luster, colour fastness is high, cost is low, complete processing is easy to the advantages such as control, is widely used in conventional plastic complete processing as injection moulding, blowing, blown film, sheet material etc.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention figure.
Claims (9)
1. a PLA degraded Masterbatch, is characterized in that, comprise the component of following weight percent:
PLA plastics 66-74%
Refining pigment 19-25%
Auxiliary agent 7-9%.
2. PLA degraded Masterbatch as claimed in claim 1, is characterized in that, described refining pigment is obtained by Banbury mixer processing banburying.
3. PLA degraded Masterbatch as claimed in claim 1, it is characterized in that, described refining pigment is pigment dyestuff or mineral dye.
4. PLA degraded Masterbatch as claimed in claim 1, it is characterized in that, the fusing point of described PLA plastics is 175 ~ 185 DEG C, and density is 1.20-1.30kg/L, and intrinsic viscosity IV is 0.2 ~ 8dl/g.
5. PLA degraded Masterbatch as claimed in claim 1, it is characterized in that, the weight-average molecular weight of described PLA plastics (poly(lactic acid)) is 40000-200000.
6. PLA degraded Masterbatch as claimed in claim 1, it is characterized in that, described poly(lactic acid) is L-type poly(lactic acid) or D type poly(lactic acid), and its melting index under 190 DEG C/2.16kg condition is 5-30g/10min.
7. the PLA degraded Masterbatch preparation method as described in any one of claim 1-6, is characterized in that, comprise the steps:
(1) recipe ingredient is taken
Described PLA plastics, refining pigment and auxiliary agent is taken respectively according to the formula of PLA degraded Masterbatch described in claim 1;
(2) mixture is prepared
The described PLA plastics taken in step (1), refining pigment and auxiliary agent are added in blender, mixes, obtain mixture;
(3) melt extrude
The described mixture obtained in step (2) is added in twin screw extruder, through melt extruding, obtain PLA degraded Masterbatch, processing condition are: extrusion temperature is 200-230 DEG C, the length-to-diameter ratio of twin screw extruder is 40:1 ~ 52:1, and the rotating speed of twin screw extruder is 300-550rpm.
8. PLA degraded Masterbatch preparation method as claimed in claim 7, it is characterized in that, in step (2), the rotating speed of described blender is 800-1200 rev/min, and mixing time is 5-20 minute.
9. PLA degraded Masterbatch preparation method as claimed in claim 7, is characterized in that, in step (3), the shape of described PLA degraded Masterbatch can be column, pearl, square piece shape or former sheet.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105400154A (en) * | 2015-12-04 | 2016-03-16 | 河南天仁生物材料研究所有限公司 | Biodegradable plastic color masterbatch and preparation method thereof |
| CN108864669A (en) * | 2018-07-26 | 2018-11-23 | 苏州宝丽迪材料科技股份有限公司 | The preparation method of PLA Biodegradable fibers master batch |
| CN109054055A (en) * | 2018-06-27 | 2018-12-21 | 青岛中新华美塑料有限公司 | A kind of dyeing and processing technology of environment-friendly type plastic material |
| CN112322010A (en) * | 2020-11-16 | 2021-02-05 | 深圳市正旺环保新材料有限公司 | Plastic color master batch capable of being efficiently biodegraded and preparation method thereof |
| CN113480750A (en) * | 2021-07-07 | 2021-10-08 | 苏州宝丽迪材料科技股份有限公司 | Preparation process of biodegradable color master batch |
| CN115716980A (en) * | 2022-12-05 | 2023-02-28 | 台州市普丽得新材料科技有限公司 | Preparation formula and process of fully-degradable PLA color master batch |
| CN116970309A (en) * | 2023-06-06 | 2023-10-31 | 哈尔滨隆之道科技有限公司 | Non-toxic and harmless colored pencil lead and preparation method thereof |
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