CN104669744B - Outer coating type high-performance PO film and preparation method thereof - Google Patents

Outer coating type high-performance PO film and preparation method thereof Download PDF

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Publication number
CN104669744B
CN104669744B CN201310637869.2A CN201310637869A CN104669744B CN 104669744 B CN104669744 B CN 104669744B CN 201310637869 A CN201310637869 A CN 201310637869A CN 104669744 B CN104669744 B CN 104669744B
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film
master batch
functional master
preparation
performance
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CN104669744A (en
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张权政
原新宝
王瑀
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Panjin Liaohe agricultural plastic products Co.
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Panjin Liaohe Agricultural Plastic Products Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties

Abstract

The invention provides an outer coating type high-performance PO film and a preparation method thereof. The outer coating type high-performance PO film is characterized by being in a two-layered structure including a PO basic film and an outer coating layer, wherein the PO basic film is composed of three laminated structures including a mechanical strength layer, a transparent heat-preservation layer and a coating carrier. The preparation method comprises the following five steps of preparation of functional master batches, preparation of the PO basic film by three-layered co-extrusion, corona treatment, on-line coating, and drying and rolling. The outer coating type high-performance PO film has the good mechanical strength, low-temperature flexibility and optical performance; the wind resistance and cold resistance are improved, and the dripping and fog clearing lasting period of a product can reach 24 months, so that the light utilization rate of an agricultural film is increased; and the main contradiction that the function and the service life of the agricultural film do not synchronize is solved, so that the use value of the agricultural film is improved and the service life of the agricultural film is remarkably prolonged.

Description

A kind of outer application type high-performance po film and preparation method thereof
Technical field
The present invention relates to a kind of agricultural film and preparation method thereof, more particularly to a kind of outer application type high-performance po film and Its preparation method, belongs to agricultural film manufacturing technology field.
Background technology
At present, feature agricultural film product mainly adopts linear low density polyethylene (lldpe) and Low Density Polyethylene (ldpe) manufacture, generally Shortcomings in terms of mechanical property；Because the mist degree that lldpe and ldpe resin has in itself is larger, And then make agricultural film light utilization efficiency, heat-insulating property aspect Shortcomings it is impossible to reaching high yield, shortening crop growth phase and minimizingization Fertilizer and the effect of Pesticide use amount.Meanwhile, more than traditional agricultural film by the way of inner additive type non-drop fog-eliminating agent, use in agricultural film In, under the extracting effect of film surface water droplet in canopy, the drip agent adding in thin film, fog dispersal agent molecule constantly move to film surface Move and run off with water droplet, thus gradually losing drip fog dispersal function, traditional approach drip fog dispersal effect duration is typically only 5-7 Month, asynchronous with agricultural film service life, lead to agricultural film to lose use value due to the forfeiture of partial function.
Po is referring to of polyolefine material, comprises multiple high molecular polymer such as pe, pp, eppe, poe, eva, its characteristic Have nothing in common with each other with purposes, agricultural po film is a kind of new agricultural film, its transparency, heat-insulating property and persistently fog dispersal, drip ability ratio More prominent, its production technology abroad has very big difference with domestic, and Japan typically adopts double face printing process, its product homogeneous, There is obvious advantage in stability.But, typically below 10 meters, wide cut generally requires right the current width of japanese product Connect.Domestic po film manufacturer uses coating stoving process, and its product quality is uneven, and typically all blowing completes Directly sprayed using the temperature of film afterwards, effect can only achieve half a year to 1 year.
Content of the invention
It is an object of the invention to solving the problems referred to above that prior art exists, after research repeatedly and many experiments, lead to Cross reasonable selection and optimum organization, give the outer application type high-performance po film of a kind of high transparent, high intensity, long-acting anti-dropping type And preparation method thereof.
The present invention adopts the technical scheme that: a kind of outer application type high-performance po film, it is characterized in that: by outer coat and po Ranvier's membrane is constituted, and described po Ranvier's membrane is made up of mechanical strength layer, heat-insulation layer, coated carrier layer, wherein po Ranvier's membrane raw material Including: mlldpe, ldpe, eppe, poe, long-lived functional master batch, transparent heat-insulation functional master batch.
The outer application type high-performance po film that the present invention is given can also adopt the following technical scheme that.
Described po Ranvier's membrane, is characterized in that.
The mass percent of mechanical strength layer consists of:
Mlldpe/eppe resin: 87 ~ 92%, long-lived functional master batch 8 ~ 13%.
The mass percent of heat-insulation layer consists of:
Eppe/poe resin 85 ~ 90%, transparent heat-insulation functional master batch 10 ~ 15%.
The mass percent of coated carrier layer consists of:
Poe/eva resin 87 ~ 92%, long-lived functional master batch 8 ~ 13%.
Wherein.
The prescription quality percentage of long-lived functional master batch is:
Low Density Polyethylene (ldpe) 75 ~ 85%, hindered amine as light stabilizer 6 ~ 8%, UV absorbent 2 ~ 4%,
Composite antioxidant 2 ~ 4%, transparent nucleater 3 ~ 7%, dispersant 3 ~ 5%, slipping agent 1 ~ 3%,
Ppa processing aid 1-2 ‰.
The prescription quality percentage of transparent heat-insulation functional master batch is:
Eppe/poe resin 50 ~ 65%, hindered amine as light stabilizer 3 ~ 5%, UV absorbent 2 ~ 4%,
Composite antioxidant 1 ~ 3%, transparent heat-insulation agent 30 ~ 40%, dispersant 5 ~ 8%.Ppa processing aid 1-2 ‰.Wherein.
Mlldpe is the linear low density polyethylene resin of metallocene catalysis, has narrow molecular weight distribution, and mechanical strength is high Feature, the mlldpe resin of preferably mi=1.0 ~ 1.5g/10min, tensile break strength >=37mpa.
Eppe is the novel polyethylene resin that a kind of molecular structure is concluded the speech between lldpe and ldpe, has excellent low temperature Outside the performances such as heat sealability, high intensity, also there is high transparency, high glaze, the easily characteristic, preferably mi=0.5g/ such as processing 10min.
Poe is the abbreviation of ethylene-octene copolymer, and feature is that resistance to low temperature, pliability are excellent, with prominent saturating Bright property and processing characteristics, preferably mi=1.0 ~ 1.5g/10min.
Eva is the abbreviation of ethylene-vinyl acetate copolymer, has outstanding low temperature flexibility and the transparency, preferably mi= 1.0~1.5g/10min.
Hindered amine as light stabilizer is th-944: poly- [[6- [(1,1,3,3- tetramethyl butyl) amine] -1,3,5- triazine -2,4- Diyl] [(2,2,6,6- tetramethyl -4- piperidines) imines] -1,6- two dihexyl [(2,2,6,6- tetramethyl -4- piperidines) imines].
UV absorbent is uv-327:2-(2 '-hydroxyl -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole and uv- 531:2- hydroxyl -4- oxy-octyl benzophenone compounds.
Composite antioxidant is b215: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and three [2.4- di-tert-butyl-phenyl] phosphite ester compounding.
Transparent nucleater is Sorbitol benzal derivant dbs, and dispersant is low molecular weight polyethylene wax (pe-wax), feels well Lubrication prescription is erucyl amide, and transparent heat-insulation agent is a nanometer aluminum magnesium hydrocarbonate.Processing aid ppa is a kind of fluorine-containing polymer.
The preparation method of this outer application type high-performance po film that the present invention is given, has been characterized in following steps.
(1) po film dedicated parent material preparation: this masterbatch is inhaled by 40 ~ 65% powder carrier resin, 3 ~ 5% hindered amine ultraviolet Receive agent, 3 ~ 5% hindered phenol composite antioxidant, 1 ~ 3% dispersant, 3 ~ 7% transparent nucleater, 20 ~ 45% transparent heat-insulation agent Composition.Necessary dispersant and processing aid is added in preparation process.Preparation technology is: each component of precise in proportion, warp Extrude on shj-65 parallel double-screw extruder after super mixer mixing, temperature is 140 ~ 190 DEG C, then water cooled, lead Draw, air-cooled, pelletizing, drying.
The ethylene-octene copolymer (poe) by octene content 5% ~ 10% for the described vector resin, the second of va content 8%-14% Alkene-acetate ethylene copolymer (eva) or mi=1 ~ 2g/10minldpe) one or more of composition.
Hindered amine as light stabilizer is one or more of 622,944.
UV absorbent by uv531, one or more of 327 form.
Hindered phenol antioxygen be antioxidant 1010,1076, one or more of st-252, b215.
(2) preparation of three-layer co-extruded po Ranvier's membrane: three-layer co-extruded po Ranvier's membrane is by mechanical strength layer, high heat-insulation layer, coating Carrier layer is constituted.Mechanical strength layer is raw materials used to be preferably mlldpe/eppe/ mixing, and ratio is 45 ~ 55/55 ~ 45；High insulation Layer is raw materials used to be preferably eppe/poe/ insulation masterbatch mixing, is preferably in a proportion of 40 ~ 50/25 ~ 35/15 ~ 20；Coated carrier layer The raw materials used poe/eva that is preferably mixes, and is preferably in a proportion of 35 ~ 45/40 ~ 60/.
(3) sided corona treatment: most of plastic sheetings (as poly- hydrocarbon thin film) belong to non-polar polymer, surface tension is relatively low, and one As in 29-30mn/m, theoretically, if the surface tension of object is less than 33mn/m, the ink being currently known and binding agent All therefore cannot to carry out corona method process to its surface in adhesion-tight above.Its handling principle is to apply on a processing device Increase frequency, high-tension electricity so as to produce high frequency, electrion, produce tiny intensive hyacinthine spark.Produce after air ionization Plastic sheeting in the presence of highfield, in acceleration shock treatment device for the various ions.The chemical bond of plastic molecules is made to break Split and degrade, increase surface roughness and surface area.Substantial amounts of ozone also can be produced, ozone is a kind of strong oxidizer during electric discharge, Plastic molecules can be made to aoxidize, produce carbonyl and the stronger group of peroxide isopolarity, thus improve its surface energy.Make film table Face reaches 40-42 dyne, and such solution is easier to be attached to film surface.
(4) online coating: outer for preprepared coating liquid deionized water is diluted in proportion, deionized water electrical conductivity Control in 5.0-10.0 μ s/cm, the po Ranvier's membrane after sided corona treatment immerses coating liquid and with the speed of 20 ~ 25m/min from painting Covering in groove derives, and completes to coat online operation.
(5) winding is dried: import drying baker through the po film of coating and dried, drying temperature is set as 70 ~ 80 DEG C, receive Volume speed is synchronous with coating speed: 20 ~ 25m/min.
Compared with prior art, the invention has the beneficial effects as follows.
Using new type resin eppe and poe in the production process of outer application type high-performance po film, in long-lived functional master batch Middle use transparent nucleater dbs, is substantially improved po film light transmittance, thus getting a promotion to the utilization rate of light, reaching raising and using The purpose of efficiency.
Due to the use of new type resin eppe and poe, make po film have more preferable mechanical strength and low temperature flexibility, make po Film wind resistance cold performance gets a promotion, and improves the service life of po film.
Outer coat is more preferable with the combination of po Ranvier's membrane, extends drip effect duration.
Because transparent heat insulating material selects properly, thus to lifting temperature of shed, shortening the generation of plant growth time beneficial Effect.
Specific embodiment
Embodiment 1.
Prepare specifically comprising the following steps that of outer application type high-performance po film
A, the preparation of long-lived functional master batch
Low Density Polyethylene (mi=1.0g/10min) 75
Hindered amine as light stabilizer th944 2
Ultraviolet absorbent uv-327/uv-531 0.5/1.5kg
Composite antioxidant b215 0.6kg
Transparent nucleater dbs 2.2kg
Dispersant pe-wax 0.5kg
Slipping agent 0.3kg
Processing aid ppa 0.08kg
B, the preparation of transparent heat-insulation functional master batch
Eppe(mi=1.0g/10min) 25kg
Poe(mi=1.5g/10min) 25kg
Hindered amine as light stabilizer th944 1.2
Ultraviolet absorbent uv-327/uv-531 0.3/1.0kg
Composite antioxidant b215 0.4kg
Nanometer aluminum magnesium hydrocarbonate 27kg
Dispersant pe-wax 0.8kg
Processing aid ppa 0.15kg.
The each component precise of above a, b masterbatch, puts into high-speed mixer mixing, enters through 65 parallel double-screw extruders Row pelletize, stand-by after being dried.
The preparation of c, po Ranvier's membrane.
The preparation of described po Ranvier's membrane is using three-layer co-extruded blow molding process, and resin used by each layer is by following requirement choosing With being proportionally added into a, b functional master batch, through three-layer co-extruded technique blow molding, overall film thickness is 0.1mm, layer thickness proportion For 1/2/1, each layer raw material is chosen as follows by mass percentage:
Outer layer (coated carrier layer)
Poe(mi=1.0g/10min) 40%
Eva(mi=1.5g/10min, va content 12%) 48%
Functional master batch a 12%
Middle level (transparent insulating layer)
Eppe(mi=0.5g/10min) 45%
Poe(mi=1.0g/10min) 43%
Functional master batch b 12%
Internal layer (mechanical strength layer)
Mlldpe(mi=0.8g/10min) 45%
Eppe(mi=0.5g/10min) 43%
Functional master batch a 12%.
The material weighing enters the mixing that mixer carries out 3-5min, makes a gift to someone respectively in three extruders, extrudes captain For 30:1, die head is three layers of complex centre feed type to footpath ratio, material respectively the melting through three extruders, plastify, be expressed into three Layer co-extrusion die head continues plasticizing through spirillum, is jointly extruded by circular port mould, is combined tubular membrane tube, film from circular die extrusion The lower cross directional stretch of compressed air inflation effect that the Guan Mo heart blows into, passes through the air cooling in circular air port and upper traction nip rolls simultaneously Longitudinal drawing-off and be obtained po Ranvier's membrane.
D, sided corona treatment: before po Ranvier's membrane immersion coating liquid, sided corona treatment is carried out to thin film, by surge, in height In the presence of piezoelectric field, electron stream carries out strong impact to po Ranvier's membrane, makes film wildness, becomes coarse, increases table Area, thus improving the immersional wetting to Ranvier's membrane surface for the coating liquid, the Ranvier's membrane surface tension requirements after sided corona treatment reach 42 dynes per centimeter.
E, coating operation: pre-configured coating liquid is poured in coating groove, and the po Ranvier's membrane after sided corona treatment is qualified exists Passed through from coating groove with the speed of 20 ~ 25m/min under deflector roll effect, complete to coat.
F, drying winding: the po film completing to coat enters drying baker, speed is synchronously 20 ~ 25m/min with coating operation, dries 75 DEG C of dry temperature.Rolling, note rice, weighing, inspection, packaging and storage.
G, performance test: the outer coating functions po film prepared according to process above is carried out with performance test, tests content For: light transmittance, tensile strength, elongation at break, drip effect duration, result record such as subordinate list.
Embodiment 2(conventional functionality agricultural film).
A, b step are with embodiment 1.
The preparation of c, po Ranvier's membrane.
The preparation of described po Ranvier's membrane is using three-layer co-extruded blow molding process, and each layer selects high performance resin on request, It is proportionally added into a, b functional master batch, through three-layer co-extruded technique blow molding, overall film thickness is 0.1mm, and layer thickness proportion is 1/ 2/1, each layer raw material is chosen as follows by mass percentage:
Outer layer (coated carrier layer)
Lldpe(mi=1.0g/10min) 45%
Eva(mi=1.5g/10min, va content 12%) 43%
Functional master batch a 12%
Middle level (transparent insulating layer)
Ldpe(mi=0.5g/10min) 45%
Lldpe(mi=1.0g/10min) 43%
Functional master batch b 12%
Internal layer (mechanical strength layer)
Mlldpe(mi=0.8g/10min) 55%
Ldpe(mi=0.5g/10min) 33%
Functional master batch a 12%
Method for manufacturing thin film and d e f g step and embodiment 1 with.
Subordinate list: outer coating functions po film detects performance table

Claims (1)

1. a kind of outer application type high-performance po film is it is characterised in that be made up of outer coat and po Ranvier's membrane, described po Ranvier's membrane It is made up of mechanical strength layer, heat-insulation layer, coated carrier layer, wherein:
Po Ranvier's membrane raw material includes: mlldpe, ldpe, eppe, poe, long-lived functional master batch, transparent heat-insulation functional master batch；
The composition of described po Ranvier's membrane:
The mass percent of mechanical strength layer consists of:
Mlldpe/eppe resin: 87 ~ 92%, long-lived functional master batch 8 ~ 13%；
The mass percent of heat-insulation layer consists of:
Eppe/poe resin 85 ~ 90%, transparent heat-insulation functional master batch 10 ~ 15%；
The mass percent of coated carrier layer consists of:
Poe/eva resin 87 ~ 92%, long-lived functional master batch 8 ~ 13%；
The formula of described longevity functional master batch is:
Low Density Polyethylene mi=1.0g/10min 75
Hindered amine as light stabilizer th944 2
Ultraviolet absorbent uv-327 0.5kg
uv-531 1.5kg
Composite antioxidant b215 0.6kg
Transparent nucleater dbs 2.2kg
Dispersant pe-wax 0.5kg
Slipping agent 0.3kg
Processing aid ppa 0.08kg；
The formula of described transparent heat-insulation functional master batch is:
eppe mi=1.0g/10min 25kg
poe mi=1.5g/10min 25kg
Hindered amine as light stabilizer th944 1.2
Ultraviolet absorbent uv-327 0.3kg
uv-531 1.0kg
Composite antioxidant b215 0.4kg
Nanometer aluminum magnesium hydrocarbonate 27kg
Dispersant pe-wax 0.8kg
Processing aid ppa 0.15kg.
CN201310637869.2A 2013-12-03 2013-12-03 Outer coating type high-performance PO film and preparation method thereof Active CN104669744B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105479708A (en) * 2015-11-25 2016-04-13 罗敏聪 Production equipment for agricultural PO light-conversion film
CN106633563B (en) * 2016-10-09 2019-01-29 聊城华塑工业有限公司 Polyolefin skins film masterbatch with dust reduction capability and its application in greenhouse films
CN109511424A (en) * 2018-11-10 2019-03-26 盘锦益丰农业科技发展有限公司 High heat preservation PO film of infrared ray barrier and preparation method thereof
CN112476836A (en) * 2020-11-17 2021-03-12 王彩云 Preparation method of polyethylene flame-retardant plastic master batch
CN113103702B (en) * 2021-05-17 2023-04-18 山东清田塑工有限公司 High-dustproof high-heat-preservation pesticide-resistant PO (polyolefin) film functional master batch, five-layer co-extruded PO film and preparation method thereof

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CN202805849U (en) * 2012-09-25 2013-03-20 天津市天塑科技集团有限公司第二塑料制品厂 Coating-type light transferring membrane
CN103213361A (en) * 2013-04-19 2013-07-24 山东天鹤塑胶股份有限公司 Coating type persistent dripping polyethylene greenhouse film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202805849U (en) * 2012-09-25 2013-03-20 天津市天塑科技集团有限公司第二塑料制品厂 Coating-type light transferring membrane
CN103213361A (en) * 2013-04-19 2013-07-24 山东天鹤塑胶股份有限公司 Coating type persistent dripping polyethylene greenhouse film

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