CN1040006C - Preparation method of weather-resistant polyethylene film - Google Patents

Preparation method of weather-resistant polyethylene film Download PDF

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Publication number
CN1040006C
CN1040006C CN 90101638 CN90101638A CN1040006C CN 1040006 C CN1040006 C CN 1040006C CN 90101638 CN90101638 CN 90101638 CN 90101638 A CN90101638 A CN 90101638A CN 1040006 C CN1040006 C CN 1040006C
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film
masterbatch
polyethylene
light
new ldpe
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CN 90101638
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CN1056696A (en
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叶永成
姜诚德
宋玉春
刘福菊
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention belongs to a method for manufacturing a weather-resistant plastic film. Hindered amine is selected as a main light stabilizer, benzophenone and triazine are selected as auxiliary light stabilizers, phenol is selected as an antioxidant, phthalocyanine series and azo series pigments are matched with an ultraviolet light stabilizer to form a visible light regulator, and a low molecular weight polymer is selected as a carrier. Adding the light stabilizer, the antioxidant and the visible light modifier to prepare a master batch. The weather-resistant polyethylene film with the service life of 2-3 years is prepared by taking polyolefin resin (polyethylene or polyolefin blend mainly containing polyethylene) as raw material resin, adding master batch, other auxiliary agents and visible light regulator.

Description

The preparation method of wear well polythene film
The invention belongs to a kind of manufacture method of weather resistant plastic film.
As agricultural plastic film, mainly adopted polyvinyl chloride (PVC) RESINS is raw material in the past.Though polyvinyl chloride film is than weather-resistant, tensile strength is higher, and heat-insulating property is better and be easy to bonding.But owing to contain a large amount of softening agent, processing and use in softening agent volatilize in addition that the resin decomposition can cause environmental pollution.Greenhouse canopy internal surface water of condensation is easily extracted the film internal plasticizer out and is vertically dripped, cause crop pest, also because resistance to low temperature is bad, comparatively high temps is easy to again relax, easily absorption dust and density of film are bigger, cost up in the unit surface, shortcoming such as not easy to store is replaced by polyethylene film in recent years gradually.
The day disclosure special permission wear well polythene plastic sheeting for farm use that JP86203147 released, used resin and stablizer are:
Linear low density of polyethylene (d, 0.922g/cm 3) 90 parts
10 parts of ethene---acetate ethylene copolymers (sholexBM05-6)
(VA content 5%)
326 0.8 parts of ultraviolet absorbers Tinuvin
327 0.5 parts of ultraviolet absorbers Tinuvin
In this technology, because used resin is linear low density of polyethylene and ethene---the blend of acetate ethylene copolymer, has higher initial mechanical property so can guarantee film, but stablizer cooperates system unreasonable, do not use oxidation inhibitor again, only use two kinds of benzotriazole compounds as ultraviolet absorbers in the prescription, Tinuvin326 and Tinuvin327 itself is just bad to polyethylene light stabilising effect, and almost there is not a thermal oxidation resistance ability, therefore stronger thermal oxidative reaction must take place in resin in hot-work, produce oxy radicals such as carbonyl and hydroperoxide, can quicken the photooxidation reaction of film under atmospheric condition, shorten the work-ing life of film.In addition, used ultraviolet absorbers is always put higherly in the prescription, accounts for 1.3% of film weight greatly, increased the cost of film, the photo-stability efficiency of UV light stabilizing agent depends primarily on to be selected for use and cooperates, and not proportional with add-on, 1.3% has exceeded normal add-on.
The used resin of wear well polythene plastic sheeting for farm use that Romania patent RomRO8846 2 releases is the new LDPE (film grade) of MI0.3, it is thicker again to make film, so initial mechanical properties value is higher, it is improper that subject matter is that stablizer is selected for use, though also be to select for use a kind of hindered amine and a kind of benzophenone in the prescription as photostabilizer, and add the epoxy Fatty Alcohol(C12-C14 and C12-C18) as the fill-in light stablizer, but selected hindered amine is relatively poor to the polyethylene photo-stability efficiency, and the thermooxidizing of reinforcement effect is arranged in hot-work.Though attempt in the prescription with the epoxy Fatty Alcohol(C12-C14 and C12-C18) as the fill-in light stablizer because and can't form collaboration system between other stablizer, and itself is all not good to heat, light stability, so although film is very thick, weathering resistance only can reach about 2 years.All photostabilizer total amounts are up to 5.4% in this technology, and antioxygen dosage is up to 0.7%, and the total add-on of auxiliary agent is too high, reaches 14.6%, far exceeds normal add-on.Thickness promoter addition greatly in addition is too high, and the film cost is increased significantly, also brings difficulty to processing simultaneously.
The objective of the invention is to select hindered amines as the key light stablizer, with benzophenone, triazines is the fill-in light stablizer, make oxidation inhibitor with phenols, match with phthalocyanine series and azo series pigment and with UV light stabilizing agent and to be combined into the visible light conditioning agent, putting polymkeric substance with low molecule is carrier, be added with above-mentioned photostabilizer, oxidation inhibitor and visible light conditioning agent are made masterbatch.With polyethylene or based on the polyolefin blends of polyethylene, in add lubricant oleic acid acid amides, modifier polyethylene wax and masterbatch prepare the wear well polythene film that reaches 2-3 work-ing life.
The used polyolefin resin of the present invention is new LDPE (film grade) (melt refers to imitate 0.2-3.0), linear low density of polyethylene (melt index 0.5-3.0), the blend of new LDPE (film grade) (melt index 0.2-3.0) and linear low density of polyethylene (melt index 0.5-3.0).(first kind of blend).New LDPE (film grade) (melt index 0.2-3.0) and ethylene-vinyl acetate copolymer (melt index 0.5-3.0, VA content 2-15%) blend (second kind of blend).Linear low density of polyethylene (melt index 0.5-3.0) and ethylene-vinyl acetate copolymer (melt index 0.5-3.0, VA content 2-15%) blend (the third blend).In first kind of blend, linear low density of polyethylene content 5-30%, ethylene-vinyl acetate copolymer content 5-15% in second kind of blend, ethylene-vinyl acetate copolymer content 5-20% in the third blend, sneak into a small amount of linear low density of polyethylene in the new LDPE (film grade), can improve mechanical properties in films, and the adding of ethylene-vinyl acetate copolymer mainly there is contribution to the tough property improvement weather resisteant that improves film, makes that binder resin accounts for 83-94.6% in the film.
The matrix of masterbatch is vector resin, vector resin is generally polymkeric substance or the bigger polymkeric substance of alkane body index that low molecule is put, when vector resin is new LDPE (film grade) (MI7.0), when ethylene-vinyl acetate copolymer (MI2.0) or new LDPE (film grade) (MI7.0) and new LDPE (film grade) (MI50) blend (both than be 2: 1), content is 80-91.4% in masterbatch), make that masterbatch content is 5-15% in the film.
The used main UV light stabilizing agent of the present invention is hindered amine as light stabilizer three [1,2,2,6,6-pentamethyl--4-piperidyl] phosphorous acid ester or this photostabilizer and other hindered amine as light stabilizer.As Chimassorb944, the combination of Tinuvin622 and Tinuvin144 etc.Main UV light stabilizing agent content in masterbatch is 4-11%.The weight ratio of three [1,2,2,6,6 ,-pentamethyl--4-piperazine base] phosphorous acid esters and Chimassorb944 or Tinuvin144 is 3: 2.The fill-in light stablizer is benzophenone or triazines UV light stabilizing agent.When the fill-in light stablizer is Octabenzone or triazine-5, both are 1.3-2.6% by content in masterbatch, oxidation inhibitor is phenolic antioxidant, when oxidation inhibitor was the positive octadecanol ester of 2.6-ditertbutylparacresol or β-(4-hydroxyl-3.5-di-tert-butyl-phenyl) propionic acid, both content in masterbatch was 1.3%-2.6%.
The used visible light mediator agent of the present invention is by the phthalocyanine serial pigment, azo pigment or cooperate photostabilizer to form, and when the phthalocyanine serial pigment is a pthalocyanine blue, when azo pigment was Fast Yellow G, both were 0.4-0.6% by content in masterbatch.
Other used auxiliary agent of the present invention comprises lubricant and modifier etc., as stearic amide, and glyceryl stearate, amine hydroxybenzene, ethylene two (hydroxyl stearylamide), stearic acid and salt thereof, sherwood oil, paraffin, whiteruss, polyethylene wax etc., when lubricant was amine hydroxybenzene, its add-on accounted for the 0.1-0.5% of film, when modifier is polyethylene wax, its add-on accounts for the 0.3-1.5% of film, and total add-on of auxiliary agent is no more than 3% of weight resin.After vector resin, photostabilizer, oxidation inhibitor and the pre-mixing of visible light conditioning agent,, make masterbatch with the granulation of mixing granulator machine.
Binder resin is with after masterbatch mixes, on forcing machine, press the complete processing of inflation film process blown film, make the polyethylene film that thickness is 0.10-0.16mm, processing temperature: new LDPE (film grade) or be 150-190 ℃, linear low density of polyethylene or be 175-230 ℃ based on the blend of linear low density of polyethylene based on the blend of low density ethylene.Blow-up ratio 1: 2.5-1: 3.Pulling speed 3-6m/mim, engine speed 80-110rpm.
The present invention has unique UV light stabilizing agent, oxidation inhibitor, the collaboration system that the visible light conditioning agent cooperates.Compared with similar products, the used stabilizer type of this collaboration system is less, and prescription is simple.The key light stablizer is easy to get, and add-on is less, and the consumption of key light stablizer and the total consumption of stablizer all are significantly less than the add-on in the like product in the film, so cost is low, helps suitability for industrialized production.
The visible light conditioning agent that the present invention selects for use has protects look in the use, the characteristics of not sensitization polyethylene photooxidation reaction can promote plant-growth, increasing both production and income.
Can the wider polyolefine of use range be binder resin, sufficient raw.
Be 2-3 the work-ing life of " wear well polythene film " of the present invention, i.e. in two winters of the three summer jobs, more present polyethylene warmhouse booth film and other polyethylene film life-span long lifetime are long.
Embodiment 1:
New LDPE (film grade) (MI0.3) 91.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch is composed as follows:
New LDPE (film grade) (MI7.0) 60%
New LDPE (film grade) (MI50) 30%
Three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester 5%
Triazine-5 1.5%
2.6-ditertbutylparacresol 1.5%
2-hydroxyl-4-n-octyloxy-benzophenone 1.5%
Fast Yellow G 0.5%
Above-mentioned binder resin, amine hydroxybenzene, polyethylene wax and masterbatch by the proportioning mixing, are blow molded into the 0.14mm film on PC-65 blowing unit (L/D 28: 1).
The processing temperature parameter:
Fuselage:
One district: 150-180 ℃
Two districts: 150-190 ℃
Three districts: 170-200 ℃
Head:
Four districts: 170-200 ℃
Five districts: 160-190 ℃
Working process parameter:
Blow-up ratio: 1: 2.5-1: 3
Pulling speed: 3-6m/min
Engine speed 80-110rpm embodiment 2:
New LDPE (film grade) (MI1.5%) 91.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch composition and fabrication process condition are with embodiment 1.Embodiment 3:
New LDPE (film grade) (MI0.3) 74%
Linear low density of polyethylene (MI1.5) 17.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch is composed as follows:
Ethylene-vinyl acetate copolymer (MI2.0) 91%
Three [1,2,2,6,6-pentamethyl--4-piperidyl] phosphorous acid ester 3%
Hindered amine as light stabilizer Chimassorb 944 2%
2-hydroxyl-4-n-octyloxy-benzophenone 1.5%
β-positive 18 carbon of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid
Alcohol ester 2%
Pthalocyanine blue 0.5%
Fabrication process condition is with embodiment 1.Embodiment 4:
New LDPE (film grade) (MI1.5) 74%
Linear low density of polyethylene (MI1.5) 17.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch is formed with embodiment 3, and fabrication process condition is with embodiment 1.Embodiment 5: new LDPE (film grade) (MI0.3) 74%
Ethylene-vinyl acetate copolymer (MI2.0) 17.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch is composed as follows:
New LDPE (film grade) (MI7.0) 90%
Three [1,2,2,6,6-pentamethyl--4-piperidyl] phosphorous acid ester 3%
Hindered amine as light stabilizer Tinuvin 144 2%
Octabenzone 1.5%
β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid
Positive octadecanol ester 1.5%
Triazine-5 1.5%
Fast Yellow G 0.5%
Fabrication process condition is with embodiment 1.Embodiment 6:
New LDPE (film grade) 74%
Ethylene-vinyl acetate copolymer (MI2.0) 17.9%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.5%
Masterbatch 7.5%
Wherein masterbatch is formed with embodiment 5.Fabrication process condition is with embodiment 1.Embodiment 7:
Linear low density of polyethylene (MI1.5) 91.6%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.8%
Masterbatch 7.5%
Wherein masterbatch is composed as follows:
Ethylene-vinyl acetate copolymer (MI2) 90%
Three [1,2,2,6,6-pentamethyl--4-piperidyl] phosphorous acid ester 5%
Octabenzone 1.5%
β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid positive ten
Eight carbon alcohol esters 1.5%
Triazine-5 1.5%
Fast Yellow G 0.5%
Above-mentioned binder resin, amine hydroxybenzene, polyethylene wax and masterbatch by the proportioning mixing, are blow molded into the film of 0.13mm on TOMI 60 blowing units (L/D 25: 1).
The processing temperature parameter:
Fuselage a: district: 175-195 ℃
Two districts: 185-210 ℃
Three districts: 190-230 ℃
Head: four districts: 190-230 ℃
Five districts: 190-220 ℃
Working process parameter:
Blow-up ratio: 1: 2.5-1: 3
Pulling speed: 3-6m/min
Engine speed: 80-110rpm embodiment 8:
Linear low density of polyethylene (MI1.5) 82.4%
Ethylene-vinyl acetate copolymer (MI2.0) 9.2%
Amine hydroxybenzene 0.1%
Polyethylene wax 0.8%
Masterbatch 7.5%
Wherein masterbatch is composed as follows:
New LDPE (film grade) (MI7.0) 91%
Three [1,2,2,6,6-pentamethyl--4-piperidyl] phosphorous acid ester 5%
β-(4-hydroxyl-3.5-di-tert-butyl-phenyl propionic acid
Positive octadecanol ester 2%
Phthalocyanine green 0.5%
Octabenzone 1.5%
Fabrication process condition is with embodiment 7.

Claims (1)

1. the manufacture method of a weather resistant plastic film is characterized in that this film forms (in weight %) by following component:
Polyolefin resin 83-94.6, masterbatch 5-15, auxiliary agent comprise lubricant 0.1-0.5, modifier 0.3-1.5; Masterbatch comprises vector resin 90, wherein vector resin is new LDPE (film grade) MI7.0, ethylene-vinyl acetate copolymer MI2.0 or new LDPE (film grade) MI7.0 and new LDPE (film grade) MI50 blend, both are than being 2: 1, main UV light stabilizing agent 4-11, fill-in light stablizer are cooperated with triazines as light stabilizer by benzophenone and form, and both are 1.3-2.6 by content in masterbatch, oxidation inhibitor 1.3-2.6, visible light conditioning agent 0.4-0.6.
CN 90101638 1990-03-23 1990-03-23 Preparation method of weather-resistant polyethylene film Expired - Fee Related CN1040006C (en)

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Application Number Priority Date Filing Date Title
CN 90101638 CN1040006C (en) 1990-03-23 1990-03-23 Preparation method of weather-resistant polyethylene film

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CN1040006C true CN1040006C (en) 1998-09-30

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DE69507235T2 (en) * 1994-09-30 1999-07-29 Ciba Specialty Chemicals Holding Inc., Basel Stabilization of pigmented fibers with a synergistic mixture of UV absorber and hindered amine
US6051164A (en) 1998-04-30 2000-04-18 Cytec Technology Corp. Methods and compositions for protecting polymers from UV light
CN1324080C (en) * 2003-11-20 2007-07-04 孔少云 Modified polyethylene film and its production technology
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CN102924797B (en) * 2011-08-10 2014-06-04 中国石油天然气股份有限公司 Weather-resistant polyethylene agricultural film resin composition and preparation method thereof
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