CN1814661A - Light/calcium biological synergetic environment degradeable food packing material - Google Patents
Light/calcium biological synergetic environment degradeable food packing material Download PDFInfo
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Abstract
This invention provides a wrapper of food of optical Ca biodegration cooperating with environment, which is made up of 10-70% CaSO<SUB>4</SUB>, 0.1-5% composite photosensitizer, 0.1-5% biodegration agent and polyolefin resin for rest. The preparation method includes: crushing CaSO4 to particles with the fineness greater than 800 mesh to be processed on the surface with a coupler, then to be mixed with other raw materials in a high speed mixer for 5-10 minutes then to be granulated in an extrusion granulating machine, in which, the temperature at each section is: feeding section: 120-160deg.C, the mixing section: 180-220deg.C, transporting section: 180-200deg.C, extrusion head: 170-190deg.C, the raw material particles are got to be processed further to get various wrapping products for food.
Description
Technical field
The present invention relates to a kind of light/calcium biological synergetic environment degradeable food packing material, belong to the material technology field.
Background technology
Degradative plastics can be divided into two big classes: a class is the matrix material that inorganic powder, plastics and various auxiliary agent are composited, and another kind of is the matrix material that modified starch class material (comprising cellulose family), plastics and various auxiliary agent are composited.
The inorganic powder that mainly uses on the present market is CaCO
3(comprising marble and rhombspar), talcum powder, this mainly is based on two reasons, and the one, these two kinds of powder sources are wide, cheap; The 2nd, manufacturer is more, and the purchasing of raw materials is easy.By present state of the art, loading level is about 30% mostly, and its ASTM experimental result biological degradability only is 2 grades, measures biodegradability and press existing standard, adopts international generation CO
2Method measure, its " degradation rate " also can't reach standard.
With CaCO
3For the material of main weighting material during as the disposable fast food tool, by general international standard, its acetic acid leachable should≤300mg/L, and because the generation that following reactive chemistry changes:
Cause the acetic acid leachable to exceed standard.
Experiment showed, that particle diameter is the CaCO of 5 μ m
3Content 〉=5% of powder in matrix material o'clock, its acetic acid leachable promptly can exceed standard, and becomes the technology barrier that can't go beyond in the packaging material for food production technology.
And be the matrix material of main weighting material with talcum powder, because the gloomy color belt of goods is given people's visual effect extreme difference, thereby limited its application in packaging material for food; Talcous major ingredient is SiO simultaneously
2, it has insoluble infusible characteristic, and after people's life-time service was the compound package material of main weighting material with talcum powder, talcum powder easily produced calculus in the human body inner accumulated, was detrimental to health, thereby was forbidden using in packaging material for food by a lot of countries.
For the starch system composite biological degradation plastic, though can overcome above-mentioned CaCO
3With some shortcomings of talcum powder matrix material, but, cause the intensity of wrapping material to reduce, thereby limited its addition, general starch content≤15% because it is big to the mechanical property damage of plastics own; Starch plastic is responsive to processing temperature simultaneously, processing difficulties, and the scrap stock in the course of processing are easily burnt in secondary processing and can't be utilized again; If making moist very easily to produce in storage and transportation, product goes mouldy; The color of goods is impure simultaneously, causes visual effect undesirable, all makes it be subjected to great obstruction in applying.
Therefore, seek a kind of suitable packing material, carry out rational formulating of recipe, make it both have CaCO
3Deng the advantage of inorganic powder, have the good biodegradability properties of starch plastic again, and the disposable fast food tool proprietary material of ideal visual effect becomes the needs in market.
Summary of the invention
The object of the present invention is to provide a kind of light/calcium biological synergetic environment degradeable food packing material.
Described material is obtained by following weight part feedstock production:
CaSO
4(anhydrous plaster powder) 10-70%
Complex photosensitizer 0.1-5%
The plain 0.1-5% of biological degradation
Surplus is polypropylene or polyethylene.
Described CaSO
4(anhydrous plaster powder) is preferably the 30-60% weight part.
The preferred 0.5-2% of described complex photosensitizer.
Described biological degradation element is preferably 2-3%.
Described CaSO
4Make through ore dressing, cleaning, calcining, pulverizing, whiteness answers 〉=90%, and particle diameter fineness 〉=800 orders should be through the coupling agent surface treatment before application.
Described coupling agent by the 0.3-1.2% weight part (with respect to CaSO
4) aluminic acid ester (main coupling agent) and the 0.4-0.6% weight part (with respect to CaSO
4) rare earth soap (helping coupling agent) form.
Described aluminic acid ester can be aluminate coupling agent DL-411-A, DL-411-AF or DL-411-DF.
Processing mode is: with CaSO
4Powder heated and stirred in high-speed mixer to remove top layer moisture, adds aluminic acid ester and the 0.4-0.6% rare earth soap of 0.3-1.2% to 80-90 ℃ then, mixes.
Described biological degradation element is the mixture of stearate, fatty acid amide and sodium alginate, and wherein three's blended part by weight is 1: 1: 2, by stearate, the fatty acid amide surface coating to sodium alginate, has improved the hydrophobic nature of the finished product.
Described stearate is preferably calcium stearate or iron stearate.
The preferred amine hydroxybenzene of described fatty acid amide, linolic acid acid amides or stearic amide.
Described complex photosensitizer is mixed by rare earth soap and organic photosensitive agent, and its part by weight is 1: 1～1: 2, and the use of complex photosensitizer has increased the absorption intensity of UV-light, improves about 20% approximately, and has widened the extinction spectrum of photosensitizers.
Described rare earth soap can be rare-earth stearate salt, Whitfield's ointment rare-earth salts, lauric acid rare-earth salts, oleic acid rare-earth salts, linolic acid rare-earth salts etc.; Preferred rare-earth stearate La, Whitfield's ointment Rare-Earth Ce, linolic acid rare earth Pr.
Described organic photosensitive agent can be ferric dimethyl dithiocarbamate, ferric diethyldithiocarbamate, dibutyl dithiocaarbamate iron; Preferred dibutyl dithiocaarbamate iron.
Described polypropylene preferably adopts the mixture of homo-polypropylene and Co-polypropylene, and blending ratio is preferably 1: 1.
Product preparation method of the present invention can for: at first calcium sulfate is crushed to particle fineness greater than 800 orders; by coupling agent it is carried out surface treatment then; after the processing; itself and each component raw material were mixed in high-speed mixer 5-10 minute; enter granulation in the extruding granulator then; each section temperature is set at: feeding section 120-160 ℃; mixing section 180-220 ℃; transportation section 180-200 ℃; extruder head 170-190 ℃, get feed particles, this feed particles is through further handling; get various food product pack goods, as food bag, disposable lunch-box or the like.
Described coupling agent by 0.3-1.2% (with respect to CaSO
4) aluminic acid ester (main coupling agent) and 0.4-0.6% (with respect to CaSO
4) rare earth soap (helping coupling agent) form.
Described surface treatment is: with CaSO
4Powder heated and stirred in high-speed mixer to remove top layer moisture, adds aluminic acid ester and the 0.4-0.6% rare earth soap of 0.3-1.2% to 80-90 ℃ then, mixes.
Described extruding granulator preferred parallel twin screw extruder.
Content ratio of the present invention is weight ratio.
The complex photosensitizer of amount of the present invention, through surveying the mechanical property that does not influence material, its light degradation property reaches the GB18006.1-1999 technical requirements; After photoinduction, material can continue oxidative degradation under no optical condition, has improved the thoroughness of degraded; Waste bury or compost after, because photodegradation makes material degradation, increased the wetting ability of plastics, help bacterium or microorganism breeds in plastics, help biodegradation process to carry out, itself and biological degradation element act synergistically, and have increased the biological degradability of material, realized that matrix material carries out the transition to oxidative degradation by photodegradation, promptly entered biodegradable conversion process.
The biological degradation element is the sub-compound of hydrophilic aliquot, helps the biological degradation of material, is easily eaten by bacterium, because its consumption is few, can produce big influence to the water-intake rate of matrix material, thereby can easy generation not go mouldy as starch plastic; Because molecular weight and molecular weight adds a kind of composition in the complex photosensitizer, can reduce the temperature that plastics burn.
Use the wrapping material of the formulation of product of the present invention, combinations color and lustre is pure white, non-variegation, good visual effect; CaSO
4Be insoluble to HAC, after a large amount of the filling, the acetic acid leachable of goods does not exceed standard; Prepared goods are generally (by the thickness and the intensity of illumination decision of goods) about 10-60 days through the photoinduction after date, can continue oxidative degradation under the lucifuge condition, until biological degradation; Utilize the bioaffinity and the oilness of calcium stearate and aliphatic amide, replace paraffin, realized coating, improved the affinity of PPG and matrix plastic the plain sodium alginate of biological degradation (PPG), because do not have paraffin in the prescription, its hexanaphthene leachable can not exceed standard; Owing to used a large amount of inorganic powder CaSO
4, make waste energy and municipal wastes realize synchronous processing, as burning and composting; The waste of product of the present invention can not pollute underground water, has good environment compatibility, and is specific as follows:
CaSO
4Be resourceful inorganic mineral, chemical property is stable, does not contain heavy metal, and waste can not constitute pollution to underground water source, and environmental hazard is less.
inorganic materials filled plastics are saved petroleum resources: calculate by inorganics filled 50% (W%), being converted into volume is 18%-20%, being converted into oil saves about 40% approximately, this had profound historical significance in today that petroleum resources lack day by day, angle from material and environmental protection coordinated development, replace macromolecular material to produce plastics with deriving from nature and returning in the inorganic mineral of nature, this itself is exactly the contribution to environmental protection.
The environmental protection effect that the inorganic mineral burns plastics: unrenewable plastic refuse enters garbage system the most at last, its processing mode is consistent with rubbish, wherein the burning effect of plastic refuse is one of gordian technique, waste incineration and generating electricity has obtained general applying in worldwide as the recycling of the energy.Plastic components easy coking when burning, easily agglomerating, hindered the abundant burning of inner component, the incomplete combustion of plastics will cause producing a large amount of CO gas, have extremely strong Greenhouse effect, and imperfect combustion part is attached on furnace wall and the fire grate, the conveying of rubbish and the circulation of air-flow are impacted, and quickened damage the furnace wall.The inorganic mineral filled plastics are equivalent to dilute plastic component, simultaneously CaSO
4Deng in burning process, having bulking effect, the perfect combustion of plastics had fabulous promoter action.
In a word, packaging material for food of the present invention has been considered the sanitary characteristics as packaging material for food, the characteristic that has possessed simultaneously general light, biodegradable plastic again, realize that refuse can be from the photoinduction degraded to biodegradable conversion, make the refuse can be by composting or burning disposal, can with the municipal wastes synchronous processing.Therefore promoting the use of of this material will have a tremendous social and economic benefits.
Embodiment
Embodiment 1
Present embodiment is the preparation of PE film product.
Calcium sulfate is crushed to 800 orders, gets 45Kg, enter in the high-speed mixer heated and stirred to 80 ℃, divide three times then 135g aluminate coupling agent DL-411-A and 270g rare-earth stearate La added high-speed mixer, mixing and stirring;
Get PE (7000F) raw material 51Kg, rare-earth stearate La500g, dibutyl dithiocaarbamate iron 500g, calcium stearate 750g, amine hydroxybenzene (Ningbo associating biotechnology limited liability company) 750g, sodium alginate 1.5Kg, add high-speed mixer, mixed 10 minutes, enter granulation in the parallel double-screw extruding granulator then, each section temperature is set at: 160 ℃ of feeding sections, 180 ℃ of mixing sections, 200 ℃ of transportation sections, 170 ℃ of extruder heads, extruding pelletization makes food bag through blown film; Thickness 30-40 μ m.
Embodiment 2
Present embodiment is the preparation of PP cutlery box.
Calcium sulfate is crushed to 1000 orders, gets 56Kg, enter in the high-speed mixer heated and stirred to 90 ℃, add 672g aluminate coupling agent DL-411-AF and 224g Whitfield's ointment Rare-Earth Ce then, mixing and stirring;
Get PP (1300) and each 20Kg of PP (8303), Whitfield's ointment Rare-Earth Ce 333g, ferric dimethyl dithiocarbamate 666g, calcium stearate 750g, linolic acid acid amides 750g, sodium alginate 1.5Kg, add high-speed mixer, mixed 10 minutes, enter granulation in the parallel double-screw extruding granulator then, each section temperature is set at: 120 ℃ of feeding sections, 220 ℃ of mixing sections, 180 ℃ of transportation sections, 190 ℃ of extruder heads, extruding pelletization makes disposable snack box through plastics sucking moulding; Box body thickness is 0.8-1.0mm.
Embodiment 3
Present embodiment is the preparation of PE film product.
Calcium sulfate is crushed to 1200 orders, gets 30Kg, heated and stirred to 85 ℃ in high-speed mixer adds 180g aluminic acid ester DL-411-DF and 150g linolic acid rare earth Pr, mixing and stirring then;
Get PE (1F7B) raw material 66Kg, linolic acid rare earth Pr 1000g, ferric diethyldithiocarbamate 1000g, iron stearate 500g, stearic amide 500g, sodium alginate 1000g, add high-speed mixer, mixed 5 minutes, enter granulation in the parallel double-screw extruding granulator then, each section temperature is set at: 135 ℃ of feeding sections, 200 ℃ of mixing sections, 195 ℃ of transportation sections, 180 ℃ of extruder heads, extruding pelletization makes food bag through blown film; Thickness 40-50 μ m.
Embodiment 4
Present embodiment is the preparation of PP cutlery box.
Calcium sulfate is crushed to 800 orders, gets 70Kg, heated and stirred to 85 ℃ in high-speed mixer adds 630g then
Aluminate coupling agent DL-411-A and 350g rare-earth stearate La, mixing and stirring;
Get PP (1300) 4.5Kg and each 20Kg of PP (8303), rare-earth stearate La200g, dibutyl dithiocaarbamate iron 300g, calcium stearate 1.25Kg, amine hydroxybenzene 1.25Kg, sodium alginate 2.5Kg, add high-speed mixer, in high-speed mixer, mixed 10 minutes, enter granulation in the parallel double-screw extruding granulator then, each section temperature is set at: 145 ℃ of feeding sections, 195 ℃ of mixing sections, 185 ℃ of transportation sections, 185 ℃ of extruder heads, extruding pelletization makes disposable snack box through plastics sucking moulding; Box body thickness is 0.5-0.7mm.
Experimental example 1
The outdoor exposure experiment that this experimental example carries out for embodiment 3 products and the Light lysis Film that does not add inorganics.
The Light lysis Film that does not add inorganics is according to the preparation of the consumption of embodiment 3 and method, and difference is, not the sulfur acid calcium powder.
Experimental technique: film sample is fixed on the framework, is positioned on the outdoor roof platform and tans by the sun, sample is towards south, and obliquity is 45 °, and sample plot is Beijing, and the time is 7-9 month.
Following table is an experimental result, is that sample photodegradation PE film is under the situation of particular value at CI, the time of being experienced, has shown the degradation property of different PE films thus.
| Photodegradation PE film | Contain 30%CaSO4 photodegradation PE film | |
| The time of CI=6 (my god) | 6 | 5 |
| The time of CI=45 (my god) | 35 | 30 |
Conclusion: inorganic mineral has promoter action to plastic degradation.
Mechanism: behind a large amount of content inorganic fillings, increased the O of material self in the PE Light lysis Film
2Transmitance, thereby help the material oxidation degraded.
Comparative example 1
This comparative example compares the influence aspect the chemical oxygen demand (COD) of water at its waste by the like product (plastics containing starch) to the embodiment of the invention 2,4 products and prior art, and the environmental protection characteristic of the embodiment of the invention 2 products is described.
Under equal conditions, the embodiment of the invention 2 products are in 15-20 days time, and embrittlement becomes the fragment of diameter less than 5mm, with the waste of plastics containing starch the influence that the chemical oxygen demand (COD) (COD) of water produces seen the following form:
| Sample | Contain 15% starch plastic | Embodiment 2 | Embodiment 4 |
| COD | 96 | 0 | 0 |
As seen, the waste of product of the present invention does not influence the chemical oxygen demand (COD) of water resources.
Comparative example 2
This comparative example is the degradation experiment comparative data of the embodiment of the invention 1 product and prior art products.
Common 10 days CI of photodegradation PE film illumination (carbonyl index) is 20, but after soil buried 1 year, the CI value was 28, M
η(viscosity-average molecular weight) changes little still greater than 10000.
10 days the CI of PE film illumination that uses material of the present invention to make is 15, and after soil was buried 60 months, its CI value was 50, M
ηBe reduced to 4000.
Above-mentioned description of test material of the present invention behind light induction, have tangible lucifuge and continue oxidative degradation and biodegradable characteristic, after its soil is buried 1 year, its viscosity-average molecular weight reduces to 4000, this moment, plastics entered during the embrittlement, the embrittlement product can be by water infiltration, microorganism can breed on relatively little molecular chain, enters the biological decomposition phase; Existing photodegradation PE film does not then have this characteristic.
Claims (10)
1, a kind of light/calcium biological synergetic environment degradeable food packing material is characterized in that, described material is obtained by following weight part feedstock production:
Complex photosensitizer 0.1-5% CaSO
410-70%
The plain 0.1-5% surplus of biological degradation is polypropylene or polyethylene.
2, wrapping material according to claim 1 is characterized in that, described CaSO
4Be preferably the 30-60% weight part;
The preferred 0.5-2% of described complex photosensitizer; Described biological degradation element is preferably 2-3%.
3, wrapping material according to claim 1 and 2 is characterized in that, described CaSO
4Make through ore dressing, cleaning, calcining, pulverizing, whiteness answers 〉=90%, and particle fineness should be through the coupling agent surface treatment before application greater than 800 orders.
4, wrapping material according to claim 3 is characterized in that, described coupling agent is made of aluminic acid ester and the 0.4-0.6% rare earth soap of 0.3-1.2%, and described content is all with respect to CaSO
4Calculate.
5, wrapping material according to claim 1 is characterized in that, described complex photosensitizer is mixed by rare earth soap and organic photosensitive agent, and its part by weight is 1: 1～1: 2.
6, wrapping material according to claim 5 is characterized in that, described rare earth soap can be rare-earth stearate salt, Whitfield's ointment rare-earth salts, lauric acid rare-earth salts, oleic acid rare-earth salts, linolic acid rare-earth salts; Preferred rare-earth stearate La, Whitfield's ointment Rare-Earth Ce, linolic acid rare earth Pr; Described organic photosensitive agent can be ferric dimethyl dithiocarbamate, ferric diethyldithiocarbamate, dibutyl dithiocaarbamate iron; Preferred dibutyl dithiocaarbamate iron.
7, wrapping material according to claim 1 is characterized in that, described biological degradation element is the mixture of stearate, fatty acid amide and sodium alginate, and wherein three's mixed weight ratio is 1: 1: 2; Described stearate is preferably calcium stearate or iron stearate; The preferred amine hydroxybenzene of described fatty acid amide, linolic acid acid amides or stearic amide.
8; the preparation method of any described light/calcium biological synergetic environment degradeable food packing material of claim 1-7; it is characterized in that; described method is: calcium sulfate is crushed to particle fineness greater than 800 orders; with coupling agent it is carried out surface treatment then; after the processing; itself and each component raw material were mixed in high-speed mixer 5-10 minute; enter granulation in the extruding granulator then; each section temperature is set at: feeding section 120-160 ℃, and mixing section 180-220 ℃, transportation section 180-200 ℃; extruder head 170-190 ℃; get feed particles, this feed particles gets various food product pack goods through further handling.
9, preparation method according to claim 8 is characterized in that, described coupling agent is made up of the aluminic acid ester of 0.3-1.2% and the rare earth soap of 0.4-0.6%; Described surface treatment is with CaSO
4Powder heated and stirred in high-speed mixer to remove top layer moisture, adds aluminic acid ester and the 0.4-0.6% rare earth soap of 0.3-1.2% to 80-90 ℃ then, mixes; Described content ratio is all with respect to CaSO
4Calculate.
10, according to Claim 8 or 9 described preparation methods, it is characterized in that described extruding granulator preferred parallel twin screw extruder.
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|---|---|---|---|
| CNB2006100026933A CN100451062C (en) | 2006-01-27 | 2006-01-27 | Light/calcium biological synergetic environment degradeable food packing material |
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|---|---|---|---|
| CNB2006100026933A CN100451062C (en) | 2006-01-27 | 2006-01-27 | Light/calcium biological synergetic environment degradeable food packing material |
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| CN1814661A true CN1814661A (en) | 2006-08-09 |
| CN100451062C CN100451062C (en) | 2009-01-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295793A (en) * | 2011-07-07 | 2011-12-28 | 宋旭 | Highly extended oxidation-degradable high-molecular packaging material and preparation method thereof |
| CN102391557A (en) * | 2011-07-07 | 2012-03-28 | 宋旭 | High-filling controllable oxidative degradation packaging material and preparation method thereof |
| CN106750773A (en) * | 2016-12-06 | 2017-05-31 | 宁波芸生纺织品科技有限公司 | A kind of biological packing material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094068A (en) * | 1994-04-09 | 1994-10-26 | 福建省测试技术研究所 | The light-sensitive catalyst of organic rare-earth complex compound of degradable polyethylene film and purposes |
| CN1074778C (en) * | 1997-07-17 | 2001-11-14 | 田长澄 | Degradeable plastic and plant composite material and its preparation |
-
2006
- 2006-01-27 CN CNB2006100026933A patent/CN100451062C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295793A (en) * | 2011-07-07 | 2011-12-28 | 宋旭 | Highly extended oxidation-degradable high-molecular packaging material and preparation method thereof |
| CN102391557A (en) * | 2011-07-07 | 2012-03-28 | 宋旭 | High-filling controllable oxidative degradation packaging material and preparation method thereof |
| CN106750773A (en) * | 2016-12-06 | 2017-05-31 | 宁波芸生纺织品科技有限公司 | A kind of biological packing material and preparation method thereof |
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| CN100451062C (en) | 2009-01-14 |
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