CN102019736B - Oxo-biodegradable BOPP (biaxially-oriented polypropylene) film and preparation method thereof - Google Patents
Oxo-biodegradable BOPP (biaxially-oriented polypropylene) film and preparation method thereof Download PDFInfo
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- 229920006378 biaxially oriented polypropylene Polymers 0.000 title abstract description 23
- 239000011127 biaxially oriented polypropylene Substances 0.000 title abstract description 23
- 229920001237 Oxo Biodegradable Polymers 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006065 biodegradation reaction Methods 0.000 claims description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 42
- 239000004743 Polypropylene Substances 0.000 claims description 35
- -1 polypropylene Polymers 0.000 claims description 35
- 229920001155 polypropylene Polymers 0.000 claims description 35
- 210000002615 epidermis Anatomy 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 29
- 230000002457 bidirectional effect Effects 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 22
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000008104 plant cellulose Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000009736 wetting Methods 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 8
- 150000003973 alkyl amines Chemical class 0.000 claims description 7
- 238000003851 corona treatment Methods 0.000 claims description 7
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract 4
- 239000010410 layer Substances 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000010408 film Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000011475 lollipops Nutrition 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Abstract
The invention discloses an oxo-biodegradable BOPP (biaxially-oriented polypropylene) film and a preparation method thereof, belonging to the technical field of the processing of BOPP films. The oxo-biodegradable BOPP film comprises an upper surface layer, a sandwich layer and a lower surface layer, and is prepared by the following steps of: adding 0.5-1.0 percent of an oxygen-containing biodegradable agent and other constituents into the upper surface layer, the sandwich layer and the lower surface layer, melting and extruding by utilizing a double-screw extruder at low temperature of 220-230 DEG C, and then biaxially stretching on a Germany Bruckner machine. The structure of the traditional equipment is not changed in the invention, at the same time, the oxo-biodegradable BOPP film can solve the problem of white pollution, can not change the function and appearance of the traditional BOPP and produce harmful substances to the environment during decomposition process, and has the advantages of controlled degradation period, non-toxicity and the like.
Description
Technical field
The present invention relates to a kind of oxidation-type biodegradation bidirectional stretching polypropylene film and manufacture method thereof, belong to the bidirectional stretching polypropylene film processing technique field.
Background technology
Existing plastic refuse processing mode generally has four kinds: tradition is buried, is incinerated, recovery, compost.Studies confirm that plastic cement need to be taken more than 400 years the time and just can slowly decompose, so tradition is buried with compost and can not fundamentally be solved environmental pollution.Incinerate discarded plastic cement and can produce great amount of carbon dioxide and toxic gas, weighting ring environment pollution and greenhouse effects.Main is that above processing method only limits to the situation that discarded plastic cement is collected.Bidirectional stretching polypropylene film (being the BOPP film) is widely used in the aspect packings such as stationery, photograph album, clothes, cigarette, cake, ice lolly as a kind of outstanding packaging material.The scattered property of its packing and the uncertainty of use cause after the use basically discardedly, can not be collected in other words and be collected fully.More than 600 ten thousand tons of the actual year consumption figures of present global BOPP film, China accounts for wherein 30%, and global demand also maintains 8% higher increase level.The BOPP film becomes the important component part of " white pollution "." white pollution " defiantly ball-joint is subjected to the limit.Solving the plastic cement pollution problem is the difficult problem of present packaging industry, also is the difficult problem that present international environmental protection faces.Countries is hereby made laws and is supported plastic cement degraded (such as the U.S., Japan, Brazil, Romania etc.) in the world, and China successively lists light/biodegradable plastic, degradable plastics mulch film in country " eight or five ", " 95 " emphasis program for tackling key problems in science and technology especially.All strengthening research aspect the BOPP film degradation both at home and abroad at present, and obtaining more achievement, especially aspect light degradation and biodegradation, but the light degradation behavior can only occur in the place of light, and certain limitation is arranged.Biodegradation realizes by adding modified starch, but it has certain influence to product function and outward appearance, and some product is difficult to final decomposition.The oxidation-type biodegradation just can be decomposed in the place of aerobic, final decomposed substance on environment without impact, it does not affect product function and outward appearance, so Development and Production oxidation-type biodegradation BOPP novel thin film is international and domestic trend of the times, is the needs of environment for human survival.Will substitute existing universal BOPP film future fully.
Summary of the invention
The invention provides a kind of oxidation-type biodegradation bidirectional stretching polypropylene film and manufacture method thereof, this film is nontoxic, degradation cycle is controlled, can not change existing BOPP function and outward appearance, can not produce the material that environment is had harm in the decomposable process.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of oxidation-type biodegradation bidirectional stretching polypropylene film, comprise upper epidermis, sandwich layer, lower top layer, the component that described upper epidermis selects percentage by weight to be respectively polypropylene 96.5-98%, antitack agent 1.5-2.5%, contain oxygen biodegradation agent 0.5-1.0% is formulated; The component that sandwich layer selects percentage by weight to be respectively HOPP 93-97.5%, antistatic additive 1.0-3.0%, slipping agent 1.0-3.0%, contain oxygen biodegradation agent 0.5-1.0% is formulated; Lower top layer select percentage by weight be respectively polypropylene 96.5-98%, antitack agent 1.5-2.5%, contain the component of oxygen biodegradation agent 0.5-1.0% formulated or select percentage by weight to be respectively delustring material 99.0-99.5%, the component that contains oxygen biodegradation agent 0.5-1.0% is formulated.
Further preferred as such scheme, antitack agent, the antitack agent in the lower top layer in the described upper epidermis are synthetic silica class antitack agent; Polypropylene in the upper epidermis is a kind of in HOPP or the COPP; Polypropylene in the lower top layer is a kind of in HOPP or the COPP; Upper epidermis, lower top layer and the selected HOPP of sandwich layer, its molten how all are 2.6-3.2g/10min.
Described antistatic additive is the alkyl amine antistatic additive; Described slipping agent is erucyl amide class slipping agent, is BOPP routine additive.
The described oxygen biodegradation agent that contains is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.
Described iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.
The thickness of described upper epidermis is that the thickness of 1.0 μ, sandwich layer is that the thickness on 10.0-58.0 μ, lower top layer is 1.0-3.0 μ.
Oxidation-type biodegradation bidirectional stretching polypropylene film is a kind of in light film, heat-sealing film, the matt film.
A kind of manufacture method of oxidation-type biodegradation bidirectional stretching polypropylene film comprises the steps:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder by percentage by weight claimed in claim 1.
(2) with 220-240 ℃ of low temperature extrusion plasticizing.Low temperature is conducive to the stable of biodegradation agent, and double screw extruder is conducive to the abundant melting of biodegradation agent and disperses.
(3) slab cooling: the water temperature of sharp cooling roll is controlled at 30-40 ℃, and the water temperature of tank is controlled at 30-40 ℃.
(4) longitudinal stretching: stretching ratio 4.7-5.0.
(5) cross directional stretch: stretching ratio 10.0-12.0.
(6) traction: Thickness Measurement by Microwave, carry out sided corona treatment, guarantee that the film wetting tension is greater than 38 dyne.
(7) rolling.
(8) timeliness is three days: under 35 ℃ temperature environment, left standstill 3 days.(stress relaxation and additive migration)
Key technical feature of the present invention is to utilize the catalytic capability of transition metal ions iron, manganese, nickel to make large molecular olefine chain oxidative scission for being engulfed little strand by microorganism, improve the speed of growing of microorganism by the natural plant cellulose that is added in the product, accelerate product and finally be decomposed into carbon dioxide and water.
Because being the needed by human body trace element, nontoxic.Can control degradation cycle by content, to satisfy the product life cycle.Because the life cycle of BOPP is 1 year, adding proportion of the present invention is 1%, after degradation cycle is 1 year.
The present invention utilizes the double screw extruder advantage to adopt 220-240 ℃ of low temperature expressing technique, is conducive to the abundant melting of biodegradation agent and disperses and be difficult for thermal cracking to lose efficacy.
It is lower that the present invention adds the shared total content of active ingredient, less than 1100ppm, so can not change outward appearance and the function of common BOPP, because being a kind of adding technology, can produce on existing German Bruckner biaxial tension line.
The oxidation-type biodegradation bidirectional stretching polypropylene film of manufacturing of the present invention compares outward appearance with common bidirectional stretching polypropylene film and physical property does not have large variation, but oxidation-type biodegradation bidirectional stretching polypropylene film obviously decomposes fast (testing standard is ASTM6954) than common bidirectional stretching polypropylene film in 320 hours UV aging processes detect.
Antitack agent in the upper epidermis is that the model that Constant general company in Suzhou produces is the synthetic silica class antitack agent of AB6018CPP or AB6018PP; Antitack agent in the lower top layer is that the model that Constant general company in Suzhou produces is the synthetic silica class antitack agent of AB6018CPP or AB6018PP; The delustring material is that the model that Zhejiang Prov Kaili Packaging Materials Co., Ltd produces is the delustring material of XG-01.
The specific embodiment
The invention will be further described below by specific embodiment, but the present invention is not limited by following examples.
Embodiment 1:
Oxidation-type biodegradation Biaxially oriented polypropylene light film of the present invention, the component that its upper epidermis selects percentage by weight to be respectively HOPP 96.5%, antitack agent 2.5%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The component that sandwich layer selects percentage by weight to be respectively HOPP 93%, antistatic additive 3.0%, slipping agent 3.0%, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.Antistatic additive is the alkyl amine antistatic additive; Slipping agent is erucyl amide class slipping agent.The component that lower top layer selects percentage by weight to be respectively HOPP 96.5%, antitack agent 2.5%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The THICKNESS CONTROL of upper epidermis is that the THICKNESS CONTROL of 1.0 μ, sandwich layer is that the THICKNESS CONTROL on 12.0 μ, lower top layer is 1.0 μ.Containing the oxygen biodegradation agent is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.Iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.
Concrete manufacture method is as follows:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder.
(2) extrusion plasticizing: each component in double screw extruder, is melt extruded under 240 ℃ temperature conditions.
(3) slab cooling: the extruder melt extrusion is extruded through sharp cooling roll and tank through flat film mouth slit and is cooled to sheet, mouthful die slot crack 2.5mm, and the water temperature of sharp cooling roll is controlled at 35 ℃, and the water temperature of tank is controlled at 35 ℃.
(4) longitudinal stretching: sheet is 138 ℃ of 28 seconds of lower preheating in preheat temperature, stretches 4.8 times 1.5 seconds of typing under 140 ℃ of temperature under 130 ℃ of temperature.
(5) cross directional stretch: sheet in transverse stretching machine under 170 ℃ of temperature 7 seconds of preheating, under 157 ℃ of temperature, laterally stretch 10.0 times 7 seconds of typing under 170 ℃ of temperature.
(6) traction: hauling speed 440m/min, Thickness Measurement by Microwave is carried out sided corona treatment, guarantees that the film wetting tension equals greatly 38 dyne.
(7) rolling: film is rolled into semi-finished product (common process is just seldom given unnecessary details at this) under suitable tension.
(8) timeliness is three days: under 35 ℃ temperature environment, leave standstill 3 days (stress relaxation and additive migration).
Embodiment 2:
Oxidation-type biodegradation Biaxially oriented polypropylene light film of the present invention, the component that its upper epidermis selects percentage by weight to be respectively HOPP 97.5%, antitack agent 1.5%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The component that sandwich layer selects percentage by weight to be respectively HOPP 97%, antistatic additive 1.0%, slipping agent 1.0%, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.Antistatic additive is the alkyl amine antistatic additive; Slipping agent is erucyl amide class slipping agent.The component that lower top layer selects percentage by weight to be respectively HOPP 97.5%, antitack agent 1.5%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The THICKNESS CONTROL of upper epidermis is that the THICKNESS CONTROL of 1.0 μ, sandwich layer is that the THICKNESS CONTROL on 35.0 μ, lower top layer is 1.0 μ.Containing the oxygen biodegradation agent is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.Iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.Concrete manufacture method is as follows:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder.
(2) extrusion plasticizing: each component in double screw extruder, is melt extruded under 230 ℃ temperature conditions.
(3) slab cooling: the extruder melt extrusion is extruded through sharp cooling roll and tank through flat film mouth slit and is cooled to sheet, mouthful die slot crack 2.7mm, and the water temperature of sharp cooling roll is controlled at 30 ℃, and the water temperature of tank is controlled at 30 ℃.
(4) longitudinal stretching: sheet is 140 ℃ of 40 seconds of lower preheating in preheat temperature, stretches 4.8 times 2.2 seconds of typing under 142 ℃ of temperature under 130 ℃ of temperature.
(5) cross directional stretch: sheet in transverse stretching machine under 170 ℃ of temperature 10 seconds of preheating, under 157 ℃ of temperature, laterally stretch 10.0 times 10 seconds of typing under 170 ℃ of temperature.
(6) traction: hauling speed 297m/min, Thickness Measurement by Microwave is carried out sided corona treatment, guarantees that the film wetting tension equals greatly 38 dyne.
(7) rolling: film is rolled into semi-finished product (common process is just seldom given unnecessary details at this) under suitable tension.
(8) timeliness is three days: under 35 ℃ temperature environment, leave standstill 3 days (stress relaxation and additive migration).
Embodiment 3:
The component that oxidation-type biodegradation Biaxially oriented polypropylene Double-side hot sealer of the present invention, its upper epidermis select percentage by weight to be respectively COPP 97.5%, antitack agent 1.5%AB6018CPP, contain oxygen biodegradation agent 1.0% is formulated.The component that sandwich layer selects percentage by weight to be respectively HOPP 95%, antistatic additive 2.0%, slipping agent 2.0%, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.Antistatic additive is the alkyl amine antistatic additive; Slipping agent is erucyl amide class slipping agent.The component that lower top layer selects percentage by weight to be respectively COPP 97.5%, antitack agent 1.5%AB6018CPP, contain oxygen biodegradation agent 1.0% is formulated.The THICKNESS CONTROL of upper epidermis is that the THICKNESS CONTROL of 1.0 μ, sandwich layer is that the THICKNESS CONTROL on 23.0 μ, lower top layer is 1.0 μ.Containing the oxygen biodegradation agent is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.Iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.Concrete manufacture method is as follows:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder.
(2) extrusion plasticizing: each component in double screw extruder, is melt extruded under 230 ℃ temperature conditions.
(3) slab cooling: the extruder melt extrusion is extruded through sharp cooling roll and tank through flat film mouth slit and is cooled to sheet, mouthful die slot crack 2.7mm, and the water temperature of sharp cooling roll is controlled at 35 ℃, and the water temperature of tank is controlled at 35 ℃.
(4) longitudinal stretching: sheet is 128 ℃ of 35 seconds of lower preheating in preheat temperature, stretches 4.8 times 1.8 seconds of typing under 128 ℃ of temperature under 120 ℃ of temperature.
(5) cross directional stretch: sheet in transverse stretching machine under 170 ℃ of temperature 8.8 seconds of preheating, under 157 ℃ of temperature, laterally stretch 10.0 times 8.8 seconds of typing under 165 ℃ of temperature.
(6) traction: hauling speed 350m/min, Thickness Measurement by Microwave is carried out sided corona treatment, guarantees that the film wetting tension equals greatly 38 dyne.
(7) rolling: film is rolled into semi-finished product (common process is just seldom given unnecessary details at this) under suitable tension.
(8) timeliness is three days: under 35 ℃ temperature environment, leave standstill 3 days (stress relaxation and additive migration).
Embodiment 4:
Oxidation-type biodegradation Biaxially oriented polypropylene single face heat-sealing film of the present invention, the component that its upper epidermis selects percentage by weight to be respectively HOPP 97.0%, antitack agent 2.0%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The component that sandwich layer selects percentage by weight to be respectively HOPP 95%, antistatic additive 2.0%, slipping agent 2.0%, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.Antistatic additive is the alkyl amine antistatic additive; Slipping agent is erucyl amide class slipping agent.The component that lower top layer selects percentage by weight to be respectively COPP 97.5%, antitack agent 1.5%AB6018CPP, contain oxygen biodegradation agent 1.0% is formulated.The THICKNESS CONTROL of upper epidermis is that the THICKNESS CONTROL of 1.0 μ, sandwich layer is that the THICKNESS CONTROL on 23.0 μ, lower top layer is 1.0 μ.Containing the oxygen biodegradation agent is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.Iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.Concrete manufacture method is as follows:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder.
(2) extrusion plasticizing: each component in double screw extruder, is melt extruded under 230 ℃ temperature conditions.
(3) slab cooling: the extruder melt extrusion is extruded through sharp cooling roll and tank through flat film mouth slit and is cooled to sheet, mouthful die slot crack 2.7mm, and the water temperature of sharp cooling roll is controlled at 35 ℃, and the water temperature of tank is controlled at 35 ℃.
(4) longitudinal stretching: sheet is 128 ℃ of 35 seconds of lower preheating in preheat temperature, stretches 4.8 times 1.8 seconds of typing under 128 ℃ of temperature under 120 ℃ of temperature.
(5) cross directional stretch: sheet in transverse stretching machine under 170 ℃ of temperature 8.8 seconds of preheating, under 157 ℃ of temperature, laterally stretch 10.0 times 8.8 seconds of typing under 165 ℃ of temperature.
(6) traction: hauling speed 350m/min, Thickness Measurement by Microwave is carried out sided corona treatment, guarantees that the film wetting tension equals greatly 38 dyne.
(7) rolling: film is rolled into semi-finished product (common process is just seldom given unnecessary details at this) under suitable tension.
(8) timeliness is three days: under 35 ℃ temperature environment, leave standstill 3 days (stress relaxation and additive migration).
Embodiment 5:
Oxidation-type biodegradation Biaxially oriented polypropylene matt film of the present invention, the component that its upper epidermis selects percentage by weight to be respectively HOPP 97.0%, antitack agent 2.0%AB6018PP, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.The component that sandwich layer selects percentage by weight to be respectively HOPP 95%, antistatic additive 2.0%, slipping agent 2.0%, contain oxygen biodegradation agent 1.0% is formulated, and the molten how of HOPP is 2.6-3.2g/10min.Antistatic additive is the alkyl amine antistatic additive; Slipping agent is erucyl amide class slipping agent.The component that lower top layer selects percentage by weight to be respectively delustring material 99.0%, contain oxygen biodegradation agent 1.0% is formulated.And the THICKNESS CONTROL of upper epidermis is that the THICKNESS CONTROL of 1.0 μ, sandwich layer is that the THICKNESS CONTROL on 14.0 μ, lower top layer is 3.0 μ.Containing the oxygen biodegradation agent is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP.Iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires little 5 μ that equal.Concrete manufacture method is as follows:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder.
(2) extrusion plasticizing: each component in double screw extruder, is melt extruded under 240 ℃ temperature conditions.
(3) slab cooling: the extruder melt extrusion is extruded through sharp cooling roll and tank through flat film mouth slit and is cooled to sheet, mouthful die slot crack 2.5mm, and the water temperature of sharp cooling roll is controlled at 40 ℃, and the water temperature of tank is controlled at 40 ℃.
(4) longitudinal stretching: sheet is 135 ℃ of 31 seconds of lower preheating in preheat temperature, stretches 4.8 times 1.6 seconds of typing under 135 ℃ of temperature under 125 ℃ of temperature.
(5) cross directional stretch: sheet in transverse stretching machine under 170 ℃ of temperature 7.7 seconds of preheating, under 157 ℃ of temperature, laterally stretch 10.0 times 7.7 seconds of typing under 170 ℃ of temperature.
(6) traction: hauling speed 400m/min, Thickness Measurement by Microwave is carried out sided corona treatment, guarantees that the film wetting tension equals greatly 38 dyne.
(7) rolling: film is rolled into semi-finished product (common process is just seldom given unnecessary details at this) under suitable tension.
(8) timeliness is three days: under 35 ℃ temperature environment, leave standstill 3 days (stress relaxation and additive migration).
Table 1: be the comparison test data of oxidation-type biodegradation bidirectional stretching polypropylene film case study on implementation 1 of the present invention with the universal product:
| Test item title and unit | Embodiment 1 | The universal product | Examination criteria |
| Thickness (μ) | 15 | 15 | / |
| Carbonylic absorbance (%) | 0.0116 | 0.0088 | ASTM6954 |
| Hot strength (vertical/horizontal stroke) Mpa | 149.6/298.8 | 151.5/296.6 | ASTM D-882 |
| Elongation at break (vertical/horizontal stroke) % | 163.5/62 | 168.4/61.2 | ASTM D-882 |
| Percent thermal shrinkage (vertical/horizontal stroke) % | 4.0/0.9 | 4.2/0.6 | ASTM D-1204 |
| Coefficient of friction (quiet/moving) | 0.324/0.315 | 0.331/0.313 | ASTM D-1894 |
| Mist degree % | 1.12 | 1.20 | ASTM D-1003 |
| Glossiness % | 93.8 | 91.5 | ASTM D-2457 |
| Heat seal strength | / | / | TAPPI-683 |
| Wetting tension mN/m | 38 | 38 | ASTM D-2578 |
(annotate: check data is timeliness measurement data after three days, below identical)
Table 2: be the comparison test data of oxidation-type biodegradation bidirectional stretching polypropylene film case study on implementation 2 of the present invention with the universal product:
| Test item title and unit | Embodiment 2 | The universal product | Examination criteria |
| Thickness (μ) | 35 | 35 | / |
| Carbonylic absorbance (%) | 0.0106 | 0.0081 | ASTM6954 |
| Hot strength (vertical/horizontal stroke) Mpa | 137.95/324.3 | 144.88/329.28 | ASTM D-882 |
| Elongation at break (vertical/horizontal stroke) % | 179.2/52.3 | 181.8/56 | ASTM D-882 |
| Percent thermal shrinkage (vertical/horizontal stroke) % | 3.2/1.0 | 3.3/0.7 | ASTM D-1204 |
| Coefficient of friction (quiet/moving) | 0.547/0.410 | 0.534/0.444 | ASTM D-1894 |
| Mist degree % | 1.08 | 1.23 | ASTM D-1003 |
| Glossiness % | 92.38 | 89.91 | ASTM D-2457 |
| Heat seal strength | / | / | TAPPI-683 |
| Wetting tension mN/m | 39 | 39 | ASTM D-2578 |
Table 3: be the comparison test data of oxidation-type biodegradation bidirectional stretching polypropylene film case study on implementation 3 of the present invention with the universal product:
| Test item title and unit | Embodiment 3 | The universal product | Examination criteria |
| Thickness (μ) | 25 | 25 | / |
| Carbonylic absorbance (%) | 0.0110 | 0.0078 | ASTM6954 |
| Hot strength (vertical/horizontal stroke) Mpa | 134.3/278.9 | 139.7/285.3 | ASTM D-882 |
| Elongation at break (vertical/horizontal stroke) % | 171/54 | 167/59 | ASTM D-882 |
| Percent thermal shrinkage (vertical/horizontal stroke) % | 4.0/0.6 | 3.9/0.5 | ASTM D-1204 |
| Coefficient of friction (quiet/moving) | 0.251/0.248 | 0.249/0.257 | ASTM D-1894 |
| Mist degree % | 1.80 | 1.73 | ASTM D-1003 |
| Glossiness % | 90.8 | 89.99 | ASTM D-2457 |
| Heat seal strength | 3.62 | 3.51 | TAPPI-683 |
| Wetting tension mN/m | 42 | 42 | ASTM D-2578 |
Table 4: be the comparison test data of oxidation-type biodegradation bidirectional stretching polypropylene film case study on implementation 4 of the present invention with the universal product:
| Test item title and unit | Embodiment 4 | The universal product | Examination criteria |
| Thickness (μ) | 25 | 25 | / |
| Carbonylic absorbance (%) | 0.0098 | 0.0069 | ASTM6954 |
| Hot strength (vertical/horizontal stroke) Mpa | 149.6/298.8 | 147.5/295.3 | ASTM D-882 |
| Elongation at break (vertical/horizontal stroke) % | 158/56 | 156/59 | ASTM D-882 |
| Percent thermal shrinkage (vertical/horizontal stroke) % | 3.79/0.6 | 3.8/0.6 | ASTM D-1204 |
| Coefficient of friction (quiet/moving) | 0.281/0.278 | 0.278/0.293 | ASTM D-1894 |
| Mist degree % | 1.63 | 1.65 | ASTM D-1003 |
| Glossiness % | 91.02 | 88.98 | ASTM D-2457 |
| Heat seal strength | 3.53 | 3.48 | TAPPI-683 |
| Wetting tension mN/m | 38 | 38 | ASTM D-2578 |
Table 5: be the comparison test data of oxidation-type biodegradation bidirectional stretching polypropylene film case study on implementation 5 of the present invention with the universal product:
| Test item title and unit | Embodiment 5 | The universal product | Examination criteria |
| Thickness (μ) | 18 | 18 | / |
| Carbonylic absorbance (%) | 0.0109 | 0.0083 | ASTM6954 |
| Hot strength (vertical/horizontal stroke) Mpa | 129.9/278.1 | 132.3/269.2 | ASTM D-882 |
| Elongation at break (vertical/horizontal stroke) % | 164/56 | 161/54 | ASTM D-882 |
| Percent thermal shrinkage (vertical/horizontal stroke) % | 4.1/0.5 | 4.2/0.5 | ASTM D-1204 |
| Coefficient of friction (quiet/moving) | 0.331/0.387 | 0.328/0.461 | ASTM D-1894 |
| Mist degree % | 80.5 | 80.22 | ASTM D-1003 |
| Glossiness % | 4.01 | 3.57 | ASTM D-2457 |
| Heat seal strength | / | / | TAPPI-683 |
| Wetting tension mN/m | 38 | 38 | ASTM D-2578 |
Annotate: the corresponding raw material of above contrast product, additive are identical, and tester is identical.
From table 1, table 2, table 3, table 4, table 5, can find out, oxidation-type biodegradation bidirectional stretching polypropylene film of the present invention is compared with universal bidirectional stretching polypropylene film, physical property does not have the variation because of the interpolation of biodegradation agent, and its function is unaffected.Oxidation-type biodegradation bidirectional stretching polypropylene film is obviously fast than universal bidirectional stretching polypropylene film decomposition solution speed on biological decomposition.
Claims (6)
1. oxidation-type biodegradation bidirectional stretching polypropylene film, comprise upper epidermis, sandwich layer, lower top layer, it is characterized in that: the component that described upper epidermis selects percentage by weight to be respectively polypropylene 96.5-98%, antitack agent 1.5-2.5%, contain oxygen biodegradation agent 0.5-1.0% is formulated; The component that sandwich layer selects percentage by weight to be respectively HOPP 93-97.5%, antistatic additive 1.0-3.0%, slipping agent 1.0-3.0%, contain oxygen biodegradation agent 0.5-1.0% is formulated; Lower top layer select percentage by weight be respectively polypropylene 96.5-98%, antitack agent 1.5-2.5%, contain the component of oxygen biodegradation agent 0.5-1.0% formulated or select percentage by weight to be respectively delustring material 99.0-99.5%, the component that contains oxygen biodegradation agent 0.5-1.0% is formulated;
Wherein, the described oxygen biodegradation agent that contains is transition metal ions iron, manganese, nickel and natural plant cellulose and HOPP melt blended material, wherein the percentage composition of iron in blend is 3%, manganese, the nickel percentage composition in blend respectively is 2%, the percentage composition of natural plant cellulose in blend is 4%, and all the other are HOPP;
Described iron, manganese, nickel exist with ionic forms; Natural plant cellulose is the broken thing of natural plants, and its particle diameter requires less than or equal to 5 μ.
2. oxidation-type biodegradation bidirectional stretching polypropylene film as claimed in claim 1 is characterized in that: antitack agent, the antitack agent in the lower top layer in the described upper epidermis are synthetic silica class antitack agent; Polypropylene in the upper epidermis is a kind of in HOPP or the COPP; Polypropylene in the lower top layer is a kind of in HOPP or the COPP; Upper epidermis, lower top layer and the selected HOPP of sandwich layer, its molten how all are 2.6-3.2g/10min.
3. oxidation-type biodegradation bidirectional stretching polypropylene film as claimed in claim 1 or 2, it is characterized in that: described antistatic additive is the alkyl amine antistatic additive; Described slipping agent is erucyl amide class slipping agent.
4. oxidation-type biodegradation bidirectional stretching polypropylene film as claimed in claim 1 or 2 is characterized in that: the thickness of described upper epidermis is that the thickness of 1.0 μ, sandwich layer is that the thickness on 10.0-58.0 μ, lower top layer is 1.0-3.0 μ.
5. oxidation-type biodegradation bidirectional stretching polypropylene film as claimed in claim 4 is characterized in that: for a kind of in light film, heat-sealing film, the matt film.
6. the manufacture method of oxidation-type biodegradation bidirectional stretching polypropylene film as claimed in claim 1 is characterized in that comprising the steps:
(1) feeds intake: each component on upper epidermis, sandwich layer, lower top layer is put into respectively in each self-corresponding double screw extruder by percentage by weight claimed in claim 1;
(2) with 220-240 ℃ of low temperature extrusion plasticizing;
(3) slab cooling: the water temperature of sharp cooling roll is controlled at 30-40 ℃, and the water temperature of tank is controlled at 30-40 ℃;
(4) longitudinal stretching: stretching ratio 4.7-5.0;
(5) cross directional stretch: stretching ratio 10.0-12.0;
(6) traction: Thickness Measurement by Microwave, carry out sided corona treatment, guarantee that the film wetting tension is greater than 38 dyne;
(7) rolling;
(8) timeliness is three days: under 35 ℃ temperature environment, left standstill 3 days.
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| CN102950857B (en) * | 2012-11-14 | 2016-03-30 | 海南赛诺实业有限公司 | A kind of degradable Biaxially oriented polypropylene cigarette packaging film and manufacture method thereof |
| CN103587187B (en) * | 2013-05-22 | 2017-02-08 | 上海优珀斯材料科技有限公司 | Controllable degradation antiadherent film and preparation method |
| CN103895298B (en) * | 2014-04-12 | 2015-09-09 | 广东威孚包装材料有限公司 | Complete biodegradable salivation polypropylene film and manufacture method thereof |
| CN104553218B (en) * | 2015-01-13 | 2015-09-23 | 浙江凯利新材料股份有限公司 | Ultra-low temperature heat sealing bidirectional stretching polypropylene film and manufacture method thereof |
| CN108467585A (en) * | 2018-04-08 | 2018-08-31 | 厦门长塑实业有限公司 | Oxidation-type biodegradation biaxial tension biology base nylon film and preparation method thereof |
| CN110936687A (en) * | 2019-12-13 | 2020-03-31 | 福建兰天包装材料有限公司 | Low-glossiness anaerobic biodegradable biaxially oriented polypropylene film |
| CN111574774A (en) * | 2020-05-26 | 2020-08-25 | 安徽国风塑业股份有限公司 | Biodegradable BOPP film and preparation method thereof |
| CN113580704A (en) * | 2021-05-25 | 2021-11-02 | 安徽国风塑业股份有限公司 | Anaerobic biodegradable BOPP film and preparation method thereof |
| CN113736174A (en) * | 2021-08-25 | 2021-12-03 | 绍兴耐特塑胶有限公司 | Oxidized biodegradable biaxially oriented polypropylene net and manufacturing method thereof |
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| CN1426427A (en) * | 2000-05-30 | 2003-06-25 | 巴塞尔聚烯烃有限公司 | For producing propylene polymers that are suited for fiber spinning |
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