CN102019705A - Method for manufacturing biobased macromolecule shoe material - Google Patents
Method for manufacturing biobased macromolecule shoe material Download PDFInfo
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- CN102019705A CN102019705A CN2009101746475A CN200910174647A CN102019705A CN 102019705 A CN102019705 A CN 102019705A CN 2009101746475 A CN2009101746475 A CN 2009101746475A CN 200910174647 A CN200910174647 A CN 200910174647A CN 102019705 A CN102019705 A CN 102019705A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920002521 macromolecule Polymers 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims abstract description 41
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- 238000004898 kneading Methods 0.000 claims abstract 2
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- 235000019698 starch Nutrition 0.000 claims description 46
- 239000008107 starch Substances 0.000 claims description 46
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 39
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 39
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
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- 210000001161 mammalian embryo Anatomy 0.000 claims description 6
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
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- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
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Abstract
一种生物基高分子鞋材的制造方法，包括下列步骤：提供一混合物进行混炼以形成一鞋材配料，该混合物包括预定比例相混合的改性的淀粉组分、EVA组分、填充剂组分、聚烯烃组分、发泡剂组分、发泡助剂组分、润滑剂组分及架桥剂组分。将该鞋材配料制成一片状或颗粒状的发泡材料，取片状的发泡材料经油压发泡成型、或取粒状的发泡材料经射出发泡成型以制成一鞋材成品。由此，应用改性的淀粉组分的特性以增加其与塑料原料的兼容性，就能在减少EVA组分用量的情形下制出鞋材成品，以降低对石化原料的依赖，除了能节能减碳外，仍能符合实用效果。
A method for manufacturing a bio-based polymer shoe material, comprising the following steps: providing a mixture for kneading to form a shoe material ingredient, the mixture including a modified starch component, an EVA component, and a filler mixed in a predetermined ratio Components, polyolefin components, foaming agent components, foaming aid components, lubricant components and bridging agent components. The shoe material is made into a sheet or granular foam material, and the sheet foam material is foamed by hydraulic pressure, or the granular foam material is injection foamed to make a shoe material. finished product. Therefore, by using the properties of the modified starch component to increase its compatibility with plastic raw materials, the finished shoe material can be produced under the condition of reducing the amount of EVA component, so as to reduce the dependence on petrochemical raw materials. In addition to energy saving In addition to carbon reduction, it can still meet the practical effect.
Description
Technical field
The present invention relates to a kind of manufacture method of footwear material, particularly relate to a kind of manufacture method that helps bio-based macromolecule (bio-base polymer) the footwear material of carbon reduction.
Background technology
The energy, environment, economy are the 21st century important issue that faced of human social development, and wherein the aspect that influences of environment more relates to and comprises all species on the human earth.The most obvious direct example of the change of circumstances is global warming, in recent years because emerging nation develops rapidly and actively carry out industrialization, the result who depends on petrochemical material unduly produces a large amount of greenhouse gas emissions, and the global warming problem that also makes greenhouse effects and caused heals and becomes serious.
Petrochemical material is made through refinement again, is main fuel and moulding material material source, the main arch-criminal that the great amount of carbon dioxide that is discharged in atmosphere after these products process burnings or the incineration is considered to cause global warming.In order to alleviate negative effect, solution petrochemical industry shortage of resources to environment, reach a large amount of discarded objects and greenhouse gas emission and cause problems such as the deterioration of the ecological environment, each state all is devoted to develop the bio-based resource.
Angle with the carbon footprint, the bio-based resource still produces carbon dioxide at its life cycle end, but during the bio-based plant growth, can carry out photosynthesis, with fixedly Atmospheric Carbon Dioxide and synthetic carbohydrate and form carbon cycle, compare with petrochemical material, the discharge capacity of its net carbon dioxide is zero, therefore replaces petrochemical material with the bio-based resource and can effectively reduce emission of carbon-dioxide.
Ethylene-vinyl acetate copolymer (ethylene-vinyl acetate copolymer, abbreviate EVA as) through foaming processing, have light weight and soft comfortable characteristic, and can reach the effect of shock-absorbing bounce-back, and become the material that is used in a large number in sport footwear, the playshoes.Yet EVA footwear material also is from traditional petrochemical material, at its finished product life cycle tail end, faces equally and can't decompose and the problem that easily causes environmental pressure.
In order to reduce dependence to traditional petrochemical material, to reach carbon reduction and to reduce the problem that environment is impacted, utilize biomaterial (biomaterial), for example, starch, it is the direction of present industry development effort that replacement parts of traditional petrochemical material is made bio-based macromolecule footwear material.Need bear gravity and the frequent operating characteristic of wearing and tearing in response to the footwear material, compare, except still will possessing functions such as light weight, soft comfortable and shock-absorbing bounce-back, higher structural strength will be arranged also, just can meet predetermined durability with other plastic products.The mode that adopts is to use the bio-based materials of predetermined ratio to mix as footwear material raw material with the EVA raw material at present, reduces the use amount of EVA whereby.Wherein, reach good binding, must reach by the particular process of manufacture of employing HTHP or the biomaterial of modification in order to make biomaterial and EVA raw material.Yet, adopt the HTHP preparation process need expend a large amount of energy, cause energy cost to increase on the contrary.Therefore, utilize the biomaterial of modification to make it form the direction that stable bond is worth developmental research with EVA.But, even develop the biomaterial that can form the modification of stable bond with EVA, still need cooperate special formulation and preparation process, to make finished product with predetermined rerum natura and durability, can make the bio-based macromolecule footwear material of being made not only meet the purpose of carbon reduction thus, can also reach practical effect.
Summary of the invention
The objective of the invention is is providing a kind of ratio that can increase the biomaterial consumption, to reduce the manufacture method to the bio-based macromolecule footwear material of traditional petrochemical material dependency degree.
The manufacture method of bio-based macromolecule footwear material of the present invention comprises the following steps:
(i) it is mixing to form footwear material batching to provide a mixture to carry out, this mixture comprises the starch ingredients of the modification of 5～50 weight portions, the ethylene-vinyl acetate copolymer of 95～50 weight portions (EVA) component, the filler component of 5～30 weight portions, the polyolefin component of 0～50 weight portion, 2.0 the blowing agent component of～8.0 weight portions, 0.5 the blowing promotor component of～3.0 weight portions, 0.5 the bridging agent component of the lubricant composition of～2.0 weight portions and 0.4～1.2 weight portion, the starch ingredients of this modification is the starch material by scheduled volume, via hydrolysis, after esterification formed esterification starch, drying was handled and is made again;
(ii) this footwear material batching is made expanded material, this expanded material be selected from sheet or granular in one of form; With
The expanded material of (iii) getting sheet is via the oil pressure foaming, or gets granular expanded material via shot foamed moulding, and making a kind of footwear material finished product, and this footwear material finished product is to be selected from the end and the form of footwear at the big end in shoe-pad, the footwear.
Beneficial effect of the present invention is with main effect: the effect of the processing by modifications such as hydrolysis, esterifications, when the starch ingredients of modification is mixed mutually with the EVA component, except making via hydrolysis the intermolecular contact area of itself and EVA increases, form the result of ester group on the starch surface via esterification treatment, also help itself and the intermolecular compatibility of EVA, make the starch ingredients of this modification can be with higher ratio and EVA component mixing and form stable combining thus; And it is because compatible good, starch ingredients based on this modification also can be as traditional E VA raw material with the mixture of EVA component, carry out foaming processing, the footwear material of being made still can be kept light weight and soft comfortable characteristic, and other rerum natura also can meet footwear material rerum natura specification.Therefore, the consumption that manufacture method of the present invention can effectively reduce the EVA component to be reaching the environmental protection purpose of carbon reduction, and can make the footwear material that has predetermined structure intensity and can meet user demand smoothly.
Description of drawings
Fig. 1 is the flow chart of first preferred embodiment of the manufacture method of bio-based macromolecule footwear material of the present invention;
Fig. 2 is the flow chart of second preferred embodiment of the manufacture method of bio-based macromolecule footwear material of the present invention.
The specific embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Consult Fig. 1, be first preferred embodiment of the manufacture method of bio-based macromolecule footwear material of the present invention, it comprises the following step:
Step 101 provides a mixture, and it carries out 6～15 minutes hot melt and mixing by a mixer 100 ℃～130 ℃ of temperature, to form footwear material batching.Wherein this mixer can select for use ten thousand horsepowers, profit internal mixture such as to take, and also can use the twin-screw extruder.This mixture comprises the starch ingredients of the modification of 5～50 weight portions, ethylene-vinyl acetate copolymer (EVA) component of 95～50 weight portions, the filler component of 5～30 weight portions, the polyolefin component of 0～50 weight portion, the blowing agent component of 2.0～8.0 weight portions, the blowing promotor component of 0.5～3.0 weight portion, the lubricant composition of 0.5～2.0 weight portion and the bridging agent component of 0.4～1.2 weight portion.Wherein, the gross weight after the starch ingredients of the modification in this mixture and the addition of ethylene-vinyl acetate copolymer component is 100 weight portions.
The starch ingredients of this modification is the starch material by scheduled volume, and behind hydrolysis, esterification formation esterification starch, drying is handled and made again.Wherein, this starch material is the inorganic acid solution with concentration 0.5～2.0N, from mean molecule quantity 〉=10
8The starch of larger molecular weight be hydrolyzed to average molecular weight range 10
4～10
7Hydrolyzed starch, carry out esterification with after forming esterification starch with acid anhydrides or organic acid again, last spray-dried mode is made the starch ingredients of this modification.At this, be to use acetic anhydride and hydrolyzed starch to carry out esterification, to utilize the carboxylic acid group in its molecule and the part alcohol radical effect on starch molecule surface, form the ester group structure, reach the effect of the starch of esterification modification.
Preferably, the particle diameter of the starch ingredients of formed this modification of spray-dried processing is 10～50 μ m, and its moisture content is 2～8% (w/w).
Preferably, this filler component is selected from calcium carbonate, talcum powder, magnesium carbonate, kaolin and their combination.This bridging agent component is cumyl peroxide (dicumyl peroxide abbreviates DCP as).This lubricant composition is hard ester acid.This blowing promotor component is a Zinc Oxide.
Step 102 is this footwear material batching to be made the expanded material of sheet form.Promptly this footwear material batching is after 101 steps are mixing, with a pair of scroll wheel device slice, to make several pieces expanded materials in the form of sheets.
The prepared sheet expanded material of step 102 can use for step 103 or step 104 respectively, to make multi-form footwear material finished product.
Step 103 is that the expanded material of getting sheet is made this footwear material finished product (shoe-pad) by the mode of oil pressure foaming.When making this footwear material finished product in the mode of oil pressure foaming, it is the expanded material of this footwear material batching being made sheet, after again several pieces sheet expanded material being stacked to a predetermined weight, inserting in the oil pressure platform mould of a preheating and carry out foaming to make foaming plate earlier.Wherein, described sheet expanded material is preferably 20～50 minutes the action time in this oil pressure platform mould, and the temperature of this oil pressure platform mould is set at 165 ℃～175 ℃, and its pressure is set at 160～200kg/cm
2Prepared foaming plate just can further be made the footwear material finished product of shoe-pad form again after suitably cutting.
Step 104 is that the expanded material of getting sheet is made foaming plate earlier by the mode of oil pressure foaming, uses for follow-up preparation process step, and the method for making of its foaming plate is identical with step 103, repeats no more.
Step 105 is that the prepared foaming plate of step 104 is carried out the processing and forming second time, cooperates mould therefor further to make the footwear material finished product of reservation shape, is mainly the end or the big end of footwear in the footwear according to the prepared footwear material of this process finished product.
Consult Fig. 2, be second preferred embodiment of the manufacture method of bio-based macromolecule footwear material of the present invention, its step 201 is identical with the step 101 of first preferred embodiment, so repeat no more.
The prepared granular expanded material of step 202 can use for step 203 or 204 respectively, further to make desired footwear material finished product.
What deserves to be explained is, mixture comprises the polyolefin component of 0～50 weight portion in step 101 and step 201, its effect mainly is in order to reduce the proportion of final footwear material finished product, when polyolefinic content high more, the proportion of final foaming finished product is low more and have the characteristic of light weight, but relatively, also can cause the rerum natura variation of footwear material finished product, in order to make footwear material finished product keep the rerum natura that meets practical specification, its consumption should not be too high.
The present invention puts up with following concrete example and is described further, but should be appreciated that this concrete example only for illustrating use, and should not be interpreted as restriction of the invention process.
Be example with the big end of the end and footwear in shoe-pad, the footwear respectively below, six concrete examples are provided, its manufacture process is described, and carry out physical property measurement at finished product of the big end of the end and footwear in the shoe-pad of being made in view of the above, the footwear, the footwear material finished product of being made with explanation has predetermined structural strength, and can meet the rerum natura requirement of footwear material finished product.
＜concrete example one 〉
Get modification starch 1000 gram, with EVA component (containing EVA 3000 grams and EVA reclaimed materials 1000 grams), polyolefin 500 grams, talcum powder 300 grams, blowing agent 133 grams, bridging agent (DCP) 25 grams, hard ester acid 60 grams and Zinc Oxide 40 grams are formulated as a mixture.Above-mentioned material is inserted small-sized profit by in the mixer behind the mix in advance, start mixer and begin to carry out 10 to 15 minutes mixing operation, treat that temperature continues to rise to about 110 ℃, and it is mixing when having carried out 6～15 minutes, can make the complete hot melt of this mixture and evenly be mixed into footwear material batching, just can be toppled over out by mixing channel this moment with this footwear material batching.Agglomerating batching placed carry out the slice program on two rollers to form the expanded material of sheet, starch-EVA the expanded material that takes by weighing the modification that has gone out sheet is to predetermined weight (capacity that cooperates the oil pressure platform mould that uses), and it is inserted in the oil pressure platform mould of preheating, be preheated to earlier about 165 ℃, at 165 ± 2 ℃ of temperature and pressure 160～200kg/cm
2Condition under act on 20～30 minutes (time length determines according to mold thickness), after making the abundant bridge formation of footwear material batching and foaming in this expanded material, open the oil pressure platform, then compression molding is the foaming plate of the starch-EVA of modification, promptly can be made into shoe-pad through suitably cutting again.Prepared shoe-pad is carried out the relevant physical property measurement of footwear material, and its result is shown in table-1.
Table-1 concrete example one prepared shoe-pad physical property measurement result
＜concrete example two 〉
It mainly is the consumption that changes each composition in the mixture, just get modification starch 1250 gram, with EVA component (containing EVA 3600 grams and EVA reclaimed materials 1100 grams), polyolefin 550 grams, talcum powder 380 grams, blowing agent 160 grams, bridging agent (DCP) 36 grams, hard ester acid 72 grams and Zinc Oxide 48 grams are formulated as mixture.Method for making, preparation process condition and＜concrete example one〉identical, last prepared footwear material finished product also is a shoe-pad.This shoe-pad is carried out the relevant physical property measurement of footwear material, and its result is shown in table-2.
Table-2 concrete examples two prepared shoe-pad physical property measurement results
＜concrete example three 〉
It mainly is the consumption that changes each composition in this mixture, just get modification starch 1500 gram, with EVA component (containing EVA 4500 grams and EVA reclaimed materials 1200 grams), polyolefin 630 grams, talcum powder 490 grams, blowing agent 190 grams, bridging agent (DCP) 45 grams, hard ester acid 83 grams and Zinc Oxide 56 grams are formulated as mixture.Method for making, preparation process condition and＜concrete example one〉identical, last prepared footwear material finished product also is a shoe-pad.This shoe-pad is carried out the relevant physical property measurement of footwear material, and its result is shown in table-3.
Table-3 concrete examples three prepared shoe-pad physical property measurement results
＜concrete example four 〉
Get modification starch 1000 gram, with EVA1200 gram, polyolefin 600 grams, talcum powder 300 grams, blowing agent 80 grams, bridging agent (DCP) 20 grams, hard ester acid 17 grams and Zinc Oxide 50 grams are formulated as a mixture.Above-mentioned material is inserted small-sized profit by in the mixer behind the mix in advance, start mixer and begin to carry out 10 to 15 minutes mixing operation, treat that temperature continues to rise to about 120 ℃, mixing having carried out 6～15 minutes, can make the complete hot melt of this mixture and evenly be mixed into footwear material batching, just can be toppled over out by mixing channel this moment with this footwear material batching.Agglomerating batching placed carry out the slice program on two rollers to form the expanded material of sheet, starch-EVA the expanded material that takes by weighing the modification that has gone out sheet is to predetermined weight (capacity that cooperates the oil pressure platform mould that uses), and it is inserted in the oil pressure platform mould of preheating, be preheated to earlier about 165 ℃, at 165 ± 2 ℃ of temperature and pressure 160～200kg/cm
2Condition under act on 20～50 minutes (time length is determined by mold thickness), after making the footwear material batching bridge formation and foaming in this expanded material, open the oil pressure platform, then compression molding is the foaming plate of the starch-EVA of modification, end finished product uses in the footwear for further making, this foaming plate through thermoforming processing, just can make end finished product in the footwear again.To carrying out the relevant physical property measurement of footwear material in the end in the prepared footwear, its result is shown in table-4.
Substrate property testing result in table-4 concrete examples four prepared footwear
＜concrete example five 〉
It mainly is the consumption that changes each composition in the mixture, just get modification starch 1250 gram, with EVA1400 gram, polyolefin 700 grams, talcum powder 380 grams, blowing agent 96 grams, bridging agent (DCP) 25 grams, hard ester acid 23 grams and Zinc Oxide 60 grams are formulated as this mixture.Method for making, preparation process condition and＜concrete example four〉identical, last prepared footwear material finished product is the end in the footwear.To carrying out the relevant physical property measurement of footwear material in the end in these footwear, its result is shown in table-5.
Substrate property testing result in table-5 concrete examples five prepared footwear
＜concrete example six 〉
It mainly is the consumption that changes each composition in this mixture, just get modification starch 1500 gram, with EVA1600 gram, polyolefin 700 grams, talcum powder 490 grams, blowing agent 102 grams, bridging agent (DCP) 32 grams, hard ester acid 30 grams and Zinc Oxide 70 grams are formulated as this mixture.Method for making, preparation process condition and＜concrete example four〉identical, last prepared footwear material finished product is the big ends of footwear.To carrying out the relevant physical property measurement of footwear material in the big end of these footwear, its result is shown in table-6.
The big substrate property testing of table-6 concrete examples six prepared footwear result
Result according to aforementioned six concrete examples, can find out that first three concrete example is in order to make the shoe-pad of three kinds of different hardness, the the 4th and the 5th concrete example is to be used for making at the bottom of the footwear of two kinds of different hardness, the 6th concrete example is to be used to make the big end of footwear, testing result according to table-1～table-6, the end and the big end of footwear, have predetermined strength respectively in the footwear material finished product shoe-pad that demonstration is made, the footwear, and can both meet the rerum natura requirement of footwear material.
Wherein, in shoe-pad, the footwear end different with the big end of footwear because of its application purpose, so that its rerum natura requires is also different.Shoe-pad is because of directly contacting with wearer foot, and its flexibility is had relatively high expectations, so its hardness is lower, and in the footwear end and the big end of footwear because of must cooperating the motion of foot, so its to tension intensity, percentage elongation, tearing strength, peel off having relatively high expectations of project such as tearing strength.In addition, because of the rerum natura of shoe-pad require relatively low, so have part can use the EVA reclaimed materials in the EVA component in its mixture, to reduce cost of material.
By above explanation as can be known, the manufacture method of bio-based macromolecule footwear material of the present invention can be obtained following effect and advantage, so can reach purpose of the present invention really:
Utilize starch after hydrolysis and esterification treatment, the usefulness of the starch ingredients of the modification that is obtained, compatibility in the time of improving it and mix mutually with the EVA component, and can form stable bond, cooperate other auxiliary composition and predetermined preparation process condition, can carry out foaming processing equally smoothly, to make constitutionally stable various footwear material finished product, the footwear material of being made still can be kept light weight and soft comfortable characteristic, and the footwear material finished product of being made, the back shows that its rerum natura can meet footwear material rerum natura specification really after testing, and has practical value.Therefore, the mixture of manufacture method of the present invention by the starch ingredients that contains the predetermined ratio modification is provided be as the raw material of making the footwear material, can effectively reduce the consumption of EVA component and can reach the environmental protection purpose of carbon reduction and reduce cost of material.The footwear material finished product of being made still can keep the structural strength of being scheduled to and can meet user demand, makes the present invention not only meet the environmental protection demand, has more the characteristic and the advantage that can reduce manufacturing cost.
Claims (24)
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| CN 200910174647 CN102019705B (en) | 2009-09-21 | 2009-09-21 | Method for manufacturing biobased macromolecule shoe material |
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| CN 200910174647 CN102019705B (en) | 2009-09-21 | 2009-09-21 | Method for manufacturing biobased macromolecule shoe material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226015A (en) * | 2011-06-11 | 2011-10-26 | 吴宝玲 | Starch composite foamed material and its production method |
| CN102775644A (en) * | 2012-03-16 | 2012-11-14 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| CN105622987A (en) * | 2014-11-25 | 2016-06-01 | 鸿明环保科技股份有限公司 | Ethylene-vinyl acetate copolymer mixture foaming material with high plant source content, and manufacturing method and application thereof |
| US9486368B2 (en) | 2013-12-05 | 2016-11-08 | Medline Industries, Inc. | Disposable hygienic article with means for diagnostic testing |
| CN107603001A (en) * | 2016-07-11 | 2018-01-19 | 鸿明环保科技股份有限公司 | Low-foaming-ratio biomass composite foamed sheet and manufacturing method thereof |
| CN114276583A (en) * | 2021-11-24 | 2022-04-05 | 深圳国至新材料科技有限公司 | Degradable foaming slipper material with high starch content and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587078A1 (en) * | 1992-09-07 | 1994-03-16 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing biodegradable resin foam |
| CN1087575A (en) * | 1992-11-30 | 1994-06-08 | 聚上企业股份有限公司 | Ethylene-vinyl acetate copolymer direct foaming one-piece molded shoe sole manufacturing method |
| CN1107777A (en) * | 1994-03-04 | 1995-09-06 | 林金昭 | EVA one-time injection foam molding shoe platform (sole) manufacturing method |
| CN1134348A (en) * | 1995-04-28 | 1996-10-30 | 财团法人鞋类设计及技术研究中心 | Quantitative extrusion manufacturing method of ethylene-vinyl acetate copolymer sole |
| CN1218991C (en) * | 1998-12-14 | 2005-09-14 | 普兰蒂克有限公司 | Biodegradable polymer |
| CN1970611A (en) * | 2006-08-02 | 2007-05-30 | 福州大学 | Process for preparing EVA/PE/starch composite foam material |
-
2009
- 2009-09-21 CN CN 200910174647 patent/CN102019705B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0587078A1 (en) * | 1992-09-07 | 1994-03-16 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing biodegradable resin foam |
| CN1087575A (en) * | 1992-11-30 | 1994-06-08 | 聚上企业股份有限公司 | Ethylene-vinyl acetate copolymer direct foaming one-piece molded shoe sole manufacturing method |
| CN1107777A (en) * | 1994-03-04 | 1995-09-06 | 林金昭 | EVA one-time injection foam molding shoe platform (sole) manufacturing method |
| CN1134348A (en) * | 1995-04-28 | 1996-10-30 | 财团法人鞋类设计及技术研究中心 | Quantitative extrusion manufacturing method of ethylene-vinyl acetate copolymer sole |
| CN1218991C (en) * | 1998-12-14 | 2005-09-14 | 普兰蒂克有限公司 | Biodegradable polymer |
| CN1970611A (en) * | 2006-08-02 | 2007-05-30 | 福州大学 | Process for preparing EVA/PE/starch composite foam material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226015A (en) * | 2011-06-11 | 2011-10-26 | 吴宝玲 | Starch composite foamed material and its production method |
| CN102226015B (en) * | 2011-06-11 | 2013-03-13 | 晋江成昌鞋业有限公司 | Starch composite foamed material and its production method |
| CN102775644A (en) * | 2012-03-16 | 2012-11-14 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| CN102775644B (en) * | 2012-03-16 | 2015-04-22 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| US9486368B2 (en) | 2013-12-05 | 2016-11-08 | Medline Industries, Inc. | Disposable hygienic article with means for diagnostic testing |
| US10583047B2 (en) | 2013-12-05 | 2020-03-10 | Medline Industries, Inc. | Disposable hygienic article with means for diagnostic testing |
| US11376166B2 (en) | 2013-12-05 | 2022-07-05 | Medline Industries, Lp | Disposable hygienic article with means for diagnostic testing |
| US12023228B2 (en) | 2013-12-05 | 2024-07-02 | Medline Industries, Lp | Disposable hygienic article with means for diagnostic testing |
| CN105622987A (en) * | 2014-11-25 | 2016-06-01 | 鸿明环保科技股份有限公司 | Ethylene-vinyl acetate copolymer mixture foaming material with high plant source content, and manufacturing method and application thereof |
| CN107603001A (en) * | 2016-07-11 | 2018-01-19 | 鸿明环保科技股份有限公司 | Low-foaming-ratio biomass composite foamed sheet and manufacturing method thereof |
| CN107603001B (en) * | 2016-07-11 | 2020-08-11 | 鸿明环保科技股份有限公司 | Biomass composite foamed sheet with low foaming ratio and method for producing the same |
| CN114276583A (en) * | 2021-11-24 | 2022-04-05 | 深圳国至新材料科技有限公司 | Degradable foaming slipper material with high starch content and preparation method thereof |
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